Brewster Angle Microscope Investigations of Two Dimensional Phase Transitions
thesisposted on 21.10.2015 by Adam W. Schuman
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The liquid-liquid interface is investigated by microscopic and thermodynamic means to image and measure interfacial properties when the system undergoes a two-dimensional (2D) phase transition of a Gibbs monolayer by varying the sample temperature. An in-house Brewster angle microscope (BAM) is constructed to visualize the interface during this transition while a quasi-elastic light scattering technique is used to determine the interfacial tension. These results complement x-ray investigations of the same systems. Evidence of interfacial micro-separated structure, microphases, comes from observations across a hexane-water interface with the inclusion of a long-chain fluorinated alcohol surfactant into the bulk hexane. Microphases take the form of spatially modulated structure to the density of the surfactant as it spans laterally across the interface. The surfactant monolayer exhibits microphase morphology over a range of a couple degrees as the temperature of the system is scanned through the 2D gas-solid phase transition. Microphase structure was observed for heating and cooling the hexane-water system and structural comparisons are given when the temperature step and quench depth of the cooling process is varied. A complete sequence of morphological structure was observed from 2D gas to cluster to labyrinthine stripe to a 2D solid mosaic pattern. Two characteristic length scales emerge giving rise to speculation of an elastic contribution to the standard repulsive and attractive competitive forces stabilizing the microphase. The benefit of BAM to laterally image very thin films across the surface of an interface on the micrometer length scale nicely complements x-ray reflectivity methods that average structural data transverse to the liquid interface on a molecular scale. To properly analyze x-ray reflectivity data, the interface is required to be laterally homogeneous. BAM can sufficiently characterize the interface for this purpose as is done for a Langmuir monolayer of a lipid-protein mixture that was later investigated by x-ray reflectivity. The same service is provided to an extractant in dodecane/water system. For this system, BAM additionally clarified the type of transition the extractant monolayer undergoes as a function of temperature.