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dc.contributor.authorLaot, Christelle Marieen_US
dc.description.abstractThe objective of this research work was to understand the molecular mechanism of gas transport through amorphous glassy polymers. Especially, emphasis was placed on determining whether or not gas transport in amorphous glassy polymers is directly correlated with the free volume content. Free volume arguments are indeed commonly used to explain the gas transport process.

The gas transport properties of bisphenol-A polycarbonate films were examined as a function of the cooling rate, physical aging, and orientation. Such conditions affect the free volume content and its size and shape distribution. Results obtained from permeation experiments were accompanied with dynamic mechanical and density measurements.

The experimental results suggest that the diffusion coefficient of small gas molecules in glassy polycarbonate is influenced by the local dynamics or mobility of the polymer chains rather than by the overall free volume content. Indeed, the diffusion coefficient of nitrogen for instance was reduced in fast-cooled samples, despite of the fact that those samples possessed a greater overall free volume content. Fast cooling rates may generate highly restricted conformations which hinder local motions, and therefore tend to increase the activation energy of diffusion. As expected, the greater the free volume content, the greater was the solubility coefficient. The increase in the polymer relaxation times with aging time is believed to restrict the local chain motions, leading to enhanced activation energies of diffusion, and therefore to reduced diffusion coefficients. The change in the solubility coefficients with physical aging revealed that the aging process might not affect all the cavity sizes in polycarbonate equally. According to free volume arguments, one would anticipate that the physical aging of fast-cooled samples (which possess more free volume) should be enhanced compared to that of slowly-cooled samples. Quite interestingly, the decrease in the diffusion coefficient with aging was found to occur much slower in fast-cooled samples, despite of the higher initial free volume content. In contrast, properties directly related to the free volume content, such as density or isothermal DMTA measurements actually showed a greater aging rate in the sample containing the greatest amount of free volume. Slow-cooled samples that are in a low energy conformational state may loose their internal degrees of freedom more rapidly, due to the closer interchain packing and the possibly restricted segmental motions. Studies dealing with orientation and gas transport were complicated by several factors. For instance the fact that the permeation experiments were performed perpendicularly to the orientation of the chains and not along the orientation axis limited the sensitivity of the gas transport properties to orientation.

This work points out that dynamic rather than static models should be developed to predict the gas transport phenomenon.

dc.publisherVirginia Techen_US
dc.rightsI hereby certify that, if appropriate, I have obtained and attached hereto a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee. I hereby grant to Virginia Tech or its agents the non-exclusive license to archive and make accessible, under the conditions specified below, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.en_US
dc.subjectgas transporten_US
dc.subjectcooling rateen_US
dc.subjectphysical agingen_US
dc.subjectfree volumeen_US
dc.titleGas transport properties in polycarbonate - Influence of the cooling rate, physical aging, and orientationen_US
dc.contributor.departmentChemical Engineeringen_US
dc.description.degreePh. D.en_US D.en_US Polytechnic Institute and State Universityen_US Engineeringen_US
dc.contributor.committeechairMarand, Evaen_US
dc.contributor.committeememberSaraf, Ravi F.en_US
dc.contributor.committeememberWilkes, Garth L.en_US
dc.contributor.committeememberDavis, Richey M.en_US
dc.contributor.committeememberMarand, Hervé L.en_US

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