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Full-Text Articles in Physical Sciences and Mathematics
Characterizing And Monitoring Changes In State Of Polymers During Cure And Use -Aging, Andrew Orschel Meyer
Characterizing And Monitoring Changes In State Of Polymers During Cure And Use -Aging, Andrew Orschel Meyer
Dissertations, Theses, and Masters Projects
Multi Angle Laser Light Scattering (MALLS) and Frequency Dependent Electromagnetic Sensing (FDEMS) provide unique characterizations of polymer systems during cure and use-aging. This research illustrates how MALLS is an extremely accurate technique for absolute characterization of macromolecules, giving molecular weight and size information that other widely used and accepted techniques are incapable of measuring. Application of MALLS to monitoring the changing state of a polyamide-11 system in a water aging environment led to the discovery of an equilibrium molecular weight which is the result of two competing reactions, hydrolysis-degradation and a newly discovered recombination-polymerization reaction. The discovery of this recombination …
Solid State Nmr Characterization Of Structural And Motional Parameter Distributions In Polyamidoammonium Dendrimers, Dariya Ivanovna Malyarenko
Solid State Nmr Characterization Of Structural And Motional Parameter Distributions In Polyamidoammonium Dendrimers, Dariya Ivanovna Malyarenko
Dissertations, Theses, and Masters Projects
The characterization of narrow distributions of structural and motional parameters, and their evolution during the broad glass transition, is performed for deuterated PAMAM dendrimer salts using solid state NMR. The broadening of deuteron quadrupole echo (QE) lineshapes is consistent with the presence of narrow hydrogen bond length distribution (sigmar < 0.25 A) at the spacer amide and branching tertiary amine sites. The temperature dependent averaging of the experimental lineshapes is explained on the basis of fast planar librations in the dendrimer interior, and fast rotation and intermediate regime libration (in an asymmetric cone) of the dendrimer termini. The amplitudes of libration are temperature dependent and higher for low generation dendrimers, while librational rates show Arrhenius behavior only within the glass transition region. In this region, the width of log-normal distribution of rates increases with temperature at sites associated with chlorine counterions. The largest distributions are still less than one order of magnitude wide, unlike the dendrimer in solution or the linear polymers. Interpenetrated low generations (G < 3), uniform intermediate generations (G = 3--5) with surface network, and backfolded high generations (G > 5), are distinguished by interior and termini dynamics.;In the regime of fast motion QE lineshapes are highly sensitive to the presence of narrow structural and motional parameter distributions, and provide constraints on motional geometry independent of rates. The precise characterization of narrow log-normal rate distributions in the intermediate regime can be …