Surface energy relations in liquid/solid systems I. The adhesion of liquids to solids and a new method of determining the surface tension of liquids

Abstract
A new method for determining the surface tension of liquids has been derived. This involves the consideration of the advancing and receding contact angles of a liquid drop on a tilted solid surface. The theory has been tested by an improved optical projection technique for a variety of liquid/solid systems and the results obtained are in agreement with the accepted values. It is shown that the advancing and receding contact angles are characteristic constants of liquid/solid systems and the calculated and measured values of the minimum receding angles are in agreement. The prevailing views of 'hysteresis' effects or 'stationary' contact angles which have arisen to account for the data available are incorrect and the discordant experimental results reported are due to inadequate technique. The difference between the adhesions corresponding to the advancing and receding angles is ascribed to the work done in removing an adsorbed unimolecular layer. The work done in gcal./mol. in forming this adsorbed layer is in reasonable agreement with that expected from studies in gas/solid systems and the forces involved are van der Waals'. Further, different solids that might be expected to show similar surface structures yield similar values for the work done. The variation in the value of the advancing angle in some liquid/solid systems and its constancy in others is reconciled with the polar character of the solid surface, i.e. it is suggested that short-range forces are involved. It has been found that monolayers of ferric stearate on glass are orientated with their hydrocarbon tails away from the interface in agreement with electron diffraction measurements. It is suggested that the methods may be useful for investigating the structure of monofilms and built-up layers of monofilms.

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