Air at hydrophobic surfaces and kinetics of three phase contact formation.

This review focuses on the importance of air presence at hydrophobic solid surfaces for wetting film rupture and kinetics of three phase contact formation. Affinity to air is a typical feature of hydrophobic surfaces, but it has been often either overlooked or not taken into consideration. When the hydrophobic surface, contacted earlier with air, is immersed into water then air can stay attached to the surface. The origin of long range hydrophobic forces and data showing that these interactions were due to the bridging of nanobubbles attached to the hydrophobic surfaces are discussed. A major part of the review is devoted to the description and analysis of data showing that air (nano-, micro-bubbles and/or air film) present at a hydrophobic surface facilitated rupture of the liquid film and three phase contact formation during bubble collisions with flat Teflon plates of different surface roughness. Although all Teflon plates were highly hydrophobic (contact angles ca. 100 degrees -130 degrees ) the time of the three phase contact (TPC) formation and attachment of the colliding bubble was strongly affected by the plate surface roughness. The time of the TPC formation was shortened from over 80 down to 2-3 ms when the roughness was increased from below 1 microm to over 50 microm. Higher surface roughness means that larger amounts of air was entrapped during the Teflon plates' immersion in water. Additional experimental evidence is given, showing that facilitation of the TPC formation and the bubble attachment was due to air presence and re-distribution over the Teflon surfaces: i) prolonging the plate immersion time resulted in quicker attachment; ii) irregular and disappearing air pockets were recorded at a Teflon surface; iii) a satellite bubble left at a Teflon surface during the first collision facilitated the attachment; iv) attachment always occurred during the first collision in the case of a very rough "Teflon V" surface, but in highly concentrated n-octanol and n-heptanol solutions there was bouncing and attachment occurred during the second collision, moreover; v) the degree of bubble kinetic energy transferred into surface energy was significantly smaller during collisions with hydrophobic (Teflon) surfaces than with the hydrophilic ones. The mechanism of air entrapment and redistribution over Teflon plates immersed in water is presented.