Date of Award

Summer 8-2014

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Polymers and High Performance Materials

Committee Chair

Sergei Nazarenko

Committee Chair Department

Polymers and High Performance Materials

Committee Member 2

Robson Storey

Committee Member 2 Department

Polymers and High Performance Materials

Committee Member 3

Robert Lochhead

Committee Member 3 Department

Polymers and High Performance Materials

Committee Member 4

Jeffrey Wiggins

Committee Member 4 Department

Polymers and High Performance Materials

Abstract

The second and fourth generations of hydroxylated dendritic polyesters (HBP2, HBP4) were combined with unmodified sodium montmorillonite clay (Na+MMT) in water to generate a broad range of polymer clay nanocomposites from 0 to 100% wt/wt Na+MMT. X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to investigate intercalation states of the clay galleries. It was shown that interlayer spacings were independent of generation number and changed over the composition range from 0.5 nm to 3.5 nm in 0.5 nm increments that corresponded to a flattened HBP conformation within the clay tactoids.

The HBP4/Na+MMT systems were investigated to study the vitrified Rigid Amorphous Fraction (RAF) induced by the clay surfaces. Differential Scanning Calorimetry (DSC) showed changes in heat capacity, ΔCp, at Tg, that decreased with clay content, until completely suppressed at 80 wt% Na+MMT due to confinement. RAF was quantified from these changes in heat capacity and verified by the analysis of orthopositronium lifetime temperature scans utilizing positron annihilation lifetime spectroscopy (PALS): verifying the glassy nature of the RAF at elevated temperatures. Mathematical relationships allowed for correlation of the interlayer spacings with ΔCp. RAF formation correlated to intercalated HBP4, and external surfaces of the clay tactoids.

The interdiffusion of a polymer pair in microlayers was exploited to increase the concentration of nanoclay particles. When microlayers of a nanocomposite composed of organically modified montmorillonite (M2(HT)2) inside maleic anhydride grafted linear low-density polyethylene (LLDPE-g-MA) and low-density polyethylene (LDPE) were taken into the melt, the greater mobility of the linear LLDPE-g-MA chains compared to the branched LDPE chains caused shrinkage of the nanocomposite microlayers, concentrating the M2(HT)2 contained within. Analysis of the clay morphology within these layers demonstrated an increase in clay particle lengths and aspect ratios, which was attributed to the growth of skewed aggregates during concentration. The melt induced clay concentration and increased clay particle dimensions caused significant decreases in the permeability of the nanocomposite microlayers and reduced the overall permeability of the multilayered films. Morphology and transport behavior of these microlayered films were compared to a series of bulk nanocomposites using a second LLDPE-g-MA containing M2(HT)2 with varying clay content.

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