Biomedical subjects

Anita J Hill

Publications and source records attributed to Anita J Hill.

3 recordsLinked to original sources

PubMed2006

Molecular simulations of physical aging in polymer membrane materials.

Poly(1-trimethylsilyl-1-propyne) (PTMSP), the most permeable polymer known, undergoes rapid physical aging. The permeability of PTMSP to gases and vapors decreases dramatically with physical aging. Cavity size (free volume) distributions were calculated in as-cast and aged PTMSP, using an energetic based cavity-sizing algorithm. The large cavities found in as-cast PTMSP disappear in aged PTMSP, which is consistent with the positron annihilation lifetime spectroscopy (PALS) measurements. We also characterized the connectivity of cavities in both as-cast and aged PTMSP membranes. Cavities are more connected in as-cast PTMSP than in aged PTMSP. The average cavity sizes calculated from computer simulation are in good agreement with PALS measurements. The transport and sorption properties of gases in as-cast and aged PTMSP are also measured by molecular simulation. Computer simulations showed the decrease of permeability and the increase of permeability selectivity in PTMSP membranes with physical aging, which agrees with experimental observations. The reduction in gas permeability with physical aging results mainly from the decrease of diffusion coefficients. Solubility coefficients show no significant changes with physical aging.

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PubMed2005

Defect-assisted conductivity in organic ionic plastic crystals.

In order to determine the role of defects (vacancies and extended lattice defects) in the conductivity mechanism of a well studied organic ionic plastic crystal electrolyte, conductivity and mean defect volumes were measured. The ionic conductivity of the salt showed a characteristic phase dependence. Defect volumes, as measured by positron annihilation lifetime spectroscopy, showed increasing rates of expansion with increasing rotational disorder. The dependence of ionic conductivity on defect volume was observed to be phase dependent. Increases in mean defect volume size below approximately 100 cm(3) mol(-1) did not always facilitate ionic conductivity. It was shown that the material undergoes a solid-solid phase transition to the most disordered phase (a plastic crystalline phase with the highest conductivity) when the mean defect volume becomes larger than the molar volume of either the rotating anionic or cationic species. Conductivity in this phase had the strongest dependence on defect volume. Critical volumes calculated from the free volume model of Cohen and Turnbull were unrealistically large.

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PubMed2003

Determination of initial and long-term microstructure changes in ultrahigh molecular weight polyethylene induced by drawing neat and pyrenyl modified films.

Deformation processes in gel-crystallized ultrahigh molecular weight polyethylene (UHMWPE) films with draw ratios (DR) as high as 96 have been investigated by X-ray diffraction (XRD), differential scanning calorimetry (DSC), and positron annihilation lifetime spectroscopy (PALS). In addition, low concentrations of pyrene molecules have been introduced at the time of film preparation from the gels or afterward by sorption after film preparation, and the polarization of their electronic absorption and fluorescence spectra at different draw ratios has been measured over a large temperature range extending to below the glass transition. The pyrene-doped films have been irradiated to introduce covalently attached 1-pyrenyl groups, and these films at two draw ratios have been employed to investigate over large temperature ranges (1) the steady-state fluorescence intensity and (2) the rates of diffusion of N,N-dimethylaniline (DMA). These data have been correlated with the XRD, DSC, and PALS information obtained on the unmodified films. On the basis of analyses of this body of information, a novel deformation model that explains the decreased crystallinity and increased mean free volumes in gel-crystallized UHMWPE at low draw ratios is proposed. It involves "stretch" and "flip" motions of microfibrils present in the undrawn films. The high crystallinity content and stiffer chains due to drawing UHMWPE films result in weak alpha- and beta-relaxation processes, slower diffusion of DMA than in undrawn films, and orientation factors for doped pyrene molecules that are constant over a large temperature range. The overall picture that emerges allows several aspects of the morphology of UHMWPE, a polymer of fundamental importance in materials research, to be understood.

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