ZrO2 CaO SiO2 systems

Calcia stabilized zirconia (CSZ) is destabilized by Al2O3, SiO2 and TiO2 at elevated
temperatures. The product of destabilization, termed partially destabilized zirconia (PDZ)
has been found to possess excellent resistance to thermal shock. The thermomechanical
properties of PDZ depend, to a great extent, on the degree of destabilization which is the
amount (in weight percent) of free ZrO2 formed as a consequence of the destabilization
reaction. PDZ is produced by the reaction of CSZ with oxides such as alumina, silica and
titania at high temperatures.
The extent of destabilization depends on various factors like the amount and nature of the
destabilizer, the reaction (sintering) temperature and time.

The destabilization of magnesia-stabilized zirconia may occur if the zirconia body is held
for a period of time in the temperature range 1,650° to 2,550° F. What is more important,
however, is that the destabilization may occur tothe zirconia body during a use in which
the body is exposed on many occasions for a relatively short time (maybe 2-3 hours) on
each occasion, i.e., cycled through the 1,650°-2,550° F. range. This temperature cycling
is typical oftreatment afforded die nibs, setter plates, crucibles, metal pouring nozzles,
heat exchangers, and grinding beads, among many other products formed of stabilized
zirconia.

there is provided a transformation-toughened zirconia body consisting essentially of

zirconia containing greater than 2 mole percent yttria and sintering aid means for
lowering the necessary sintering temperature of the body. The sintering aid means
consists essentially of a mixture of calcia, alumina, and silica. The body has a fine-grain
microstructure and a high sintered density.

The other cause of thermal stress in the zirconia body at all temperatures is the stress
caused by rapid temperature changes which result in thermal gradients within the body.
The magnitude of these stresses in the body and their effect on the strength are
determined in part by the coefficient of thermal expansion of the material. These two
causes of internal stress (structural transformation and thermal expansion) generally
require narrow limits on the amount of stabilizer in the batch. Primarily, the stabilizer is a
desirable addition which brings about stabilization of ZrO2 into the cubic or tetragonal
structure. Secondarily, the stabilizer also brings about an increase in the thermal
expansion coefficient of the composition.

The strong affinity of silica and calcia for each other, the affinity of zirconia and calcia,
and the lack of solubility of silica in CsaChs are factors which are important in the
formation of the intermediate layer.

The presence of silicon and calcium in pores at the junction suggests the formation of a
liquid phase.
Phase diagram of Zirconia calcia silica systems in crystallization of
glass.

A variety of liquid
phases can occur between silica and calcia around 1450-1550°C depending on the
composition and may explain why 1450°C is a critical temperature for bonding.
This is an attractive explanation because a liquid phase would relax stresses due to
differential shrinkage and then could provide bonding on cooling.

PDZ has been found to possess excellent resistance to damage by thermal shock [6]. This
superior thermal shock resistance of the material is a direct consequence of the
destabilization reaction which has a marked influence on the microstructure of the
product.
The presence of free zirconia and the phase transitions it undergoes during thermal
cycling are the principal factors responsible for the improved thermal shock resistance of
PDZ.
The presence of free zirconia and the phase transitions it undergoes during thermal
cycling are the principal factors responsible for the improved thermal shock resistance of
PDZ. The phase inversion from the monoclinic phase to the tetragonal phase in the
contributes to the improved thermal shock behaviour.

The phase composition of PDZ is essentially the same as that of PSZ. As in the case of
PSZ, the presence of free zirconia and the phase transitions it undergoes during thermal
cycling are the factors responsible for the excellent thermal shock resistance of the
material.

fully stabilized will mean substantially fully cubic zirconia, partially stabilized will mean
a stable body made up of cubic and monoclinic zirconia and tetrastabilized will mean a
stable body made up of tetragonal zirconia (at least about 5% by volume) with less than
10% cubic and with any remainder being monoclinic.