Lectures

LEUCITE PORCELAIN
VLADIMÍR ŠATAVA, ALEXANDRA KLOUŽKOVÁ*, DIMITRIJ LEŽAL, MARTINA NOVOTNÁ

Laboratory of Inorganic Materials,

Institute of Inorganic Chemistry ASCR and Institute of Chemical Technology, Prague,
V Holešovičkách 41, 180 00 Prague, Czech Republic
E-mail: [email protected]

*Department of Glass and Ceramics,

Institute of Chemical Technology, Prague,
Technická 5, 166 28 Prague, Czech Republic

Submitted May 14, 2001; accepted July 30, 2001.

Keywords: Leucite, Dental prosthetics, Phase transformation

INTRODUCTION achieved an aesthetically satisfactory appearance, i.e.

translucence, colour shade and also satisfactory
A number of properties of potassium and cesium strength. This technological process has therefore been
aluminoslilicates suitable for utilization in technical known for a long time, but the principles of weldability
practice have been discovered during the last fifteen with metal and the causes of brittleness of the product
years. It was above all the possibility of immobilising have been understood only not far ago. This fact can be
radioactive cesium 131Cs because its fixing into the regarded as the main reason why nowadays
tructure of borosilicate glass involves big difficulties, polyacrylates reinforced with a metallic structure are
particularly due to extractability of cesium out of the increasingly used in dental prosthetics in spite of a
materials. Tests have been carried out with alumino- number of more advantageous properties of porcelain
silicates, phosphates, titanates, and various zeolites; (hardness, colour fastness, biological tolerance,
however, the best results were obtained with pollucite resistance to the oral environment, and also durability).
(CsAlSi2O6). Its high melting temperature (above The problem of reliable weldability between ceramics
1900°C), relatively low density (3.3 g/cm3) and and metals has been satisfactorily examined by Hahn
a relatively low thermal expansion coefficient ensure and Teuchert [2] who showed that the primary
a good resistance to thermal shocks. A low creep at requirement is to reduce the difference in thermal
1400 – 1500°C and chemical inertness allow materials expansion coefficients of the ceramic material and the
suitable for high-temperature parts of combustion metal. In place of the mix used in the manufacture of
engines, gas turbines and the like to be prepared. conventional feldspar porcelain they have chosen a
However, dental prosthetics appears to be the most composition corresponding to the region of primary
significant field of application. The way was found how crystallization of leucite in the system K2O-Al2O3-SiO2
to improve the properties of dental porcelain, in and demonstrated that leucite crystallized during the
particular its fused adhesion to metals and fracture cooling of the product raises the thermal expansion
toughness. The innovation is based on the properties of coefficient of porcelain to a value close to the expansion
leucite (KALSi2O6) whose presence in porcelain allows of metal (13 – 15 × 10-6 K-1). At the same time they
its thermal expansion to be adjusted to that of metals, so found that admixtures of lithium, rubidium and cesium
that the suppression of changes occurring during the promote crystallization, which is suppressed by sodium
cooling down of the product lead to enhanced fracture admixtures. On this basis, which represented a leap
toughness of the porcelain. forward in the development of dental porcelain, it was
eventually possible to prepare leucite porcelain which
Utilization in dental prosthetics is readily fusible with many metals. This is borne out by
a number of patents [3 – 5], and also by the launching
Use of porcelain in dental prosthetics was already of industrial production of the raw material mix for
known in the 18th century [1]. In principle, a thin layer stomatological laboratories.
of the porcelain mix (quartz, feldspar, kaolin) was Further development of leucite porcelain was
applied in paste form onto the roughened surface of a influenced by several significant studies. Morena [6]
metallic skeleton and then fired at a suitable found that glasses containing dispersed crystals of
temperature, usually 900 – 980°C, at which sintering leucite exhibit higher fracture toughness than the same
took place, and on cooling down the ceramic material glasses free from leucite crystals. Mackert [7] and also

Ceramics − Silikáty 46 (1) 37-40 (2002) 37

 V. Šatava, A. Kloužková, D. Ležal, M. Novotná

Denry [8] discovered that in the vicinity of leucite

crystals in porcelain there were microcracks whose
origin they ascribed to the difference between thermal
expansion of leucite and that of the glass matrix. On the
basis of these findings, Rasmussen [9] assumed that the
mechanism of increased fracture toughness of leucite
porcelain could be similar to that of ZTA composites
(Zirconium Toughened Alumina) [10]. It has been
proved that their high fracture toughness is due to
martensitic transformation of metastable tetragonal
ZrO2 to its monoclinic form. Rasmussen supported his
hypothesis by the plausible convincing evidence for the
fact that the transformation of metastable cubic leucite
in porcelain may be initiated by stress in a mechanically
loaded material. This hypothesis had subsequently
turned the research to another direction, namely at
seeking a material exhibiting not only fusibility with
metals, but at the same time also a high fracture
toughness. It has been proved that leucite porcelain
containing 6.2vol.% of leucite in its vitreous matrix
achieves a fracture toughness higher by up to 60% than a)
the classical feldspar porcelain [11].
A completely new field of study aimed at finding
new structural materials has thus been opened for the
materials science. To understand the behaviour of
leucite, it was first necessary to study in depth its
structure and its behaviour in the course of phase
transformations.

Crystal structure
and phase transformations of leucite

The structure of leucite represents a continuous

three-dimensional skeleton formed by (Si,Al)O4
tetrahedra, each of which shares all its oxygens with its
neighbours [12, 13]. The tetrahedra are arranged into
four-, six- and eight-member rings, where the six-
member ones form a sequence of parallel layers, passed
through by open channels in the perpendicular
direction. Potassium cations are placed in the channels.
The structure of leucite is stable above the temperature
of 893 K. It is cubic, characterized the spatial group
Ia3d, and the elementary cell contains 48 tetrahedra and
16 potassium cations. b)
On cooling down the cubic structure is transformed
into a tetragonal one. This conversion is rapid, Figure 1. Temperature dependence of a) volume of the elemen-
reversible and continuous (transformation of the 2nd tary cell, b) dimensions of the elementary cell.
order). The change in the volume and size of the
elementary cell in terms of temperature is shown by
figures 1a and b. tetrahedron layers, as established by Palmer [13] on the
The cubic structure of leucite has the significant basis of neutron diffraction.
property of being extremely tolerant with respect to The transformation is martensitic, that is
change in composition. K+ cations are readily replaceable anisotropic and athermal, proceeds at the speed of
for Rb+ or Cs+, but also aluminium cations in the tetra- sound in solids and exhibits temperature hystereses. It
hedral can be easity substituted with those of boron or proceeds diffusion-free, by the slipping or twinning
iron [14]. By the substitution of alkali cations the stabi- mechanism, during which processes the atoms
lity of the cubic modification is shifted towards lower retain their neighbours and move over a distance that is
temperatures and the size of the elementary cell grows. smaller than their original mutual one. In the case of
The conversion of cubic leucite into the tetragonal leucite the martensitic transformation is facilitated
modification involves deformation of the six-member by slippage of the six-member tetrahedron ring planes.

38 Ceramics − Silikáty 46 (1) 37-40 (2002)

 Leucite porcelain

Figure 2. Temperature dependence of the structure of channels and of the placing of potassium ions.

a better understanding of the mechanisms of promoting

fracture toughness, about which very little is so far
known in contrast to the ZTA materials.

The actual aims of research

The problem of fusion joining of porcelain with

metals can be regarded as a satisfactorily resolved one.
However, attainment of a satisfactory fracture
toughness of leucite porcelain has so far remained an
open issue, both from the standpoint of dependence of
fracture toughness on the microstructure of the material,
as well as from that of viable technology.
A great problem is represented by the fact that
nucleation and growth of leucite crystals from melt, on
which the present technology of leucite porcelain
manufacture is based, are extraordinarily slow
processes requiring very long holding periods on firing
[15]. The same problem arises in connection with the
firing of precursors prepared by the sol-gel method [16]
or by decomposition of zeolites of suitable composition
Figure 3. Two mechanisms of martensitic transformation: [17]. It is also difficult to control these processes so as
twinning and slipping. to produce a homogeneous dispersion of leucite crystals
in the vitreous matrix, i.e. a microstructure that with
On the basis of a similarity between martensitic ZTA materials has been found optimal in terms of
transformation of leucite with that of ZrO2 it may be fracture toughness. As shown by Hölland [18],
assumed that the application of leucite represents a nucleation of leucite in glass takes place at the surface
promising and so far non-utilized way of preparing new only, and it may be assumed that this might also be the
structural materials. A prerequisite for this is of course case of the other precursors mentioned.

Ceramics − Silikáty 46 (1) 37-40 (2002) 39

 V. Šatava, A. Kloužková, D. Ležal, M. Novotná

A viable way of resolving the problems might be 11. Drummmond J.L., King I.J., Bapna M.S., Kofuski R.D.:
offered by hydrothermal synthesis of leucite. Dental Mater. 16, 226 (2000).
It was this method that has been proved successful 12. Liebau F.: Structural Chemistry of Silicates, Springer
in the preparation of pollucite [19, 20, 21] at a Verlag, Berlin 1985.
temperature of 220°C and with a holding period of the 13. Palmer D.C., Dove N.T., Ibberson R.M., Powell B.M.:
order of tens of minutes. Control of nucleation [22] and Am. Mineral. 82, 16 (1997).
crystal growth under hydrothermal conditions was 14. Yamase I., Kobayashi H., Mitamura T.: J. Thermal Anal.
studied in detail in connection with the synthesis of 57, 695 (1999).
zeolites [23, 24]. It may be assumed that this method 15. Taylor D., Henderson C.M.: Am. Mineral 53, 1476
could allow also leucite with a particle size of the order (1968).
of tens nanometres to be synthesized, and subsequently 16. Liu Ch., Komarneni Sri., Roy R.: J. Am. Ceram. Soc. 77,
used in preparing, with a suitable matrix, a composite 3105 (1994).
material whose fracture toughness (again due to 17. Bedard R.I., Flaningen E.M.: US Patent 5,071,801 (1991).
similarity with ZTA materials) should attain values 18. Hölland W., Frank M., Rheinberger V.: J. Non-Cryst.
exceeding several times those of exhibiting by Solids 180, 292 (1995).
contemporary leucite porcelain. 19. Yanagisawa K., Kanahara S., Nishioka M., Yanasaki N.: J.
Nucl. Sci. Technol. 21, 558 (1984).
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