Polyester-Inorganic Nanocomposite Materials Via Sol-Gel Reactions: Synthesis and Characterization of Fundamental Properties

Date of Award


Degree Type


Degree Name

Doctor of Philosophy (PhD)


Polymers and High Performance Materials

First Advisor

Kenneth A. Mauritz

Advisor Department

Polymers and High Performance Materials


A scheme was developed for producing poly(ethylene terephthalate (PET) ionomer )/silicate hybrid materials via polymer-in situ sol-gel reactions for tetraethylorthosilicate (TEOS) using different solvents. Scanning electron microscopy/EDAX studies revealed that silicate structures can be grown deep within PET ionomer films that were melt pressed from silicate-incorporated resin pellets. 29 Si solid-state NMR spectroscopy revealed considerable, successful Si-O-Si bond formation, but also a significant fraction of uncondensed SiOH groups. 23 Na solid-state NMR spectra suggested the presence of ionic aggregates within the unfilled PET ionomer and that these aggregates do not suffer major structural re-arrangements by silicate incorporation. For an ionomer treated with TEOS using MeCl2 solvent, Na + ions are less self-associated than in the unfilled control, suggesting silicate intrusion between PET-SO3- Na + ion pair associations. The ionomer treated with TEOS + tetrachloroethane had more poorly formed ionic aggregates, which illustrates the influence of solvent type on ionic aggregation. First-scan DSC thermograms for the ionomers demonstrate an increase in crystallinity after the incorporation of silicates, but solvent induced crystallization also appears to be operative. Second-scan DSC thermograms also suggest that the addition of silicate particles is not the only factor implicated in re-crystallization, and that solvent type is important even in second scan behavior. Silicate incorporation does not profoundly affect the second scan T g vs. solvent type, i.e ., chain mobility in the amorphous regions is not severely restricted by silicate incorporation. Re-crystallization and melting in these hybrids appears to be due to an interplay between a solvent induced crystallization that strongly depends on solvent type, and interactions between PET chains and in situ -grown, sol-gel-derived silicate particles. Isothermal studies confirmed that the crystallization rate and melting behavior of PET 5% Na+ ionomers depend on processing conditions. PET ionomer/ORMOSIL composites were formed via in situ sol-gel reactions using the ionic regions of PET as preferential reaction sites. TGA analysis revealed successful uptake for all three different solvents and TEOS:MTES composition ratios. TGA derivative curves suggest that for the THF and MeCl2 carrier solvent systems the MTES-generated network interacts more with the PET ionomer matrix. In the case of TCE, the TEOS-generated network interaction appears to be more operative. First scan DSC traces reveal that the in situ sol-gel processing of ORMOSIL phases induces PET ionomer crystallinity, although systems with higher silicate uptake have reduced induced crystallinity. Second scan DSC traces show that Tg is not effected by the incorporation of silicates into the PET ionomer. Also, for the ORMOSIL phases generated using THF and MeCl2 as the swelling solvent, only the pure silicate networks (synthesized using only TEOS) allow recrystallization and melting during the quick scan timeframe. It is thought that the presence of semi-organic MTES silicate networks do not allow fast nucleation onto the inorganic nuclei. (Abstract shortened by UMI.)