An experimental technique is described for simultaneously measuring the static and dynamic interactions of very thin liquid films between two surfaces as they are moved normally or laterally relative to each other. Film thickness can be measured and controlled to 1 angstrom. Initial results are presented of the transition in the physical properties of liquid films only one molecular layer thick to thicker films whose properties are practically indistinguishable from the bulk. In particular, the results show that two molecularly smooth surfaces, when close together in simple liquids, slide (shear) past each other while separated by a discrete number of molecular layers, and that the frictional force is "quantized" with the number of layers.

We have measured the shear forces between two molecularly smooth solid surfaces separated by thin films of various organic liquids. The aim was to investigate the nature of the transitions from continuum to molecular behavior in very thin films. For films whose thickness exceeds ten molecular diameters both their static and dynamic behavior can usually be described in terms of their bulk properties, but for thinner films their behavior becomes progressively more solidlike and can no longer be described, even qualitatively, in terms of bulk/continuum properties such as viscosity. The solidlike state is characterized by the ordering of the liquid molecules into discrete layers. The molecular ordering is further modified by shear, which imposes a preferred orientation. All solidlike films exhibit a yield point or critical shear stress, beyond which they behave like liquid crystals or ductile solids undergoing plastic deformation. Our results on five liquids of different molecular geometry reveal some very complex thin-film properties, such as the quantization of various static and dynamic properties, discontinuous or continuous solid–liquid transitions, smooth or stick–slip friction, and two-dimensional nucleation. Quantitatively, the ‘‘effective’’ viscosity in molecularly thin films can be 105 times the bulk value, and molecular relaxation times can be 1010 times slower. These properties depend not only on the nature of the liquid, but also on the atomic structure of the surfaces, the normal pressure, and the direction and velocity of sliding. We also conclude that many thin-film properties depend on there being two surfaces close together and that they cannot be understood from a consideration of a single solid–liquid interface. The results provide new fundamental insights into the states of thin films, and have a bearing on understanding boundary friction, thin-film lubrication and the stress–strain properties of solids at the molecular level.

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A new technique is described for sliding (shearing) two molecularly smooth surfaces laterally past each other in liquids while monitoring their exact contact area, the normal and transverse forces, and the surface separation. First, we show that the elastic deformations of two initially curved surfaces in adhesive contact are the same under static and dynamic (i.e., sliding) conditions. Detailed results are then presented of how the shear properties of thin films of water and a simple nonpolar liquid are “quantized” with the number of layers. Results with water as the intervening liquid, as well as the effects of humidity on sliding in air, reveal that more complex mechanisms are operating than with simple liquids which appear to be related to the complex “hydration” forces between two surfaces in water or in aqueous salt solutions. The results suggest a close correlation between the static forces and shear properties of very thin liquid films, and the molecular structure of the liquids confined within such films.

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