Alloying metals lattice defects

On the other hand, pit initiation which is the necessary precursor to propagation, is less well understood but is probably far more dependent on metallurgical structure. A detailed discussion of pit initiation is beyond the scope of this section. The two most widely accepted models are, however, as follows. Heine, etal. suggest that pit initiation on aluminium alloys occurs when chloride ions penetrate the passive oxide film by diffusion via lattice defects. McBee and Kruger indicate that this mechanism may also be applicable to pit initiation on iron. On the other hand, Evans has suggested that a pit initiates at a point on the surface where the rate of metal dissolution is momentarily high, with the result that more aggressive anions... 

FOLLOWING A SHORT introduction dealing with the relationship between diffusion process and field transport phenomena in tarnishing layers on metals and alloys, the mechanism of oxidation of iron is discussed. Epitaxy plays an important role on the gradient of the concentration of lattice defects and, therefore, on the validity of the parabolic rate law. Classical examples of metal oxidation with a parabolic rate law are presented and the various reasons for the deviation observed are elucidated on the systems Iron in CO/CO2 and CU2O in <>2. In addition, the oxidation of alloys with interrupted oxide-metal interfaces is treated. Finally, attention is focussed on the difficulties in explaining the low temperature-oxidation mechanism. 

Broom, T, Ham, R. K. The effects of lattice defects on some physical properties of metals. In Vacancies and other point defects in metals and alloys. London The Institute of Mettds 1958. pp. 41-78. 

This is the first book devoted to the theoretical modelling of refractory carbides and nitrides and alloys based on them. It makes use of computational methods to calculate their spectroscopic, electric, magnetic, superconducting, thermodynamical and mechanical properties. Calculated results on the electronic band structure of ideal binary transition-metal carbides and nitrides are presented, and the influences of crystal lattice defects, vacancies and impurities are studied in detail. Data available on chemical bonding and the properties of multi-component carbide- and nitride-based alloys, as well as their surface electronic structure, are described, and compared with those of bulk crystals. 

T. Broom and R. K. Ham, The effect of lattice defects on some physical properties of metals, in Vacancies and Other Point Defects in Metals and Alloys, Monograph No. 23, The Institute of Metals, London (1958). 

Now, suppose that we have a solid solution of two (2) elemental solids. Would the point defects be the same, or not An easy way to visualize such point defects is shown in the following diagram, given as 3.1.3. on the next page. It is well to note here that homogeneous lattices usually involve metals or solid solutions of metals (alloys) in contrast to heterogeneous lattices which involve compounds such as ZnS. 

The second type of impurity, substitution of a lattice atom with an impurity atom, allows us to enter the world of alloys and intermetallics. Let us diverge slightly for a moment to discuss how control of substitutional impurities can lead to some useful materials, and then we will conclude our description of point defects. An alloy, by definition, is a metallic solid or liquid formed from an intimate combination of two or more elements. By intimate combination, we mean either a liquid or solid solution. In the instance where the solid is crystalline, some of the impurity atoms, usually defined as the minority constituent, occupy sites in the lattice that would normally be occupied by the majority constituent. Alloys need not be crystalline, however. If a liquid alloy is quenched rapidly enough, an amorphous metal can result. The solid material is still an alloy, since the elements are in intimate combination, but there is no crystalline order and hence no substitutional impurities. To aid in our description of substitutional impurities, we will limit the current description to crystalline alloys, but keep in mind that amorphous alloys exist as well. 

There are certain unusual types of defects in metal systems that are noteworthy. It has been found (Taylor Doyle, 1972) that in NiAl alloys A1 atoms on the Al-rich side do not substitute on the Ni sublattice instead there are vacancies in the Ni sites. For example, at 55 at.% Al, 18% of Ni sites are vacant while the A1 sites are filled. Such vacancies determined by composition are referred to as constitutional vacancies. Other alloys have since been found to exhibit such vacancies, typical of these being NiGa and CoGA. Another rather curious aspect of defects is the formation of void lattices when metals such as Mo are irradiated with neutrons or more massive projectiles (Gleiter, 1983). Void lattices arise from agglomeration of vacancies and are akin to superlattices. Typically, neighbouring voids in Mo are separated by 200 A. An explanation for the stability of void lattices on the basis of the continuum theory of elasticity has been proposed (Stoneham, 1971 Tewary Bullough, 1972). 

Embedded atom potentials have been extensively used for performing atomistic simulations of point, line and planar defects in metals and alloys (e.g. Vitek and Srolovitz 1989). The pair potential ( ), atomic charge density pBtom(r), and embedding function F(p) are usually fitted to reproduce the known equilibrium atomic volume, elastic moduli, and ground state structure of the perfect defect-free lattice. However, the prediction of ground state structure, especially the competition between the common metallic structure types fee, bcc, and hep, requires a more careful treatment of the pair potential contribution ( ) than that provided by the semiempirical embedded atom potential. This is considered in the next chapter. 

Later on [87, 88] it was observed by STM that ion bombardment of the Pt25Ni7s(l 11) surface leads to the formation of a pattern of shallow ditches (some 0.2-0.5 A deep) that have been attributed to the dislocations generated by the lattice mismatch of the top layers and the bulk ones. The top layers are enriched in Pt by ion bombardment and hence have a different lattice constant. These dislocations in sputtered alloys may provide diffusion pipes for implanted atoms to reach the surface. Diffusion of metal atoms in the surface region at relatively low temperatures has however been proven to be related to the presence of defects, such as the pinholes observed by STM at the Co/Cu( 100) interface [89]... 

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