Plastic crystal

A plastic crystal is a crystal composed of weakly interacting molecules that possess some orientational or conformational degree of freedom. The name plastic crystal refers to the mechanical softness of such phases: they resemble waxes and are easily deformed. If the internal degree of freedom is molecular rotation, the name rotor phase or rotatory phase is also used. Typical examples are the modifications Methane I and Ethane I.

In addition to the conventional molecular plastic crystals, there are also emerging ionic plastic crystals, particularly organic ionic plastic crystals (OIPCs) and protic organic ionic plastic crystals (POIPCs).[1][2] POIPCs are solid protic organic salts formed by proton transfer from a Brønsted acid to a Brønsted base and in essence are protic ionic liquids in the molten state, have found to be promising solid-state proton conductors for high temperature proton-exchange membrane fuel cells.[1] Examples include 1,2,4-triazolium perfluorobutanesulfonate[1] and imidazolium methanesulfonate.[2]

If the internal degree of freedom freezes in a disordered way, an orientational glass is obtained. The orientational degree of freedom may be an almost free rotation, or it may be a jump diffusion between a restricted number of possible orientations, as was shown for carbon tetrabromide.[3]

X- ray diffraction patterns of plastic crystals are characterized by strong diffuse intensity in addition to the sharp Bragg peaks.[1] In a powder pattern this intensity appears to resemble an amorphous background as one would expect for a liquid,[1] but for a single crystal the diffuse contribution reveals itself to be highly structured. The Bragg peaks can be used to determine an average structure but due to the large amount of disorder this is not very insightful. It is the structure of the diffuse scattering that reflects the details of the constrained disorder in the system. Recent advances in two-dimensional detection at synchrotron beam lines facilitate the study of such patterns.

  1. ^ a b c d e Jiangshui Luo; Annemette H. Jensen; Neil R. Brooks; Jeroen Sniekers; et al. (2015). "1,2,4-Triazolium perfluorobutanesulfonate as an archetypal pure protic organic ionic plastic crystal electrolyte for all-solid-state fuel cells". Energy & Environmental Science. 8 (4): 1276–1291. doi:10.1039/C4EE02280G.
  2. ^ a b Jiangshui Luo; Olaf Conrad & Ivo F. J. Vankelecom (2013). "Imidazolium methanesulfonate as a high temperature proton conductor" (PDF). Journal of Materials Chemistry A. 1 (6): 2238–2247. doi:10.1039/C2TA00713D.
  3. ^ Jacob C. W. Folmer; Ray L. Withers; T. R. Welberry; James D. Martin (2008). "Coupled orientational and displacive degrees of freedom in the high-temperature plastic phase of the carbon tetrabromide α-CBr4". Physical Review B. 77 (14). 144205. Bibcode:2008PhRvB..77n4205F. doi:10.1103/PhysRevB.77.144205.