Studies of Thin Liquid Films Confined between Hydrophobic Surfaces

• Main Author: Li, Zuoli
• Other Authors: Mining and Minerals Engineering
• Format: Others
• Published: Virginia Tech 2014
• Subjects: surface force; hydrophobic force; extended DLVO; thermodynamic analysis; thin water film; thin liquid film
• Online Access: http://hdl.handle.net/10919/49557

Surface force measurements previously conducted with thiolated gold surfaces showed a decrease in excess film entropy (£GSf), suggesting that hydrophobic force originates from changes in the structure of the medium (water) confined between hydrophobic surfaces. As a follow-up to the previous study, surface force measurements have been conducted using an atomic force microscope (AFM) with hydrophobic silica surfaces at temperatures in the range of 10 to 40¢XC. The silica sphere and silica plate were treated by both chemisorption of octadecyltrichlorosilane (OTS) and physical adsorption of octadecyltrimethylammonium chloride (C18TACl). A thermodynamic analysis of the results show similar results for both of the samples, that both ""Sf and excess film enthalpy ("Hf) become more negative with decreasing thickness of the water layer between the hydrophobic surfaces and decreasing temperature. |"Hf | > |T"Sf| represents a necessary condition for the excess free energy change ("Gf ) to be negative and the hydrophobic interaction to be attractive. Thus, the results obtained with both the silylated and C18TACl-adosrbed silica surfaces in the present work and the thiolated gold suefaces reported before show hydrophobic forces originate from structural changes in the medium. Thermodynamic analysis of SFA force measurements obtained at various temperatures revealed that "Sf were much more negative in the shorter hydrophobic force ranges than in the longer ranges, indicating a more significant degree of structuring in the water film when the two hydrophobic surfaces are closer together. <br /><br />It is believed that the water molecules in the thin liquid films (TLFs) of water form clusters as a means to reduce their free energy when they cannot form H-bonds to neighboring hydrophobic surfaces. Dissolved gas molecules should enhance the stability of structured cluster due to the van der Waals force between the entrapped gas molecules and the surrounding water molecules1, which may enhance the strength of the hydrophobic force. Weaker long-range attractive forces detected in degassed water than in air-equilibrated water was found in the present work by means of AFM force measurements, supporting the effect of dissolved gas on the structuring of water. At last, temperature effects on hydrophobic interactions measured in ethanol and the thermodynamic analysis revealed similar results as those found in water, indicating that the hydrophobic force originates from H-bond propagated structuring in the mediums. •<br /> === Ph. D.