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.

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.

D. Tech. (Department of Mechanical Engineering, Faculty of Engineering and Technology), Vaal University of Technology. / Cracked concrete slabs are a problem due to several factors such as poor maintenance, insufficient reinforcement or steel corrosion leading to crack propagation. There is a need to increase the load-bearing capacity of concrete slabs and increase their life span. The use of waste Polyethylene Terephthalate (PET) fibres and fly ash in a hybrid composite slab dramatically alleviates the problem of crack propagation and failure sustainably. This study aimed to optimize a waste PET fibre/fly ash hybrid cement composite for use in slabs. This study characterized the raw materials used, including fly ash and aggregates. After that, concrete test specimens were fabricated using the PET fibres and fly ash following the full factorial experimental design. The developed specimens were then tested to ascertain their material strength properties. Model development was carried out using Minitab Software Version 14, and subsequent experimental validation was carried out. After that, the PET and fly ash optimisation for maximum favourable response outcome was carried out. The fly ash was found to belong to the Class F category with particle size ranging from 0.31 μm to 800 μm. The fly ash was mainly spherical and consisted of Ca, Al, P, Si, and trace amounts of Ti and Mg. The spherical shape of the fly ash helped improve the concrete's workability. The river sand had a fineness modulus of 3.69, considered coarse sand. The fine aggregate showed uniform particle size distribution with a uniformity coefficient of 4.007. The coarse aggregate characterisation was carried out and revealed that the aggregate particle size was 13 mm in size. The coarse aggregate had a uniformity coefficient of 4.007, which implied the aggregate was well graded. The coarse aggregate had a high flakiness index of 74.82 % and an acceptable elongation index of 46.72 %. Full factorial methodology experimental design was employed to fabricate the test specimens by simultaneously varying the independent factors to develop a model for overall response variation. The slump value was observed to increase with the addition of fly ash. However, the addition of PET fibre decreased the slump value with incremental amounts of fibre. The combined effect of fibre addition and fly ash showed a general decreasing slump value for all quantities of fly ash content. The compressive strength of PET fibre only composite had maximum strength at 0.5% fibre addition, and the composite with fly ash alone had the maximum compressive strength at 15%. The combined optimum compressive strength for fibre and fly ash was at 0.5 % and 15 %, respectively, with a 15.54 N/mm2. The split tensile strength decreased with an increase in fibre content. However, the fibre provided crack retardation. Fly ash increased the split tensile strength significantly to a peak of 2.35 N/mm2 for 20 % fly ash addition. The combined addition of fibre and fly ash had an optimum split tensile strength of 2.79 N/mm2 at 0.5 % fibre and 20 % fly ash. The addition of fibre had an optimum split tensile strength at 0.5% of 1.82 N/mm2. The fly ash increased the flexural strength, with optimum strength at 15 %. The combined addition of fibre and fly ash created optimum flexural strength at 0.5% and 30 %, respectively. The trend observed by the rebound number followed that of the compressive strength. However, the non-destructive rebound hammer method gave significantly lower strength values than the destructive test method. The addition of fly ash had the effect of lowering the cost of producing the slab. However, the addition of fibres marginally increased the cost. The combined effect of fibre and fly ash resulted in a significant cost saving. Numerical optimisation was carried out concerning the fibre reinforced concrete's fresh and hardened mechanical properties. Predictive modified quadratic equations were developed for slump value, compressive, flexural, split tensile strength and total cost. Analysis of variance test carried out for all the responses indicated that the model could predict the slump value and mechanical properties of the fibre reinforced concrete correctly and effectively with a coefficient of determination in the range of 0.4151 to 0.9467. The developed model can predict the required fibre reinforced fresh and hardened properties in order to assist in decision making in construction in slabs. The optimum constituent combination for maximum mechanical strength at the lowest possible cost was found to be 15.7576 % Fly ash and 0.3232 % PET fibre with optimum responses as shown in Table 4-26. These predictions were validated experimentally, and a good correlation was observed between the actual and predicted values based on the observed standard deviations of 0.1335, 0.031, 0.005, 0.676, 0.02 for compressive strength, flexural strength, tensile strength, slump value and cost, respectively. Concrete slabs were optimised for various possible end uses, and the optimum PET fibre % and fly ash % were ascertained as shown in Table 4-27.

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.

The relaxation characteristics of rubbery poly(ethylene oxide) [PEO] networks have been investigated as a function of network composition and architecture via dynamic mechanical analysis and broadband dielectric spectroscopy. A series of model networks were prepared via UV photopolymerization using poly(ethylene glycol) diacrylate [PEGDA] as crosslinker: variations in crosslink density were achieved either by the introduction of water in the prepolymerization reaction mixture, or by the inclusion of mono-functional acrylate such as poly(ethylene glycol) methyl ether acrylate [PEGMEA] or poly(ethylene glycol) acrylate [PEGA]. Copolymerization with mono-functional acrylate led to the insertion of flexible branches along the network backbone, and the corresponding glass-rubber relaxation properties of the copolymers (i.e., Tg, relaxation breadth, fragility) were a sensitive function of network architecture and corresponding fractional free volume. Relatively subtle variations in network structure led to significant differences in relaxation characteristics, and a systematic series of studies was undertaken to examine the influence of branch length, branch end-group, and crosslinker flexibility on viscoelastic response. Dielectric spectroscopy was especially useful for the elucidation of localized, sub-glass relaxations in the polymer networks: the imposition of local constraint in the vicinity of the crosslink junctions led to the detection of a distinctive fast relaxation process in the networks that was similar to a comparable sub-glass relaxation observed in crystalline PEO and in the confined regions of PEO nanocomposites. Gas permeation studies on the model PEGDA networks confirmed their utility as highly-permeable, reverse-selective membrane materials, and strategic control of the network architecture could be used to optimize gas separation performance. Dynamic mechanical and dielectric measurements have also been performed on a semicrystalline polyester, poly(trimethylene terephthalate) [PTT], in order to assess the influence of processing history on the resultant morphology and corresponding viscoelastic relaxation characteristics. Studies on both quenched and annealed PTT revealed the presence of a substantial fraction of rigid amorphous phase (RAP) material in the crystalline samples: dielectric measurements showed a strong increase in relaxation intensity above the glass transition indicating a progressive mobilization of the rigid amorphous phase with increasing temperature prior to crystalline melting.

The feasibility of using oriented polymer technology in the design and manufacture of mechanical power transmission belts has been investigated. Working from an initial selection of polymers a die-drawing technique for orienting the polymers was devised, and the static and dynamic mechanical properties of the oriented polymers were investigated. These results indicated that PP, PBT, PPS and PEEK were suitable for further research. Of these 4 materials PBT was selected as the most appropriate material for belt manufacture based on cost, processability (drawing temperature, natural draw ratio) and limitations of laboratory equipment. A technique based on free-tensile drawing combined with simultaneous rotational motion was designed and used to manufacture oriented PBT flat belts from cylindrical injection moulded preforms. The technique used a tensile machine with two pulley-clamps, a fitted heated chamber and an electric motor to provide rotational motion to the belt during drawing. Two types of oriented PBT flat belts with different cross sections were produced successfully, termed 'thick' and 'thin'. These belts were tested on a purpose-built rig comprising two equal diameter pulleys, one driven by an electric motor and the other connected to a generator to provide load. The belt life and power transmission performance was investigated at various conditions of speed, transmitted torque and tension, and the results indicated that despite their smaller cross section 'thin' flat belts demonstrated up to 3 times longer life. However life was only 100hours, which was very low compared with conventional flat belts that last for many thousands of hours at higher speeds and much greater power transmission capacity. Synchronous belts were then produced through the same manufacturing method used for flat belts. This aspect of the research concentrated on the initial pitch design and size, i.e. the timing. Initially a rectangular tooth profile was selected for its simplicity in terms of manufacture. The produced belts exhibited high pitch length variation as well as deformed teeth and were not usable for synchronous power transmission. An extra timing feature was included to control orientation; reducing the pitch length variation enabling consistent tooth production. It was observed that the areas between the extra timing feature and the tooth edges did not orient completely with some regions remaining undrawn. Finite Element Analysis (FEA) was used to predict the drawing behaviour of different shapes and dimensions of the timing features. The results suggested that a 4mm wide and 7mm long slot provided the highest possible extension and the minimum non-oriented regions on the groove. Whilst, the thickness and width of the drawn belt timing features showed differences to the FEA predictions, manufactured synchronous belts based on that design had much better controlled dimensions and the lowest achieved pitch length variation ( ±1%), compared to initial attempts. It is concluded that oriented polymers have the potential to be used in power transmission belts since they offer higher stiffness, tensile strength and creep resistance compared with isotropic polymers that are currently used in commercially available belts such as thermoplastic polyurethane (TPU) and polyvinyl chloride (PVC). The main disadvantages were the lack of dimensional stability and number of cycle to failure.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Na reação de desidrogenação oxidativa de propano (ODHP), propano reage com oxigênio da superfície de metais de transição para produzir propeno e água, em temperaturas de 300-700C. Porém, o propeno pode facilmente oxidar, formando CO e CO2. Assim, busca-se catalisadores que promovam a seletividade do propeno. Compostos tipo hidrotalcitas estão sendo apontados como catalisadores de grande potencial para a reação. Portanto, o principal objetivo desse trabalho foi sintetizar precursores tipo hidrotalcitas (contendo íons Ni2+, Mg2+ e Al3+ e tereftalato, heptamolibdato e decavanadato como ânions de compensação) para serem testados na reação de desidrogenação oxidativa de propano. Esses precursores foram sintetizados com uma razão Al/(Al+Ni+Mg)=0,5, variando a razão de Ni/Mg. Além disso, realizou-se a troca iônica do tereftalato (TA) por heptamolibdato (Mo7O24) e decavanadato (V10O28). Esses compostos foram calcinados, obtendo-se assim, óxidos mistos de NiMgAl, NiMgAlMo e NiMgAlV que foram testados como catalisadores na reação de ODHP. Para a determinação das propriedades dos catalisadores foram usadas as técnicas de caracterização: DRX, TGA, volumetria de N2, TPR, Raman e FTIR e ICP. Os resultados indicaram que os materiais tipo hidrotalcita foram obtidos com sucesso. No caso dos precursores preparados por troca iônica a cristalinidade foi menor que os da série NiMgAl-TA. Estes mesmos precursores quando calcinados apresentaram áreas muito altas. Nas três séries, os precursores calcinados são constituídos por óxidos mistos como NiO, NiMoO4, Ni2V2O7 cristalinos e espécies de alumínio e magnésio não detectados na DRX. No teste catalítico de ODHP, observou-se que com o aumento da conversão diminuía a seletividade de propeno, para os óxidos mistos que não continham molibdênio. Os catalisadores da série molibdênio foram os que obtiveram melhor desempenho com altas seletividades, mesmo em altas conversões e a série de cujo precursor foi o tereftalato foi a que exibiu maiores conversões, mas com seletividades menores que da série de Mo / In the reaction of oxidative dehydrogenation of propane (ODHP), propane reacts with oxygen in the transition metal surface to produce propylene and water at temperatures of 300-700 C. However, the propylene can easily oxidize, forming CO and CO2. Thus, catalysts that promote the selectivity of propylene are being searched. Hydrotalcites type compounds are identified as potential major catalysts for the reaction. Therefore, the main objective of this work was to synthesize precursors hydrotalcites type (containing Ni2+, Mg 2+ and Al 3+ ions and terephthalate, heptamolybdate and decavanadate as compensation anions) to test in the reaction of oxidative dehydrogenation of propane.These precursors were synthesized with Al/(Ni+Mg+Al) = 0.5 for different ratios of Ni/Mg. In addition, there was the ion exchange terephthalate (TA) by heptamolybdate (Mo7O24) and decavanadate (V10O28). These compounds were calcined, to obtain NiMgAl, NiMgAlMo and NiMgAlV mixed oxides and tested as catalysts in the ODHP reaction.For determining the properties of the catalysts the following characterization techniques were used: XRD, TGA, N2 volumetry, TPR, ICP, FTIR and Raman spectroscopy. The results indicated that the hydrotalcite-like materials were successfully obtained. In the case of the precursors prepared by ion exchange crystallinity was lower than those of NiMgAl-TA series. These same precursors when calcined had very high areas. In three series, the calcined precursors are comprised by mixed oxides such as crystalline NiO, NiMoO4, Ni2V2O7 and Al an Mg species not detected by XRD. In ODHP catalytic test, it was observed that with increasing conversion the propylene selectivity decreased to the mixed oxides containing no molybdenum. The catalysts of molybdenum series were those who performed better with high selectivity even at high conversions and the terephthalate precursor series shows the highest conversions, but with lower selectivity than Mo series

The compound 2,6-anthracenedicarboxylic acid is used as a comonomer for the synthesis of poly(ethylene terephthalate). The resulting copolymers are characterized and further functionalized by Diels-Alder grafting or crosslinking through the anthracenate unit. Diels-Alder reaction is used to graft small molecules and oligomers endcapped with maleimide as dienophiles on to poly(ethylene terephthalate-co-2,6-anthracenedicarboxylate),PET-co-A. Maleimide-capped poly(ethylene glycol) is grafted onto PET-co-A to improved its hydrophilicity. 2,6-Anthracenedicarboxylic acid is also incorporated into the known liquid crystalline polymer, LCP, poly(4-oxybenzoate-co-1,4-phenylene isophthalate), HIQ40. The resulting copolymer, poly(4-oxybenzoate-co-1,4-phenylene isophthalate-co-2,6-phenylene anthracenate), HIQ40-co-A, shows LCP behavior. These HIQ40-co-A copolymers are grafted with maleimide end-capped monomers and polymers andcrosslinked with bismaleimides through a Diels-Alder mechanism.

Transport of amorphous and semi-crystalline, oriented, annealed and non-annealed PET films has been studied using pure and mixed gas/vapor feeds to understand the influence of flavor molecules on the efficacy of the barrier material. Methanol has been used as the flavor molecule simulant, and pure methanol vapor sorption studies show swelling and relaxation effects in the polymer. Multi-component transport of O2/methanol and O2/CO¬2/methanol mixtures, performed at different activities of methanol, shows that vapor induced plasticization leads to increases in O2 and CO2 permeability. Annealed, semi-crystalline PET is shown to be most resistant to plasticization effects. It has been shown that the non-annealed film is less stable despite similar crystallinity as the annealed film due to the presence of orientation related stress in the material. Presence of crystals also restricts the chain motion, and helps suppress the plasticization effects. The results have been compared with the predictions of the dual mode model for multi-component mixtures. Plasticization effects at the high activities have been analyzed within the framework of the free volume theory. It has been proposed that only the densified domains of a glassy polymer be considered when evaluating fractional free volume change due to swelling in the polymer-penetrant system. The free volume parameter- BA has been evaluated for O2 and CO2 in PET and is found to be different from that for other high permeability polymers.

In this studing, application of the digital image correlation method (DIC) for determining the coefficient of thermal expansion (CTE) of Indium Tin Oxide/Polyethylene Terephthalate(ITO/PET) thin film/flexible substrate was proposed and the effects of thinkness variations of ITO and PET, respectively, on the CTE of the specimens was disscussed. The observation range of experimental temperature was chosen from room temperature to the glass transfer temperature of PET, 70¢J. A novel DIC experimental process for reducing the errors caused from the variations of the refractive index of the surrounding heated air was proposed. As a result, the experimental error of CTE measurement was reduced form 10~17% to less than 5%. The experimental results showed that the CTE of ITO/PET specimen is anisotropic. Futhermore, the CTE of an ITO/PET specimen will be increased by decreasing the thinkness of PET flexible substrate, and increased by increasing the thinkness of ITO film - which means decreasing the surface resistance of ITO film.