Dissertation/Thesis Abstract

Interfacial structure and dynamics of nematic 4-n-pentyl-4'-cyanobiphenyl liquid crystals on silver, silica and modified silica substrates
by Yoo, Heemin, Ph.D., The University of Arizona, 2009, 285; 3359811
Abstract (Summary)

The process of forcibly dewetting a solid substrate from a bulk liquid so as to leave a thin residual layer on the surface is referred to as forced dewetting. This novel experimental approach helps to investigate interfacial species by minimizing the interference of the bulk liquid when coupled with spectroscopy. In this work, the scope of liquids investigating using this approach has been expanded from simple fluids to one type of complex fluid, a nematic liquid crystal, 4-n-pentyl-4’-cyanobiphenyl (5CB).

In order to better understand the interfacial behavior of the simple fluids, water, chloroform, and n-pentane vapors were adsorbed onto ω-terminated SAM-modifed Ag (11-mercaptoundecanoic acid, 11-mercaptoundenanol, and undecanethiol) surfaces under vapor-saturated conditions. The kinetics of solvent adsorption on each of these surfaces were investigated and the thicknesses of the adsorbed layer were compared to predictions from Lifshitz theory of long-range van der Waals interactions. Although the predicted thicknesses do not match the experimental values for adsorbed films, the predicted thicknesses do match those observed experimentally using forced dewetting. The correlation between these predicted and observed thicknesses implies that residual film formation under the conditions of forced dewetting used in this laboratory is not appropriately described by fluid dynamic models as previously thought. Instead, residual film formation appears to be dictated by interfacial forces alone.

The surface adsorption behavior of 5CB was investigated using surface-enhanced Raman spectroscopy with the aid of localized surface plasmon resonances-surface plasmon polaritron coupling. The average orientation of the thin 5CB layer (∼1 nm) was 20 evaluated using SERS surface selection rules. The results clearly indicate that 5CB is adsorbed to smooth Ag surface in a facial orientation with π-d orbital interaction suggested.

Finally, forced dewetting studies of bare, —NH2-terminated SAM, and —CH3-terminated SAM modified-SiO2 substrates from 5CB were undertaken. Residual layer thicknesses were monitored as a function of substrate velocity (1–1726 μm/s). The transition from the regime in which interfacial forces dictate residual layer thickness to the regime in which fluid dynamic forces dictate thickness was observed for the first time and was evaluated in terms of the average 5CB director orientation. Unlike simple fluids, 5CB has strong interfacial interactions from surface anchoring depending on the chemical nature of the substrate, which makes the residual layer thicknesses at least 100 times larger than observed in simple fluids. These results are important in understanding the coherence length over which surface anchoring is important as a function of surface free energy.

Indexing (document details)
Advisor: Pemberton, Jeanne E.
Commitee: Enemark, John H., Evans, Dennis H., Miranda, Katrina M., Saavedra, Scott
School: The University of Arizona
Department: Chemistry
School Location: United States -- Arizona
Source: DAI-B 70/06, Dissertation Abstracts International
Subjects: Analytical chemistry
Keywords: Forced dewetting, Lifshitz theory, Liquid crystals, Nematic liquid crystals, Pentylcyanobiphenyl, Silica substrates
Publication Number: 3359811
ISBN: 978-1-109-22189-3
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