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Substitutional solid solution strengthening occurs when the solute atom is large enough that it can replace solvent atoms in their lattice positions. Some alloying elements are only soluble in small amounts, whereas some solvent and solute pairs form a solution over the whole range of binary compositions.
Hume-Rothery rules, named after William Hume-Rothery, are a set of basic rules that describe the conditions under which an element could dissolve in a metal, forming a solid solution. There are two sets of rules; one refers to substitutional solid solutions, and the other refers to interstitial solid solutions.
The propensity for any two substances to form a solid solution is a complicated matter involving the chemical, crystallographic, and quantum properties of the substances in question. Substitutional solid solutions, in accordance with the Hume-Rothery rules, may form if the solute and solvent have: Similar atomic radii (15% or less difference)
Notice the strain in the lattice that the solute atoms cause. The interstitial solute could be carbon in iron for example. The carbon atoms in the interstitial sites of the lattice creates a stress field that impedes dislocation movement. This is a schematic illustrating how the lattice is strained by the addition of substitutional solute.
Steel is an example of an interstitial alloy, because the very small carbon atoms fit into interstices of the iron matrix. Stainless steel is an example of a combination of interstitial and substitutional alloys, because the carbon atoms fit into the interstices, but some of the iron atoms are substituted by nickel and chromium atoms. [8]
Example on bottom where albite (Na Al Si 3 O 8) changes to anorthite (Ca Al 2 Si 2 O 8), Al 3+replaces Si 4+ and Ca 2+ for Na +. Coupled substitution is the geological process by which two elements simultaneous substitute into a crystal in order to maintain overall electrical neutrality and keep the charge constant. [1]
In the crystal solid state, diffusion within the crystal lattice occurs by either interstitial or substitutional mechanisms and is referred to as lattice diffusion. [1] In interstitial lattice diffusion, a diffusant (such as C in an iron alloy), will diffuse in between the lattice structure of another crystalline element.
Then there is the Hume-Rothery rule, which states that two metals that differ by more than 15% in their atomic radius will not form substitutional solid solutions. This rule can only be used reliably (90 % success) to predict poor solubility; it cannot predict good solubility.