Oriented thermoplastics offer interesting opportunities for making structural automotive components due to their higher strengths. A new process, referred to as the axial feed hot oil tube forming (AF-HOTF) process, has been developed and studied for the forming of oriented thermoplastic tubes. The starting material for AF-HOTF process is an oriented polypropylene (OPP) tube produced by the solid state extrusion process. AF-HOTF was used to study forming and fracture behaviour of OPP tubes at large strains. Mechanical properties and molecular orientation of starting and post-formed materials were investigated to gain a better understanding of structure-property-process relationships during solid state extrusion and subsequent forming of OPP tubes. The development of molecular orientation and other microstructural changes and damage development in extruded and bulged OPP tubes during solid state extrusion and AF-HOTF processes were studied with optical microscopy, wide-angle X-ray diffraction (WAXD) and field emission scanning electron microscope (FE-SEM) techniques. Also, the development of large strains during AF-HOTF of OPP samples were experimentally studied in the form of spatial strain maps, strain/stress state and forming limit strains using an on-line strain mapping method based on digital image correlation (DIC). In addition, tensile tests have been carried out at room temperature on samples machined from the extruded and bulged tubes along the axial and hoop directions. Experimental quantitative relationships amongst molecular orientation parameters and extrusion and AF-HOTF process parameters such as draw ratio, strain and strain state have been obtained. These relationships in the form of White and Spruiell biaxial orientation factors provide a useful insight into molecular reorientation that occurs during extrusion and subsequent forming of OPP tubes. Also, an analytical model for forming limit prediction that takes into account OPP tube properties, tube dimensions and AF-HOTF process parameters was developed based on existing model of tube hydroforming in the literature. In addition, a new biaxial ball stretching test (BBST) system was developed and utilized to subject the thermoplastic tube to biaxial stretching. The design of the test-rig and results were presented for polypropylene (PP) tubes subjected to BBST at various temperatures. The BBST system was combined with an available on-line imaging and strain analysis system (ARAMIS® system from GOM) to observe the development of strains in the biaxial tensile region during the test. BBST samples were studied with wide angle X-ray diffraction (WAXD) pole figures. Three different hot forming processes (Solid-state extrusion, AF-HOTF and BBST) were used in this research. The structure of the extruded samples at draw ratio 5 and higher was completely changed to fibrils structure, and the yield strength and elastic modulus increased by 50%. Also the crystallinity increased from 47% to 68% with an increase in draw ratio. An increase in axial feed during the hot forming process resulted in higher formability (strains values of 0.55 major strain and -0.25 minor strain) and delayed failure. The analytical model prediction of bursting shows good agreement with the experimental results. The results provide an understanding of the orientation development in solid state extrusion of PP tubes as well as an understanding of tube formability, flow localization and fracture characteristics of PP tube from AF-HOTF process and other related processes. / Thesis / Doctor of Philosophy (PhD)

Made available in DSpace on 2016-12-08T17:19:36Z (GMT). No. of bitstreams: 1 Marcia Adriana Tomaz.pdf: 5577367 bytes, checksum: c8f9d4ee034ae6bd90f26bb87ca29b3c (MD5) Previous issue date: 2004-03-10 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Aiming the development of high-performance biodegradable polymeric materials, the properties and the processing behavior of poly(3-hydroxibutyrate), PHB, and their blends with poly(ε-caprolactone), PCL, have been investigated. Two sample of PHB obtaneid from sugarcane and characterized by infrared spectroscopy and X-ray diffraction, with molecular weights of 2,4 x 105 g.mol 1, PHB(A) and 3,0 x 105 g.mol 1,PHB(B), were used. Differential scanning calorimetry (DSC) showed that the sample were different regarding the crystallinity degree, 49% for the PHB(A) and 60% for the PHB(B), the glass transition temperature (Tg), 2,0oC (A) and 4,4 oC (B), and the melting temperature, 178oC (A) and 171oC (B). The samples have been processed through high-pressure compacting,solid state extrusion, and injection molding. Cylindrical billets of PHB prepared by compaction at 200 MPa showed high shore hardness, 71,3 (±0,9) D, and compression strength, 51,7 (± 1,0) MPa. The solid state processing was carried out by uniaxial compression, at temperature between the Tg and the melting point, through conical dies with extrusion draw ratio of 25 . It has produced extremely fragile materials with very high crystalline degrees (ca. 90%). Specimens of PHB(B) obtaneid by injection molding showed tensile strength, 24.53 (±0,77) MPa, and modulus ,3.82 (± 0,06) GPa, compatible to diverse type of applications. A small decrease on the tensile strength, 21,88 (± 0,40) MPa, and modulus, 2,17 (±0,25) GPa, and a high increase on the elongation at break, 86.7% (±20,0) were noted for PHB(B)/PCL (70/30) blends prepared by injection molding. DSC analyses of this blend showed two Tg´s, at 10,6oC for the PHB matrix, and at 62,9 oC for the PCL domains. The significant decrease on the Tg of PHB in the blend is possibly related to a partial miscibility of PCL in PHB. Thermal degradation studies of PHB were carried out by thermogravimetric methods, showing that the degradations occurs in only one step and that the presence of oxygen does not interfere in the degradation process. / Visando o desenvolvimento de materiais poliméricos biodegradáveis de alta performance estudaram-se as propriedades e o processamento de poli(3-hidroxibutirato), PHB, e de suas blendas com poli(ε-caprolactona), PCL. Foram utilizadas duas amostras de PHB, obtidas a partir de cana de açúcar,com massas molares de 2,4 x 105 g mol-1, PHB(A) e 3,0 x 105 g mol-1, PHB(B), cujas identidades foram confirmadas por espectroscopia na região do infravermelho. A calorimetria diferencial exploratória (DSC) mostrou que as amostras se diferenciam quanto ao grau de cristalinidade, 49% para o PHB(A) e 60% para o PHB(B), e em relação às temperaturas de transição vítrea, que variaram de 2 oC a 4,4oC, e de fusão, de 178 oC a 171 oC. Os materiais foram processados por compactação a alta pressão, extrusão em estado sólido e injeção em molde. O material compactado a 200 MPa apresentou elevada dureza, 71,30 (±0,9) unidades Shore D, e alta resistência à compressão, 51,7 (± 1,0) MPa. Observou-se que o processamento no estado sólido com razão de extrusão de 25 e em temperaturas até 175oC geram materiais extremamente frágeis, sendo que a caracterização por microscopia eletrônica de varredura mostra que o material não estava consolidado. A análise de DSC deste material revelou um alto grau de cristalinidade (93%), o que provavelmente está relacionado com a grande dificuldade de se obter PHB ou suas blendas com PCL por extrusão sólida. Corpos de prova de PHB(B) obtidos por injeção em molde apresentaram valores de resistência à tração, 24,53 (± 0,77) MPa,compatíveis com diversos tipos de aplicações, enquanto que as blendas de PHB(B)/PCL (70/30) injetadas apresentaram módulo de elasticidade igual a 2,17 (± 0,25) GPa e resistência à tração de 21,88 (± 0,40) MPa. A análise de DSC da blenda apresentou duas Tg´s, uma em -10,6 oC, da matriz de PHB, e outra a 62,9 oC, referente aos domínios de PCL. A diminuição acentuada na Tg do PHB(B) pode estar associada a uma provável solubilidade do PCL em PHB. Estudos da degradação térmica do PHB(B) por análise termogravimétrica, mostram que a degradação ocorre em apenas uma etapa e que a presença de oxigênio não interfere na degradação. Na análise da blenda de PHB(B)/PCL (70/30) é possível observar dois estágios de degradação provenientes do PHB(B) e do PCL e uma diminuição nas temperaturas de início de degradação do PCL e do PHB, quando comparadas com as dos materiais não processados.