No description available.

Thesis (Ph. D.)--Princeton University, 1930.

The study deals with the formulation development and thermorheological properties of crumb rubber/ethylene vinyl acetate (EVA) modified bitumen with the aim of optimizing the amount of crumb rubber and EVA loadings in bitumen based on thermorheological parameters complex shear modulus, phase angle and rutting parameter. In the modified binders EVA offers plastomer properties whereas the crumb rubber confers elasticity to the bitumen. 13.75% crumb rubber and 2.5% EVA loadings based on aging indices gave the best optimized mixture. The thermorheological behaviour of the best optimized mixture was compared to industrial grade EVA (AP-1) and crumb rubber (AR-1) modified bitumen. Improving aging behaviour of the bitumen was evaluated using four antioxidants: carbon black, hydrated lime, Irganox 1010 and Irgafos 168. The least aging indices at 58˚C and 64˚C were obtained from a 1:1:1 Irganox 1010/hydrated lime/carbon black mixture. SARA (saturates, aromatics, resins and asphaltene) analysis gave the chemical background for application of antioxidants to reduce the propensity of short term aging. To further improve the EVA/crumb rubber optimized mixture for workability FT wax (Sasobit®) was assayed at loadings from 0-2.5%. This was done to match the EVA content and maintain the original maximum loading of 2.5% in the optimized mixture. The phase change abilities of FT wax owing to the high latent heat enabled co-crystallization with the EVA with the elastomeric backbone of crumb rubber acting as support material. The energy-sustainability nexus was found to have worked at less than 1% loading of FT wax in the EVA/crumb rubber modified bitumen. Response surface methodology approach to all the sections of work was used to come up with the optimized mixtures based on rheological parameters complex shear modulus, phase angle and rutting parameter at test temperature 64˚C. The interaction chemistry of bitumen, crumb rubber, EVA and FT wax was found to be first and second order in all cases involving individual contributions and co-interaction amongst the factors. Project costing for each section of work (optimizing section, antioxidant section and FT wax section) was conducted involving the raw materials used, equipment used, labour involved and other costs incurred for all the project work.

Thesis (M.S.)--University of Wisconsin--Madison, 1983. / Typescript. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 228-230).

Thesis (Ph. D.)--Lehigh University, 2000. / Includes vita. Includes bibliographical references (leaves 41, 81, 130, 183, 270, 315, 336).

No description available.

Experiments have been conducted to identify the fouling mechanism during the crossflow filtration of a model yeast fermentation broth of Vinyl Acetate particles suspended in a Bovine Serum Albumin (BSA) solution. These have been conducted with filter modules, to obtain quantitative data for the rate and the extent of flux decline due to membrane fouling, and with filter coupons, to obtain quantitative data for the build up of the fouling layer with each individual system and the mixed system. The data from the individual systems have been analysed and then used to determine their fouling mechanisms; this information has been used to predict the fouling mechanism for the mixed system. Finally, this prediction has been compared to the actual fouling mechanism determined by analysis of the mixed system data. For the model particulate suspension, the fouling was due to the build up of a cake layer, as with dead end filtration; however, fouling was limited by membrane scouring. For the model macromolecular solution, a four part fouling mechanism was identified: initially aggregates formed within the pores; the concentration at the membrane surface increased until protein came out of solution as strands; the strands disappeared causing increased aggregation in the pores; finally, a mesh formed on the membrane surface. For the mixed system, fouling was due to the formation of a particle cake on the membrane surface with protein aggregates forming in the pores. The fouling kinetics could be predicted by considering the results from the individual systems; however, the fouling mechanism could not be predicted without using visualisation experiments due to the interactions between the particles and the macromolecules.

The concept of a unique ceramifiable Ethylene vinyl acetate (EVA) based polymer composite was based on the incorporation of inorganic compounds such as aluminium hydroxide, calcium carbonate, muscovite mica, and calcined kaolinite within a 95 percent EVA/ 5 percent Polydimethylsiloxane (PDMS) polymer matrix such tha t upon heating to elevated temperatures of about 1000 oC, a solid end-product with ceramic-like properties would be formed. The ceramifiable EVA based polymer composite was developed to be used as electric cable insulation or sheath as the formation of a ceramic based material at elevated temperatures would provide flame retardant properties during fire situations. The flame retardant properties at elevated temperatures would ensure that the insulation remains at such temperatures due to some of the properties of the resultant ceramic such as reasonably high flexural strength, high thermal stability, non-reactivity and high melting point. During a fire this would ensure that flames would not be propagated along the length of the cable and also protect the underlying conducting wires from being exposed to the high temperatures of the fire. Its application as a cable insulation also required that the material functions as a cable insulator under ambient temperature conditions where the ceramifiable polymer composite should retain certain polymer properties such as the post-cure tensile strength (MPa), degree of polymer elongation (percent), thermal expansion, thermal slacking, limited oxygen index and electrical insulation. This study made use of a composite experimental design approach that would allow for the optimization of the amounts of the additives in the ceramifiable polymer composite giving both the desired mechanical properties of the material under normal operating temperatures as a polymer and also as a ceramic once exposed to elevated temperatures. The optimization of additives used in the ceramifiable polymer composite was done by using a D-optimal mixture design of experiments (DoE) which was analyzed by multiple linear regression.

Processos industriais de polimerização em emulsão são usualmente realizados em reatores tipo tanque agitado em batelada (ou semi-batelada) ou em contínuo (CSTR). Reatores contínuos tem a vantagem de serem comparativamente de menor porte, e propiciarem melhor controle da qualidade do produto pela redução de variações de batelada a batelada. Reatores tipo CSTR podem exibir oscilações periódicas e autosustentadas de conversão, de tamanho e concentração de partículas. Estas oscilações podem ser minimizadas nos reatores tubulares pulsados devido à diminuição da dispersão axial em relação aos reatores do tipo CSTR. Na presente tese, desenvolveu-se um novo tipo de reator tubular, a Coluna Pulsada de Pratos Perfurados, CPPP, para uso no processo de polimerização contínua do acetato de vinila em emulsão. O reator é operado com escoamento pulsado e contém pratos perfurados como dispositivos internos. Inicialmente foram realizados ensaios de distribuição de tempos de residência, em um reator montado em vidro, com o objetivo de caracterizar o escoamento no reator CPPP quanto ao grau de mistura axial. Os dados foram interpretados usando o modelo de escoamento pistonado com dispersão axial. Valores do coeficiente de dispersão axial foram medidos e correlacionados para diferentes condições de freqüência e amplitude de pulsação, vazão, espaçamento entre pratos, e viscosidade do fluido. Verificou-se que o grau de mistura axial pode ser variado em faixas relativamente amplas pela manipulação da freqüência e amplitude de pulsação. Foi também montado um reator em aço inox e encamisado, com as mesmas dimensões, onde foram realizados ensaios de polimerização em emulsão de acetato de vinila, medindo-se a conversão e a distribuição de tamanhos de partículas (DTP), na saída do reator em regime transiente e permanente, e também ao longo do reator em regime permanente. Verificou-se que as condições operacionais (tempo médio de residência e grau de dispersão axial) influenciam várias características do produto, como, a conversão, tamanho médio e concentração de partículas, porém, não influencia, significativamente, a viscosidade da emulsão produzida, para a receita da reação de polimerização e as condições operacionais estudadas. Os resultados experimentais foram interpretados usando um modelo matemático do reator, o qual foi estabelecido com base em um modelo cinético publicado na literatura para o processo de polimerização em emulsão de acetato de vinila em batelada. Tal modelo foi adaptado incluindo-se os termos convectivos e dispersivos nas equações de balanço de massa, e resolvido numericamente. Foram ajustados apenas dois parâmetros neste modelo, para todas as condições operacionais estudadas e os resultados simulados reproduziram adequadamente o comportamento das principais variáveis de processo para a condição de regime permanente. O novo tipo de reator contínuo apresentado neste trabalho mostrou-se ser possível obter altas conversões em tempos médios de residência da ordem ou mesmo inferiores aos do processo em batelada e atingir regime permanente de operação em um a dois tempos médios de residência. O reator é eficiente, robusto, construtivamente simples, de fácil limpeza e manutenção, e mostrou-se promissor para utilização industrial em processo de polimerização em emulsão de acetato de vinila. / Industrial emulsion polymerization processes are usually carried out in stirred tanks operated in batch/semibatch or in continuous mode (CSTR). In comparison to batch processes, continuous reactors present several advantages such as lower volumes and better quality control by reducing batch-to-batch variations. Continuous emulsion polymerization in CSTR may exhibit sustained oscillations in conversion, particle size and particle concentration. Such oscillations may be reduced in pulsed tubular reactors due to less axial mixing. In this thesis a new type of tubular reactor, called Pulsed Sieve Plate Column, PSPC, was developed for the continuous process of vinyl acetate emulsion polymerization. This reactor is operated using oscillatory pulsed flow and uses perforated plates as internals. Residence time distribution runs were carried out in a glass reactor in order to characterize the axial mixing and flow patterns in the PSPC. The data were treated using the axially dispersed plug flow model. Axial dispersion coefficient was measured for different conditions of pulse frequency and amplitude, flow rate, plate spacing and viscosity. It was found that the degree of axial mixing can be varied in wide ranges by manipulating pulsation frequency and/or amplitude. Vinyl acetate continuous emulsion polymerization runs were carried out in a jacketed stainless steel reactor (with the same size of the glass reactor). Monomer conversion and particle size distribution was measured both at the reactor exit in transient state and along the reactor length at steady-state. It was found that average residence time and degree of axial mixing affect process and product quality variables, such as monomer conversion, mean particle size and concentration, but did not affect the viscosity of the emulsion produced, for the recipe and conditions used. A mathematical model for the reactor was developed. The model used, based on a well-known kinetic model previously developed in the literature for batch emulsion polymerization, was adapted to the continuous tubular reactor by adding the dispersion and convective terms to the balance equations. The model was numerically solved. Only two parameters were adjusted in this model and the simulated results showed excellent agreement with the experimental results, for steady state conditions. The proposed tubular reactor allows to reach high monomer conversion with similar or even lower residence time than those in batch processes and reaches steady state operation in just one to two mean residence times. The reactor is efficient, easy-to-built, easy-to-clean, robust and promising for use in industrial continuous emulsion polymerization of vinyl acetate.

Processos industriais de polimerização em emulsão são usualmente realizados em reatores tipo tanque agitado em batelada (ou semi-batelada) ou em contínuo (CSTR). Reatores contínuos tem a vantagem de serem comparativamente de menor porte, e propiciarem melhor controle da qualidade do produto pela redução de variações de batelada a batelada. Reatores tipo CSTR podem exibir oscilações periódicas e autosustentadas de conversão, de tamanho e concentração de partículas. Estas oscilações podem ser minimizadas nos reatores tubulares pulsados devido à diminuição da dispersão axial em relação aos reatores do tipo CSTR. Na presente tese, desenvolveu-se um novo tipo de reator tubular, a Coluna Pulsada de Pratos Perfurados, CPPP, para uso no processo de polimerização contínua do acetato de vinila em emulsão. O reator é operado com escoamento pulsado e contém pratos perfurados como dispositivos internos. Inicialmente foram realizados ensaios de distribuição de tempos de residência, em um reator montado em vidro, com o objetivo de caracterizar o escoamento no reator CPPP quanto ao grau de mistura axial. Os dados foram interpretados usando o modelo de escoamento pistonado com dispersão axial. Valores do coeficiente de dispersão axial foram medidos e correlacionados para diferentes condições de freqüência e amplitude de pulsação, vazão, espaçamento entre pratos, e viscosidade do fluido. Verificou-se que o grau de mistura axial pode ser variado em faixas relativamente amplas pela manipulação da freqüência e amplitude de pulsação. Foi também montado um reator em aço inox e encamisado, com as mesmas dimensões, onde foram realizados ensaios de polimerização em emulsão de acetato de vinila, medindo-se a conversão e a distribuição de tamanhos de partículas (DTP), na saída do reator em regime transiente e permanente, e também ao longo do reator em regime permanente. Verificou-se que as condições operacionais (tempo médio de residência e grau de dispersão axial) influenciam várias características do produto, como, a conversão, tamanho médio e concentração de partículas, porém, não influencia, significativamente, a viscosidade da emulsão produzida, para a receita da reação de polimerização e as condições operacionais estudadas. Os resultados experimentais foram interpretados usando um modelo matemático do reator, o qual foi estabelecido com base em um modelo cinético publicado na literatura para o processo de polimerização em emulsão de acetato de vinila em batelada. Tal modelo foi adaptado incluindo-se os termos convectivos e dispersivos nas equações de balanço de massa, e resolvido numericamente. Foram ajustados apenas dois parâmetros neste modelo, para todas as condições operacionais estudadas e os resultados simulados reproduziram adequadamente o comportamento das principais variáveis de processo para a condição de regime permanente. O novo tipo de reator contínuo apresentado neste trabalho mostrou-se ser possível obter altas conversões em tempos médios de residência da ordem ou mesmo inferiores aos do processo em batelada e atingir regime permanente de operação em um a dois tempos médios de residência. O reator é eficiente, robusto, construtivamente simples, de fácil limpeza e manutenção, e mostrou-se promissor para utilização industrial em processo de polimerização em emulsão de acetato de vinila. / Industrial emulsion polymerization processes are usually carried out in stirred tanks operated in batch/semibatch or in continuous mode (CSTR). In comparison to batch processes, continuous reactors present several advantages such as lower volumes and better quality control by reducing batch-to-batch variations. Continuous emulsion polymerization in CSTR may exhibit sustained oscillations in conversion, particle size and particle concentration. Such oscillations may be reduced in pulsed tubular reactors due to less axial mixing. In this thesis a new type of tubular reactor, called Pulsed Sieve Plate Column, PSPC, was developed for the continuous process of vinyl acetate emulsion polymerization. This reactor is operated using oscillatory pulsed flow and uses perforated plates as internals. Residence time distribution runs were carried out in a glass reactor in order to characterize the axial mixing and flow patterns in the PSPC. The data were treated using the axially dispersed plug flow model. Axial dispersion coefficient was measured for different conditions of pulse frequency and amplitude, flow rate, plate spacing and viscosity. It was found that the degree of axial mixing can be varied in wide ranges by manipulating pulsation frequency and/or amplitude. Vinyl acetate continuous emulsion polymerization runs were carried out in a jacketed stainless steel reactor (with the same size of the glass reactor). Monomer conversion and particle size distribution was measured both at the reactor exit in transient state and along the reactor length at steady-state. It was found that average residence time and degree of axial mixing affect process and product quality variables, such as monomer conversion, mean particle size and concentration, but did not affect the viscosity of the emulsion produced, for the recipe and conditions used. A mathematical model for the reactor was developed. The model used, based on a well-known kinetic model previously developed in the literature for batch emulsion polymerization, was adapted to the continuous tubular reactor by adding the dispersion and convective terms to the balance equations. The model was numerically solved. Only two parameters were adjusted in this model and the simulated results showed excellent agreement with the experimental results, for steady state conditions. The proposed tubular reactor allows to reach high monomer conversion with similar or even lower residence time than those in batch processes and reaches steady state operation in just one to two mean residence times. The reactor is efficient, easy-to-built, easy-to-clean, robust and promising for use in industrial continuous emulsion polymerization of vinyl acetate.