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A Schönhals

Publications and source records attributed to A Schönhals.

6 recordsLinked to original sources
PubMed2003

Temperature and pressure dependence of the dynamics in a poly(methyl acrylate) side-chain liquid-crystalline polymer.

The molecular dynamics of a side-chain polymer liquid crystal with a poly(methyl acrylate) backbone and a (p-alkoxy-phenyl)-benzoate mesogenic group have been studied in the unaligned state as a function of temperature and pressure using dielectric spectroscopy. Polarizing optical microscopy, differential scanning calorimetry, and pressure-volume-temperature (PVT) measurements revealed three transition temperatures separating four phases (glass, smectic, nematic, and isotropic). Different dynamic processes have been identified reflecting librational modes (gamma process), local relaxation of the mesogenic group (beta process), the segmental mode (alpha process) associated with the dynamic glass transition, and a slower process (delta process) reflecting the side-chain dynamics within the liquid crystal order. Pressure exerts a stronger influence on the alpha as compared to the delta process. Starting from the nematic phase, pressure was found to induce the nematic-to-smectic transformation. The associated dynamic changes were in excellent agreement with the PVT results implying that the dynamics are directly coupled to the thermodynamic state. Pressure was found to enhance the stability of the smectic order within the P-T phase diagram.

Journal Article↗
PubMed2003

Glassy dynamics of polymers confined to nanoporous glasses revealed by relaxational and scattering experiments.

The glassy dynamics of poly(propylene glycol) (PPG) and poly(dimethyl siloxane) (PDMS) confined to a nanoporous host system revealed by dielectric spectroscopy, temperature-modulated DSC and neutron scattering is compared. For both systems the relaxation rates estimated from dielectric spectroscopy and temperature-modulated DSC agree quantitatively indicating that both experiments sense the glass transition. For PPG the segmental dynamics is determined by a counterbalance of adsorption and confinement effect. The former results form an interaction of the confined macromolecules with the internal surfaces. A confinement effect originates from an inherent length scale on which the underlying molecular motions take place. The increment of the specific-heat capacity [Formula: see text] at the glass transition vanishes at a finite length scale of 1.8 nm. Both results support the conception that a characteristic length scale is relevant for glassy dynamics. For PDMS only a confinement effect is observed which is much stronger than that for PPG. Down to a pore size of 7.5 nm, the temperature dependence of the relaxation times follows the Vogel-Fulcher-Tammann dependence. At a pore size of 5 nm this changes to an Arrhenius-like behaviour with a low activation energy. At the same pore size [Formula: see text] vanishes for PDMS. Quasielastic neutron scattering experiments reveal that also the diffusive character of the relevant molecular motions --found to be characteristic above the glass transition-- seems to disappear at this length scale. These results gives further strong support that the glass transition has to be characterised by an inherent length scale of the relevant molecular motions.

Adsorption↗