Polymorphism and Allotropy

A crystalline material is one in which the atoms are situated in a repeating or periodic array over large atomic distances—that is, long-range order exists, such that upon solidification, the atoms will position themselves in a repetitive three-dimensional pattern, in which each atom is bonded to its nearest neighbor atoms. Not all solids are single crystals. For example, when liquid water starts freezing, the phase change begins with small ice crystals that grow until they fuse, forming a polycrystalline structure. In the final block of ice, each of the small crystals (called “grains“) is a true crystal with a periodic arrangement of atoms, but the whole polycrystal does not have a periodic arrangement of atoms, because the periodic pattern is broken at the grain boundaries.

Polymorphism and Allotropy

Fe-Fe3C Phase Diagram
In the figure, there is the iron–iron carbide (Fe–Fe3C) phase diagram. The percentage of carbon present and the temperature define the phase of the iron carbon alloy and therefore its physical characteristics and mechanical properties. The percentage of carbon determines the type of the ferrous alloy: iron, steel or cast iron. Source: wikipedia.org Läpple, Volker – Wärmebehandlung des Stahls Grundlagen. License: CC BY-SA 4.0

Some crystalline materials may have more than one crystal structure, a phenomenon known as polymorphism. Polymorphism is the occurrence of multiple crystalline forms of a material. According to Gibbs’ rules of phase equilibria, these unique crystalline phases are dependent on intensive variables such as pressure and temperature. Polymorphism is related to allotropy, which refers to chemical elements. That means, polymorphism is the more general term used for any crystalline material including alloys and chemical elements. Each polymorph is in fact a different thermodynamic solid state and crystal polymorphs of the same compound exhibit different physical properties, such as dissolution rate, shape (angles between facets and facet growth rates), melting point, etc. For this reason, polymorphism is of major importance in industrial manufacture of crystalline products.

One familiar example is found in carbon. Graphite (a soft, black, flaky solid, a moderate electrical conductor) is the stable polymorph at ambient conditions, whereas diamond (an extremely hard, transparent crystal, with the carbon atoms arranged in a tetrahedral lattice. A poor electrical conductor. An excellent thermal conductor.) is formed at extremely high pressures.

Also, pure iron has a BCC crystal structure at room temperature, which changes to FCC iron at 913 °C. Zirconium is HCP (alpha) up to 863°C, where it transforms to the BCC (beta, zirconium) form. Problem is that these phase transitions make this material very brittle.

See also: High Temperature Steam Oxidation of Zirconium Alloys

References:
Materials Science:
  1. U.S. Department of Energy, Material Science. DOE Fundamentals Handbook, Volume 1 and 2. January 1993.
  2. U.S. Department of Energy, Material Science. DOE Fundamentals Handbook, Volume 2 and 2. January 1993.
  3. William D. Callister, David G. Rethwisch. Materials Science and Engineering: An Introduction 9th Edition, Wiley; 9 edition (December 4, 2013), ISBN-13: 978-1118324578.
  4. Eberhart, Mark (2003). Why Things Break: Understanding the World by the Way It Comes Apart. Harmony. ISBN 978-1-4000-4760-4.
  5. Gaskell, David R. (1995). Introduction to the Thermodynamics of Materials (4th ed.). Taylor and Francis Publishing. ISBN 978-1-56032-992-3.
  6. González-Viñas, W. & Mancini, H.L. (2004). An Introduction to Materials Science. Princeton University Press. ISBN 978-0-691-07097-1.
  7. Ashby, Michael; Hugh Shercliff; David Cebon (2007). Materials: engineering, science, processing and design (1st ed.). Butterworth-Heinemann. ISBN 978-0-7506-8391-3.
  8. J. R. Lamarsh, A. J. Baratta, Introduction to Nuclear Engineering, 3d ed., Prentice-Hall, 2001, ISBN: 0-201-82498-1.

See above:

Crystal Structure