chapter four

Surface layers
The physical surface - as stated before - is considered as a heterogeneous zone between two adjoining phases. Atoms (component particles) of the surface are distributed quite differently to those inside the solid body. They are therefore subjected to entirely different energy conditions than these same atoms situated within the solid. Due to a less dense distribution at the surface they have fewer directly neighboring atoms. Therefore, the external atoms (those at the surface) have a higher potential energy than those inside the solid. In the case of an interface between a solid and a gas, the surface is acted upon from the gas phase side by forces substantially smaller. As a result, some of the forces acting on the surface particles are not compensated and the surface is energetically richer than the inside. For that reason, the energy required to remove an atom from the surface is significantly smaller than that required to remove an atom from any location in the bulk of the crystal. The asymmetry of the field of forces acting on the atom (or particle) or element of the surface - affects the value of surface tension which has a tendency to pull the surface particles (or atoms) into the bulk [1]. As has been stated before, the atomically pure surface of a solid is very active both physically and chemically. Besides surface energy and surface tension, at the surface of solids with metallic bonds there occurs electrical voltage with a very high gradient, reaching tens of millions V per cm [1]. Each contact of the surface of a solid with a material body, e.g., gas or liquid, release processes conducive to lowering of tension and to saturation of the surface with molecules of gas, liquid and solids which are situated in the vicinity of the interface. These processes which are accompanied by an accumulation of accidental substances have been given the name of sorption. Surface sorption is usually termed adsorption. The rate of attachment of substances (adsorption, sorption) by solids to the atomically pure surface and the force of their bonding with the solid are both substantially greater than in the case of a surface with earlier adsorbed foreign atoms. Processes of attaching may occur: – spontaneously - in such cases accidental substances are attached, e.g., molecules of water vapour or oxygen from the surface, particles of a lubricant, worn-off particles of metal and then a natural surface is formed;

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– artificially - as a result of intentional action, during the execution of a technological process of enhancing properties (by the creation of new surfaces) of objects embraced by the range of surface engineering. Such enhancement leads to changes in the microstructure, chemical composition, residual stresses, etc., resulting in the creation of a technological surface. It is also possible to artificially enhance the technological surface during service in which case service-generated (usable) surface is formed. In both cases a new surface is created, with properties different to those of the original surface. A sudden limitation of the atomic lattice at the time of creation of the new surface causes the formation of numerous structural defects on this newly created surface. These are formed as a result of displacements of atoms from their ideal positions which cause, among other effects, the creation of dislocations, stacking faults, etc. Each of these structural imperfections has its own free energy which exceeds the total surface energy of the solid [1]. The new technological or usable surface may be a new phase, several new phases, or it may also be a different material. In all cases, however, it constitutes a zone which differs by its state of energy from the rest of the material (substrate, core). A characteristic feature of the physical surface, besides the energy barrier, the surface tension, different character of chemical bonding from that in the bulk of the solid, as well as great physical and chemical activity, is the heterogeneous structure and hence the anisotropy of properties in directions vertical and parallel to the surface. If we assume the real surface to be a physically pure metal surface and we subject it to the action of a gas medium, the gas will have an effect on the metal, just as the metal will have an effect on the gas. As a result, on both sides of the idealized physically pure surface, an interface zone will be created, in the form of a system of layers in a direction normal to the surface. These layers will be basically parallel to the physically pure surface and their structure will be non-uniform in both the parallel as well as the normal direction to the surface. Such layers may be called surface zone layers. The layer of deformed (by the production process) metal or alloy physically (by heat, force, diffusion of foreign atoms), chemically (e.g., by oxidation) and structurally situated below the physically pure surface may be called the subsurface layer (or layers). Since the situation of this layer (or layers), relative to the core of the object, is on the side of the real surface, the term applied is superficial layer. Layers of adsorbed gas, water vapour, sweat, lubricant, and solid particles (dust, material debris), situated above the physically pure surface, may be termed supersurface layers. During technological processes of manufacturing and (although very rarely) during service, these layers form the source of nucleation of a new phase, leading to a new layer, or are removed (to activate the real surface) before being deposited on the almost physically pure surface of a layer of new material, different from that of the core. Since some 30 - 40 years ago this layer has been referred to as coating.

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Fig. 4.1 Schematic representation of surface layers.

This book, going in the footsteps of publications [1, 3 - 5], has recognized a distinction between concepts of superficial layer and coating and assigned a common term of surface layer to both (Fig. 4.1). In a narrower, stricter sense of the word, a physical surface is an inter-phase zone (interface) between a solid and gas (liquid); in a broader sense it includes the superfical layer, and in an even broader sense, the coating. Thus, surface layers constitute, in a broad meaning, a physical surface. Since a coating is manufactured from a material different than that of the core, in reality it is a different material deposited on the core of another one. Therefore, the coating has its own physical surface.

References
1. Burakowski, T., Rolinski, E., and Wierzchon, T.: Metal surface engineering (in Polish). Warsaw University of Technology Publications, Warsaw, Poland, 1992. 2. Adamson, A.: Physical chemistry of surface. Interscience Publishers, Inc., New York, Los Angeles, 1960.

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3. Burakowski, T.: Methods of manufacture of superficial layers - metal surface engineering (in Polish). Proc.: Conference on Methods of manufacture of superficial layers, Rzeszów, Poland, 9-10 June, 1988, pp. 5-27. 4. Burakowski, T.: Metal surface engineering - status and perspectives of development (in Russian). Series: Scientific-technological progress in machine-building, Edition 20. Publications of International Center for Scientific and Technical Information - A.A. Blagonravov Institute for Machine Building Research of the Academy of Science of USSR, Moscow 1990. 5. Burakowski, T.: Metal surface engineering (in Polish). Normalizacja (Standarization), No. 12, 1990, pp. 17-25.

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