ISSN 1062-8738, Bulletin of the Russian Academy of Sciences: Physics, 2007, Vol. 71, No. 2, pp. 233–237. © Allerton Press, Inc., 2007.
Original Russian Text © N.N. Ovsyuk, S.V. Goryainov, 2007, published in Izvestiya Rossiiskoi Akademii Nauk. Seriya Fizicheskaya, 2007, Vol. 71, No. 2, pp. 243–246.
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INTRODUCTION
Polyamorphism, i.e., the coexistence of different
amorphous phases of the same composition but with
different densities, has been extensively investigated
since the discovery of the high-density amorphous
phase of water [1]. The nature of transitions between
the low-density amorphous (LDA) and high-density
amorphous (HDA) phases is still not clearly understood
because the interaction between the amorphous phases
is rather complicated. This complexity most likely can
be explained by two factors. The first factor is associ-
ated with the fact that individual elementary atomic
clusters are characterized by a natural dispersion of
energies and the transitions between clusters of differ-
ent structural types can occur in two directions. As a
consequence, the energy relation between two amor-
phous phases is difficult to determine reliably. More-
over, the distributions of discrete energy minima in the
configurational space can be smeared into energy
bands. This means that, in contrast to crystals for which
the phase transition point is clearly defined by the point
of intersection of the curves describing the Gibbs free
energy, amorphous phases can undergo a continuous
transformation. The second factor, in our opinion, can
be associated with the fact that the LDA and HDA
phases belong to two different classes of amorphous
materials. The structure of the LDA phase consists of
random displacements of nuclei of the amorphous
phase that do not destroy the crystal topology, whereas
the HDA phase is a typical thermal glass with the
atomic structure topologically nonequivalent to any
crystal structure. We believe that, since the effective
Hamiltonians describing the elastic strain energy in
terms of atomic displacements in these phases should
be constructed differently, it is necessary to use differ-
ent models of amorphization. For these reasons, a gen-
eral physical concept of microscopic processes respon-
sible for the amorphous–amorphous phase transitions
has not been proposed to date. Mutual transformations
between amorphous phases can proceed continuously.
This raises a natural question as to whether the volume,
short-range order structure, and other properties
abruptly change in amorphous phases under compres-
sion. Experimental investigations have revealed that,
apart from the amorphous–amorphous phase transi-
tions accompanied by a continuous gradual change in
the volume in SiO
2
and GeO
2
oxides [2, 3], there can
occur first-order phase transitions attended by a discon-
tinuous change in the volume in H
2
O and Si [4, 5]. The
elucidation of the mechanisms of these transformations
is the most intriguing problem. In crystals, phase tran-
sitions occur either through nucleation and diffusive
growth of a new phase (diffusive transformations) or
through coherent displacements of atoms in the crystal
lattice (martensitic transformations). However, the two
aforementioned mechanisms are not appropriate for
describing transformations between amorphous phases.
In this respect, the question not only as to the mecha-
nism but also as to the possibility of abrupt structural
transformations occurring in amorphous materials
under compression has until recently remained open.
Brazhkin and Lyapin [6] analyzed the causes for exist-
ence of different scenarios of structural transformations
that lead to abrupt and smeared changes in the short-
range order structure in disordered materials. These
authors drew the conclusion that the type of transitions
is determined by the ratio between the size of the small-
est possible region with a changed short-range order
and the correlation length of the medium-range order in
a disordered medium.
In the very recent past, amorphous zeolites have
attracted the particular attention of researchers owing to
the discovery of polyamorphism in these materials.
Greaves and co-workers [7, 8] investigated the dynam-
ics of the amorphization of crystalline zeolites with the
use of X-ray diffraction and small-angle X-ray scatter-
Slow Amorphization of Zeolites
N. N. Ovsyuk and S. V. Goryainov
Institute of Geology and Mineralogy, Siberian Division, Russian Academy of Sciences,
Universitetskii pr. 3, Novosibirsk, 630090 Russia
e-mail: ovsyuk@uiggm.nsc.ru
Abstract—The dynamics of amorphization in two zeolites with different densities is investigated using high-
pressure Raman spectroscopy. Slow amorphization of the denser zeolite under pressure leads to the formation
of a low-density amorphous (LDA) phase that transforms into a more disordered high-density amorphous
(HDA) phase with a further increase in the pressure. It is revealed that the LDA–HDA transformation is a first
order phase transition occurring with an increase in the silicon coordination.
DOI: 10.3103/S1062873807020219