A NEW BASIS OF CLASSIFICATION OF

QUASICRYSTALS [8]

What leads to a Quasicrystal formation?

In a seminal paper entitled A basis for the synthesis of
quasicrystals, Rao and Sastry [9] indicated that the
occurrence of icosahedral coordination in a crystalline
compound provided favorable conditions for quasicrystal
formation and they synthesized quasicrystals in the Mg
ZnAl system. This was rapidly expanded to include
several ternary and quaternary alloys [10].

The question of the factors responsible for quasicrystal

formation has attracted a great deal of attention. Atomic
bonding factors based on differences in electronegativity,
size, and valence electron concentrations have been used.
A consensus was built up to regard quasicrystals as
essentially Hume-Rothery electron compounds associated
with specific valence electron concentrations.

While these considerations have been useful, there are

many exceptions and anomalies.
Ideally all the three factors size, electronegativity, and
valence electron concentration should be considered
together.

The pseudo-potential core radii, electronegativity

according to MartynovBatsanov prescription and the
valence electron number counted in a different way from
the other descriptions were used.
An alternative and a more comprehensive route is offered
by the Mendeleev number concept devised by Pettifor for
drawing structure maps. A major merit of this approach is
that it gives weight to the valence bond orbital as a fourth
factor. This enabled us to highlight the importance of the
largest size atom. The important element in the icosahedral
cluster is the largest size atom. Following this, we propose
a classification of quasicrystals as centered on Li-, Mg-,
Al-, Ga-, Ca-, Sc-, Y-, rare earths, and Ti, Zr, Hf.

Classification of Quasicrystals

We restrict our discussion to icosahedral quasicrystals.

Based on their thermodynamic stability, they can be stable
or metastable.
They can be classified on the basis of the majority
component and thus may be termed as Al-, Mg-, Zn-, Cd-,
Ti-, Zr-, and Hf-based quasicrystals.
It is also possible to consider the related rational
approximants such as those based on Mackay and
Bergman clusters. While this did provide a guideline, not
all systems exhibiting icosahedral coordination in their
crystalline phases have proved amenable for the synthesis
of quasicrystals.

The application of e/a ratio has been useful but has its
problems for transition metals. The classical Hume-
Rothery phases of beta, gamma, and epsilon brass
structure. The major difference comes about, when we
consider Zn- and Cd-based quasicrystals. They are seen to
be centered on rare earths, Scandium, Ytterbium, and
Calcium!
The stoichiometry of these very large atoms is in the low
range of 1015%. It is also interesting to note that when
the large size atom classification is made, all four types of
orbitals s, p, d, and f are represented.
4. Pettifor structure map approach

Pettifor introduced a phenomenological coordinate, called

the Mendeleev number M, determined by running a one-
dimensional string through the two-dimensional periodic
table. The path of the string has been chosen in a judicious
fashion so as to give the best structural separation for the
binary AB compounds. Thus elements with neighboring
atomic numbers could have very different Mendeleev
numbers and elements with different atomic numbers
could be neighbors in their Mendeleev numbers.
A classification on the basis of large atom size has opened
interesting possibilities. The Mendeleev number emerges
as the important parameter for choosing the alloys.
The atomic size is the dominant parameter in
quasicrystalline alloys rather than composition.
A minimum amount of the large size atom is necessary to
create icosahedral order throughout the phase.

Stability of Quasicrystals by Hume Rothery Rules [11]

The stability of the icosahedral quasicrystals has been

studied in terms of Hume-Rothery rules i.e., atomic size
factor, electronegativity and valence electron
concentration. It has been confirmed that most of the stable
quasicrystals can be understood within the frame work of
the Hume-Rothery rules. Even more interestingly, it is
found that stable quasicrystals are strict electron
compounds, which only form at sharp valence electron
concentration.

All of the stable quasicrystals commonly have the

corresponding valence electron concentration, but the
dependence of stability on the atomic size factor is
different among the groups. Qualitatively, the most
relevant criterion for the formation of stable quasicrystals
is that the alloy should have a definite valence electron
concentration.
On top of this, a high stability of the quasicrystal is
observed when the atomic size factor is favoured.

References
[8] A new basis for the classification of quasicrystal
H.S. Jeevan, S. Ranganathan

[9] P.R. Rao, G.V.S. Sastry, Pramana 25 (1985) L255

[10] N.K. Mukhopadhayay, G.N. Subbanna, S.

Ranganathan, K. Chattopadhyay, Scripta. Metall. 20
(1986) 525

[11] A test of Hume-Rothery rules for stable

quasicrystals A.-P. Tsai