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Thesis (Ph. D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2004. / Collard, David, Committee Co-Chair ; Schiraldi, David, Committee Member ; Liotta, Charles, Committee Member ; Weck, Marcus, Committee Member ; Srinivasarao, Mohan, Committee Member ; Kumar, Satish, Committee Co-Chair. Vita. Includes bibliographical references.

Hamburg-Harburg, Techn. Universität, Thesis (doctoral), 2002.

Thin sheets and membrane structures are widely used in space applications such as solar sails, sunshields and membrane optics. Surface flatness over a large area is one of the key requirements for many applications using the flexible thin structures. However, wrinkles are commonly observed in thin sheets. It is thus important to understand the mechanics of thin sheets for practical applications that require reliable control of surface wrinkles. In this study, a model problem of stretch-induced wrinkling of thin sheets is considered. First, a two-dimensional (2-D) finite element model was developed to determine stretch-induced stress distribution patterns in hyperelastic thin sheets, assuming no wrinkles. As a prerequisite for wrinkling, development of compressive stresses in the transverse direction was found to depend on both the length-to-width aspect ratio of the sheet and the applied tensile strain. Next, an eigenvalue analysis was performed to predict the critical conditions for buckling of the elastic sheet under the prescribed boundary conditions, followed by a nonlinear post-buckling analysis to simulate evolution of stretch-induced wrinkles. Experiments were conducted to measure stretch-induced wrinkling of polyethylene thin sheets, using the three-dimensional digital image correlation (3D-DIC) technique. It was observed that the wrinkle amplitude first increased and then decreased with increasing nominal strain, in agreement with finite element simulations for a hyperelastic thin sheet. However, unlike the hyperelastic model, the stretch-induced wrinkles in the polyethylene sheet were not fully flattened at high strains (> 30%), with the residual wrinkle amplitude depending on the loading rate. The hyper-viscoelastic and the parallel network nonlinear viscoelastic material models were adopted for finite element simulations to improve the agreement with the experiments, including the wrinkle amplitude, residual wrinkles and rate dependence. Finally it is noted that wrinkling is sensitive to defects and material inhomogeneity in thin sheets. By varying the elastic stiffness in a narrow region, numerical simulations show drastically different wrinkling behavior, including the critical strain and evolution of wrinkle amplitude and wavelength. In conclusion, a comprehensive understanding of stretch-induced wrinkling is established, where geometry, material, and boundary conditions all play important roles. / text

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This thesis presents a study of antioxidant depletion in water containing chlorinated species (water containing 10 ppm either Cl2 or ClO2, buffered to pH = 6.8), the degradation products in the aqueous phase, and polyethylene pipe degradation scenarios. A low molecular weight hydrocarbon analogue (squalane) was used instead of solid polyethylene as the host material for the antioxidants, and the depletion of antioxidants has been studied. The phenolic antioxidant Irganox 1010 was consumed ca. 4 times faster in water containing 10 ppm ClO2 than in water containing 10 ppm Cl2. The different degradation products in extracts from the aqueous phase identified by infrared, liquid chromatography and mass spectrometry revealed the different degradation mechanisms between ClO2 (" cleavage) and Cl2 (hydrogen substitution). The squalane test shows no energy barrier between 30 and 70 °C, and the activation energy of the antioxidant in solid PE was found to be ca. 21 kJ mol-1. A linear relationship has been established between the time to reach antioxidant depletion in the polyethylene tape samples and the time to reach depletion in samples based on squalane containing the same antioxidants. The surface oxidation and surface embrittlement of PE tape on long time exposure have been studied by IR and SEM. Pressure testing on medium density PE pipes with a controlled pH aqueous media (6.8 ± 0.2) containing 4 ppm either ClO2 or at 90 °C showed that the stabilizers were rapidly consumed towards the inner pipe wall and the rate of consumption in ClO2 was 4 times greater than in Cl2 solution. The subsequent polymer degradation was an immediate surface reaction. It was confirmed by differential scanning calorimetry, infrared spectroscopy and size exclusion chromatography that, in the surface layer which came into contact with the oxidizing medium, the amorphous component of the polymer was heavily oxidized leaving a highly crystalline powder with many carboxylic acid chain ends in extended and once-folded chains. / <p>QC 20130122</p>