Crystal symmetries quasicrystals

A. Csanady, K. Papp, M. Dobosy, M. Bauer, Direct Observation of the Phase Transformation of quasicrystals to Al6Mn Crystals. Symmetry 1990, 1, 75-79. 

The otiier type of noncrystalline solid was discovered in the 1980s in certain rapidly cooled alloy systems. D Shechtman and coworkers [15] observed electron diffraction patterns with sharp spots with fivefold rotational synnnetry, a syimnetry that had been, until that time, assumed to be impossible. It is easy to show that it is impossible to fill two- or tliree-dimensional space with identical objects that have rotational symmetries of orders other than two, tliree, four or six, and it had been assumed that the long-range periodicity necessary to produce a diffraction pattern with sharp spots could only exist in materials made by the stacking of identical unit cells. The materials that produced these diffraction patterns, but clearly could not be crystals, became known as quasicrystals. 

A pecuhar sohd phase, which has been discovered not too long ago [172], is the quasi-crystalline phase. Quasi-crystals are characterized by a fivefold or icosahedral symmetry which is not of crystallographic type and therefore was assumed to be forbidden. In addition to dislocations which also exist in normal crystals, quasi-crystals show new types of defects called phasons. Computer simulations of the growth of quasicrystals [173] are still somewhat scarce, but an increasing number of quasi-crystalline details are studied by simulations, including dislocations and phasons, anomalous self-diffusion, and crack propagation [174,175]. 

In the next setion we review some key concepts in Mermin s approach. After that we summarise in section III some aspects of the theory of (ordinary) crystals, which would seem to lead on to corresponding results for quasicrystals. A very preliminary sketch of a study of the symmetry properties of momentum space wave functions for quasicrystals is then presented in section IV. 

L. Pauling, Interpretation of so-called icosahedral and decagonal quasicrystals of alloys showing apparent icosahedral symmetry elements as twins of an 820-atom cubic crystal. Computers Math. Applic. 17, 337-339 (1989). 

Quasicrystals are solid materials exhibiting diffraction patterns with apparently sharp spots containing symmetry axes such as fivefold or eightfold axes, which are incompatible with the three-dimensional periodicity associated with crystal lattices. Many such materials are aluminum alloys, which exhibit diffraction patterns with fivefold symmetry axes such materials are called icosahedral quasicrystals. " Such quasicrystals " may be defined to have delta functions in their Fourier transforms, but their local point symmetries are incompatible with the periodic order of traditional crystallography. Structures with fivefold symmetry exhibit quasiperiodicity in two dimensions and periodicity in the third. Quasicrystals are thus seen to exhibit a lower order than in true crystals but a higher order than truly amorphous materials. 

Note that the low-temperature structure is neither a quasicrystal nor an icosahedral glass. Given the molecular symmetry, one might have predicted the latter, whereas icosahedral quasicrystals require two distinct structural units to satisfy space filling. While the precise energetic requirements for crystal versus icosahedral glass formation are not understood, it seems likely that the structural order at low T is driven both by a preference for close packing and,by local orientational order. 

It can be shown mathematically that five-fold axes cannot appear in a truly periodic crystal of single unit cells repeating in space. Nevertheless, some interesting quasicrystals have recently been discovered that have unusual symmetry properties. See Problem 3.39. 

Since our surroundings are three-dimensional, we tend to assume that crystals are formed by periodic arrangements of atoms or molecules in three dimensions. However, many crystals are periodic only in two, or even in one dimension, and some do not have periodic structure at all, e.g. solids with incommensurately modulated structures, certain polymers, and quasicrystals. Materials may assume states that are intermediate between those of a crystalline solid and a liquid, and they are called liquid crystals. Hence, in real crystals, periodicity and/or order extends over a shorter or longer range, which is a function of the nature of the material and conditions under which it was crystallized. Structures of real crystals, e.g. imperfections, distortions, defects and impurities, are subjects of separate disciplines, and symmetry concepts considered below assume an ideal crystal with perfect periodicity. ... 

It is worth noting that the structure in Figure 1.10 not only looks ordered, but it is perfectly ordered. Moreover, in recent decades, many crystals with five-fold symmetry have been found and their structures have been determined. These crystals, however, do not have translational symmetry in three directions, which means that they do not have a finite unit cell and, therefore, they are called quasicrystals quasi - because there is no translational symmetry, crystals - because they produce discrete, crystal-like diffraction patterns. 

Quasicrystals or quasiperiodic crystals are metallic alloys which yield sharp diffraction patterns that display 5-, 8-, 10- or 12-fold symmetry rotational axes - forbidden by the rules of classical crystallography. The first quasicrystals discovered, and most of those that have been investigated, have icosahedral symmetry. Two main models of quasicrystals have been suggested. In the first, a quasicrystal can be regarded as made up of icosahedral clusters of metal atoms, all oriented in the same way, and separated by variable amounts of disordered material. Alternatively, quasicrystals can be considered to be three-dimensional analogues of Penrose tilings. In either case, the material does not possess a crystallographic unit cell in the conventional sense. 

In the years after the discovery of aperiodic crystals (incommensurate modulated, intergrowth and quasicrystals) crystallography was for me a very rich and open field of research, but not mysterious. Even the surprising combination in snow crystals of sixfold circular rotations with hyperbolic rotations [1], leading to hexagrammal scaling symmetry, fitted into the whole because the atomic positions in ice are invariant with respect to both types of crystallographic rotations [2]. 

Quasi-crystals have macroscopic symmetries which are incompatible with a crystal lattice (Section 2.4.1). The first example was discovered in 1984 when the alloy AlMn is rapidly quenched, it forms quasi-crystals of icosahedral symmetry (Section 2.5.6). It is generally accepted that the structure of quasicrystals is derived from aperiodic space filling by several types of unit cell rather than one unique cell. In two-dimensional space, the best-known example is that of Penrose tiling. It is made up of two types of rhombus and has fivefold symmetry. We assume that the icosahedral structure of AlMn is derived from a three-dimensional stacking analogous to Penrose tiling. As is the case for incommensurate crystals, quasi-crystals can be described by perfectly periodic lattices in spaces of dimension higher than three in the case of AlMn, we require six-dimensional space. 

Fig. 9.1. Translational symmetiy radsting in crystals and its lack in quasi-crystals despite a perfect long-range order, (a) The translational symmetiy in the NaCl crystal build of Na" " and Cl ions (b) the Penrose tiling as an example of a 2-D quasicrystaL without translational symmetry (e) a medieval Arabian mosaic as an example of a long-range, non-translatimial order.

It was reported recently, that polymeric can also form quasicrystals. Hayashida et al. [50] demonstrated that certain blends of polyisoprene, polystyrene, and poly(2-vinylpyridine) form starshaped copolymers that assemble into quaskrystals. By probing the samples with transmission electron microscopy and X-ray diffraction methods, they conclude that the films are composed of periodic patterns of triangles and squares that exhibit 12-fold symmetry. These are signs of quasicrystalline ordering. Such ordering differ from conventional crystals lack of periodic structures yet are well-ordered, as indicated by the sharp diffraction patterns they generate. Quasi-crystals also differ from ordinary crystals in another fundamental way. They exhibit rotational symmetries (often five or tenfold). There are still some basic questions about their stracture. 

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