By Friedrich Kremer
This ebook describes the dynamics of low molecular weight and polymeric molecules once they are limited lower than stipulations of geometrical confinement. It covers geometrical confinement in several dimensionalities:
(i) in nanometer skinny layers or self helping motion pictures (1-dimensional confinement)
(ii) in pores or tubes with nanometric diameters (2-dimensional confinement)
(iii) as micelles embedded in matrices (3-dimensional) or as nanodroplets.
The dynamics below such stipulations were a miles mentioned and imperative subject within the concentration of severe around the world examine actions in the final twenty years. the current e-book discusses how the ensuing molecular mobility is prompted by means of the delicate counterbalance among floor results (typically slowing down molecular dynamics via appealing guest/host interactions) and confinement results (typically expanding the mobility). It additionally explains how those affects could be converted and tuned, e.g. via applicable floor coatings, movie thicknesses or pore diameters. "Dynamics in Confinement" sums up the current state of the art and introduces to the analytical tools of selection for the research of dynamics in nanometer-scale confinement.
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Additional resources for Dynamics in Geometrical Confinement
5 450 475 T [K] Fig. 5 Real part (a) and phase angle (b) of the complex differential voltage as measure of the specific heat capacity for a polycarbonate film (38 nm) at a frequency of 160 Hz. The contribution of the underlying step in heat capacity in the raw data of the phase angle (upper panel of Fig. 5b) was subtracted from the overall curve (lower panel of Fig. 5b). The heating rate was 1 K/min. Data were taken from Ref. 4 Dielectric Expansion Dilatometry Dielectric expansion dilatometry relies on the analysis of the temperature dependence of the dielectric permittivity φ∝ (T ) (or real part of the capacity C ∝ (T )) under the assumption that no dielectric active processes take place in the selected frequency and temperature range.
The data are curved when plotted versus 1/T as expected for glassy dynamics. Such a dependence can be described by the Vogel/Fulcher/Tammann(VFT-) equation [75–77] 30 H. Yin et al. 0 360 380 400 420 440 460 T [K] Fig. 8 a Normalized dielectric loss versus temperature at a frequency of 6 kHz for thin polystyrene films (MW = 1408 kg/mol) at the indicated film thicknesses. All data are taken from Ref. . b Normalized phase angle measured by specific heat spectroscopy for thin polystyrene films (MW = 1408 kg/mol) with a frequency of 360 Hz at the indicated film thicknesses.
The freestanding films show a much stronger depression of Tg with decreasing film thickness than those capped between Al-electrodes. These data demonstrate the influence of the deposited electrodes, which will lead to the formation of a boundary layer with a reduced mobility. The formation of such a boundary layer by adsorption processes was in detail discussed for polystyrene on AlOx in Ref. . This boundary layer with a reduced mobility would lead to weaker thickness dependence for a film capped between the AlOx electrodes than for freestanding films.
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