A water/supercritical CO
2 microemulsion (W/scCO
2 μE) with methyl orange (MO) and sodium bis(1
H,1
H,2
H,2
H-heptadecafluorodecyl)-2-sulfosuccinate, 8FS(EO)
2, was characterized by means of UV-visible absorption spectral and dynamic light scattering (DLS) measurements. Visual observation of the scCO
2 mixtures revealed transparent and reddish scCO
2 phases with and without separated excess water; they were identified as Winsor-II and Winsor-IV W/scCO
2 μE, respectively. The polarities of the aqueous cores in the Winsor-IV W/scCO
2 μE were examined by observing the spectral shift of the absorbance maximum of MO. It was observed that with an increase in the water-to-surfactant molar ratio (
W0c), the measured absorbance maximum shifted from 418 to 423 nm, which suggests that the polarity of the environment surrounding the MO molecules was methanol-like, and the polarity increased with
W0c. The hydrodynamic diameter of Winsor-IV W/scCO
2 μE increased drastically with
W0c but gradually with a decrease in the CO
2 density. The increase in the diameter was a result of the aggregation of the μE droplets and the fusion promoted by the increase in
W0c and the decrease in the CO
2 density, in addition to the swelling of reversed micelles.
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