Crystal Structure - Polymorphism

Polymorphism

Polymorphism refers to the ability of a solid to exist in more than one crystalline form or structure. According to Gibbs' rules of phase equilibria, these unique crystalline phases will be dependent on intensive variables such as pressure and temperature. Polymorphism can potentially be found in many crystalline materials including polymers, minerals, and metals, and is related to allotropy, which refers to elemental solids. The complete morphology of a material is described by polymorphism and other variables such as crystal habit, amorphous fraction or crystallographic defects. Polymorphs have different stabilities and may spontaneously convert from a metastable form (or thermodynamically unstable form) to the stable form at a particular temperature. They also exhibit different melting points, solubilities, and X-ray diffraction patterns.

One good example of this is the quartz form of silicon dioxide, or SiO₂. In the vast majority of silicates, the Si atom shows tetrahedral coordination by 4 oxygens. All but one of the crystalline forms involve tetrahedral SiO₄ units linked together by shared vertices in different arrangements. In different minerals the tetrahedra show different degrees of networking and polymerization. For example, they occur singly, joined together in pairs, in larger finite clusters including rings, in chains, double chains, sheets, and three-dimensional frameworks. The minerals are classified into groups based on these structures. In each of its 7 thermodynamically stable crystalline forms or polymorphs of crystalline quartz, only 2 out of 4 of each the edges of the SiO₄ tetrahedra are shared with others, yielding the net chemical formula for silica: SiO₂.

Another example is elemental tin (Sn), which is malleable near ambient temperatures but is brittle when cooled. This change in mechanical properties due to existence of its two major allotropes, α- and β-tin. The two allotropes that are encountered at normal pressure and temperature, α-tin and β-tin, are more commonly known as gray tin and white tin respectively. Two more allotropes, γ and σ, exist at temperatures above 161 °C and pressures above several GPa. White tin is metallic, and is the stable crystalline form at or above room temperature. Below 13.2 °C, tin exists in the gray form, which has a diamond cubic crystal structure, similar to diamond, silicon or germanium. Gray tin has no metallic properties at all, is a dull-gray powdery material, and has few uses, other than a few specialized semiconductor applications. Although the α-β transformation temperature of tin is nominally 13.2 °C, impurities (e.g. Al, Zn, etc.) lower the transition temperature well below 0 °C, and upon addition of Sb or Bi the transformation may not occur at all.