Dielectric Study of Molecular Mobility in Poly(propylene-graft-maleic anhydride)/Clay Nanocomposites
(2005)
Polymer/clay nanocomposite materials based on poly(propylene-graft-maleic anhydride) (PPgMAH) and two different organophilic modified clays were investigated by dielectric relaxation spectroscopy (DRS). In contrast to ungrafted polypropylene (PP), PPgMAH shows a dielectrically active relaxation process which can be assigned to localized fluctuations of the polar maleic anhydride groups. Its relaxation rate exhibits an unusual temperature dependence, which could be attributed to a redistribution of water molecules in the polymeric matrix. This is confirmed by a combination of Raman spectroscopy and thermogravimetric experiments (TGA) with real-time dielectric measurements under controlled atmospheres. In the nanocomposites this relaxation process is shifted to higher frequencies up to 3 orders of magnitude compared to the unfilled polymer. This indicates a significantly enhanced molecular mobility in the interfacial regions. In the nanocomposite materials a separate high-temperature process due to Maxwell-Wagner-Sillars (MWS) polarization was observed. The time constant of this MWS process can be correlated with characteristic length scales in nanocomposites and therefore provides additional information on dispersion and delamination/exfoliation of clay platelets in these materials. These properties also influence the diffusivity of the water molecules as revealed by real-time dielectric investigations.
The retention of chemical structure and functional groups during pulsed plasma polymerization was used for producing adhesion-promoting plasma polymer layers with high concentrations of exclusively one kind of functional groups, such as OH, NH2, or COOH. The maximum content of functional groups was 31 OH using allyl alcohol, 18 NH2 using allylamine, or 24 COOH per 100 C atoms using acrylic acid. To vary the density of functional groups, chemical co-polymerization with ethylene as 'chain-extending' co-monomer, or butadiene as 'chemical crosslinker' was initiated in the pulsed plasma. The composition of these co-polymers was investigated by XPS and IR spectroscopy. The concentrations of functional groups were measured by derivatizing with fluorine-containing reagents and using XPS. A set of plasma parameters was found to be a good compromise between a high number of functional groups and complete insolubility in water, ethanol or THF,which is needed for further chemical processing. Here, these monotype-functionalized surfaces were used in metal-polymer systems as adhesion-promoting interlayers to examine the influence of type and density of functional groups on adhesion. As expected, COOH- and OH-group-terminated interlayers showed maximum peel strengths to evaporated aluminium layers. The adhesion increased linearly with the number of OH groups to a maximum at about 27 OH per 100 C atoms. Higher concentrations of OH groups did not increase the peel strength further.
Polymers synthesized with plasma techniques are very interesting materials for electronic, optic, and bio compatible applications. Thin films of plasma polymers shows a good adhesion to metals, glass, or other polymers. But the supramolecular structure, the durability, and the chemical and mechanical behavior of these polymers is poorly understood. Therefore dielectric investigations are carried out to study the dynamic behavior of the plasma polymers. As polymer system allyl alcohol/alkene is chosen to get polymers with a defined concentration of hydroxyl groups. The dielectric investigations shows several relaxation processes and a dependency of the dielectric parameters from the ratio of allyl alcohol in the polymer is observed. This results indicated that the alkene monomers were assembled continuous into the polymer matrix.
Dielectric spectroscopy has been used to study poly(ethylene naphthalene 2,6 dicarboxylate) (PEN) samples of different morphologies obtained by thermally treating bi-axially stretched PEN films. Neat and thermally treated samples of PEN films have been characterised by differential scanning calorimetry in order to measure the glass transition and melting temperatures as well as the degrees of crystallinity. Dielectric analysis has allowed the observation of the evolution of molecular relaxation phenomena with morphology changes and has revealed three relaxation processes: ?-, ?*- and ?-relaxation (increasing temperature). The ?-relaxation is associated with local motions of ester and the ?*-relaxation with partially cooperative motions of naphthalene groups. The latter has been shown to be related to the morphology of the materials under study. The ?-relaxation associated to the glass transition of PEN corresponds to cooperative motions induced by conformational rearrangements of the main chain and depends also on the morphology of the PEN films. Dielectric relaxation behaviours were compared using the activation energies calculated from Arrhenius equation formalism for the two sub-glass processes. VogelFulcherTammann fits were performed on the ?-relaxation. Our important contribution for the bi-axially stretched PEN films study is related to the assignment of the ?*-relaxation that can be attributed to naphthalene aggregates.