A solid surface, or more exactly a solid-gas or solid-liquid interface, has a complex structure and complex properties depending on the nature of the solids, the method of surface preparation, and the interaction between the surface and the environment. Properties of solid surfaces are crucial to surface interaction because surface properties affect real area of contact, friction, wear, and lubrication. In addition to tribological functions, surface properties are important in other applications, such as optical, electrical and thermal performance, painting, and appearance.Solid surfaces, irrespective of their method of formation, contain irregularities or deviations from the prescribed geometrical form (Whitehouse, 1994;Bhushan, 1996Bhushan, , 1999aThomas, 1999). The surfaces contain irregularities of various orders ranging from shape deviations to irregularities of the order of interatomic distances. No machining method, however precise, can produce a molecularly flat surface on conventional materials. Even the smoothest surfaces, such as those obtained by cleavage of some crystals, contain irregularities, the heights of which exceed the interatomic distances. For technological applications, both macro-and micro/nanotopography of the surfaces (surface texture) are important (Bhushan, 1999a,b).In addition to surface deviations, the solid surface itself consists of several zones having physicochemical properties peculiar to the bulk material itself ( Figure 2.1 ) (Gatos, 1968;Haltner, 1969;Buckley, 1981). As a result of the forming process in metals and alloys, there is a zone of work-hardened or deformed material on top of which is a region of microcrystalline or amorphous structure that is called the Beilby layer. Deformed layers would also be present in ceramics and polymers. These layers are extremely important because their properties, from a surface chemistry point of view, can be entirely different from the annealed bulk material. Likewise, their mechanical behavior is influenced by the amount and depth of deformation of the surface layers.Many of the surfaces are chemically reactive. With the exception of noble metals, all metals and alloys and many nonmetals form surface oxide layers in air, and in other environments they are likely to form other layers (for example, nitrides, sulfides, and chlorides). Besides the chemical corrosion film, there are also adsorbed films that are produced either by physisorption or chemisorption of oxygen, water vapor, and hydrocarbons, from the environment. Occasionally, there will be a greasy or oily film derived from the environment. These films are found on metallic and nonmetallic surfaces.The presence of surface films affects friction and wear. The effect of adsorbed films, even a fraction of a monolayer, is significant on the surface interaction. Sometimes, the films wear out in the initial running period and subsequently have no effect. The effect of greasy or soapy film, if present, is more marked; it reduces the severity of surface interaction often by one or more...