Glass and Ceramics Vol. 52, Nos.

l - 2 , 1995

Science for Ceramics M a n u f a c t u r e

UDC 666.3:535.345.1.002.2

PRODUCTION OF TRANSPARENT CERAMICS (REVIEW)

A. V. B e l y a k o v a and A. N. S u k h o z h a k ~

Translated from Steklo i Keramika, Nos. 1 - 2, pp. 14 - 20, January - February, 1995.

A phenomenological description of the processes occurring at different stages of manufacturing transparent

ceramics from preparing the powder to firing is given from the standpoint of the irreversible and nonequili-
brium processes developed by Prigogine and his school. Principles for choosing compacting additions and
techniques which impede powder aggregation and local compaction in drying and firing, and the formation
of closed intercrystalline and intracrystalline pores in sintering are considered.

Transparent ceramics (transparent polycrystalline materi-
als) have a lower transmittance than monocrystals, but are
more heat resistant and sometimes even stronger. This makes
them a less expensive material, especially when the articles
have complex shapes [1, 2], and explains the growing interest
in such materials.
To be transparent, the ceramic should be poreless and
have optically perfect crystal boundaries and crystals. The
surface of a pore is a boundary between phases with sharply
different optical properties, and therefore, it intensely reflects
and refracts light. A large number of pores makes ceramics
opaque. Pores may be intercrystalline or intracrystalline. The
elimination of intracrystalline pores, even if they are submi-
cron in size, is a much longer process than elimination of
closed intercrystalline pores. Intercrystalline pores occur at
crystal boundaries which are sinks of vacancies, and this
makes their removal easier.
Intracrystalline pores may acquire equilibrium faceting
[3], which makes their removal more difficult. The impurities
that form a gaseous phase during heat treatment and create
excessive pressure inside closed pores also preserve the in-
tracrystalline porosity. Compacting additions are concen-
trated on the surface of the pores and accelerate the diffusion
processes that lead to their equilibrium faceting.
An elevated concentration of the compacting additive,
i.e., magnesium oxide, was found on the surface of the resid-
ual closed pores of translucent ceramics from aluminum ox-
ide [4]. Magnesium oxide has a much h i ~ e r saturated vapor
pressure than aluminum oxide, and therefore, when fired in
oxygen, the former creates excessive pressure in the pores. In
the process of transformation of hydroxides into oxides and
burning of the temporary technological binder from oxide ce-
D. I. Mendeleev Russian Chemical Technological University, Moscow,
Russia.
ramics, water vapor, nitrogen, and carbon can penetrate
closed pores. This makes closed pores the most dangerous
factor in production of transparent ceramics. In this connec-
tion, the prerequisites for their appearance should be ex-
cluded at all manufacturing stages.
Crystal boundaries should be thin and optically perfect.
The presence of a second phase on the crystal boundaries
which has different optical properties from the main crystal-
line phase leads to reflection and refraction of light and
makes the ceramic less transparent. For this reason, transpar-
ent ceramics are obtained from raw materials of h i ~ purity
and the amount of additive is chosen so that they completely
dissolve in the solid solution with the main phase.
The crystals in ceramics should be optically perfect. The
main requirement is the absence of optical defects, namely,
pores, inclusions of the second solid phase, aggregate
boundaries, and dislocations. In ceramics from optically an-
isotropic crystals (crystal systems other than cubic), an addi-
tional scattering of liglat arises on the boundaries because of
their arbitrary crystallographic orientation [1]. Some investi-
gators think that the size of crystals in transparent ceramics
should be minimal in order to reduce the probability that
pores will be captured by growing crystals and to shorten the
diffusion path for removal of intracrystalline pores [2]. How-
ever, this increases the lengh of the boundaries and thus the
light scattering on them.
These considerations lead us to the requirements to be
observed by manufacturers of transparent ceramics. It is nec-
essary to exclude at all manufacturing stages the causes of
the formation of intracrystalline pores and evolution of the
second phase on crystal boundaries and inside crystals.
Transparent ceramics are commonly produced with the
use of special compacting additives [5]. The additives accel-
erate diffusion processes, ensure removal of intracrystalline
and intercrystalline pores, and improve the structure of crys-

14
0361-7610/95/0102-0014512.50 9 1995 Plenum PuNishing Corporation
Production of Transparent Ceramics
tal boundaries and crystals. The amount of additives is cho-
sen so that they will not evolve as a new solid phase, but will
enter the solid solution together with the main crystalline
phase. In other words, the concentration of the additive
should be less than its ultimate solubility in the main phase at
the firing temperature.
The additives should impede crystal growth, i.e., slow
down movement of their boundaries [6, 7]. In this case, the
probability that a pore will be separated from the boundary
and transformed into an intracrystalline pore is reduced.
Moreover, the additives should accelerate surface diffusion
and thus stimulate elimination of pores situated along crystal
boundaries.
The additives are chosen using defect formation reac-
tions [8, 9]. Let us consi'der the principles for choosing addi-
tives for production of transparent ceramics frofn oxides. If
diffusion in crystals occurs by the mechanism of vacancies,
which is typical for oxides, the vacancies should be both in
the cation sublattice (metal sublattice) and in the oxygen
sublattice. At sintering temperatures, oxygen is more volatile
in oxides than in metals. As a result, oxygen vacancies Vo"
are formed in the oxygen sublattice, especially in boundary
layers of the crystal, i.e.,
MeO --+ Me~e + Vo" + I/2 0 2 + 2e'. (1)
An increase in the concentration of oxygen vacancies
[Vo"] in accordance with Eq. (3) leads to a reduction in the
concentration of vacancies in the cation sublattice by [V~e]
the Schottky equation
MeO
0 V 'e+ VO" ; (2)
<. = [Vo3, (3)
where K,. is the equilibrium constant in the formation of a
Schottky defect.
Thus we have a deficit of Vs
In complex compounds
such as oxides, diffusion is intensified if the number of va-
cancies is sufficient in both sublattices. Since there are suffi-
cient oxygen vacancies, the additive should stimulate the ap-
pearance of cation vacancies. For example, in order to inten-
sify diffusion in mag-nesium oxide, we can use additives of
scandium oxide or zirconium dioxide
MgO
Sc203 > 2SCMg- 30~ + [/M'g "
M,~O
ZrO 2 _2.~ Zr~g + 2 0 6 + VMg.
When possible, isovalent additives that form a wide
-spectrum of solid solutions with the main phase can be used
15
efficiently [9]; e.g., an additive of gadolinium oxide to pro-
duce transparent ceramics from yttrium oxide [1 O]
Y2~
Gd203 ----+ (4)
In both sublattices, vacancies emerge due to tensile
stresses caused by the difference in the radii of gadolinium
and yttrium ions. Therefore, a coefficient k << 1 is intro-
duced into reaction (4). On contrast to Schottky defects
0 Y203 2 Vy" + 3 Vo
reaction (4) is dependent not only on the temperature but also
on the concentration of the additive. It is easier to introduce
the additive in large amounts.
For a correct choice of the additive, we should know
what kind of defect is formed in the crystal in heating and
what mechanism is responsible for diffusion processes. The
diffusion mechanism can change during heating, for exam-
ple, vacancy diffusion may change into an internodal diffu-
sion [9]. It should be taken into account that at the initial sin-
tering stages, the additive may be present as an individual
phase through which the main diffusion flow occurs, whereas
in the final sintering stages it is transformed into a solid solu-
tion [5]. The additives should decrease the anisotropy of
crystal growth and make the crystal shape more isometric.
Otherwise, anisotropy o f crystal growth will lead to the ap-
pearance of tensile forces in the ceramics, which causes the
appearance of closed intercrystalline porosity.
In firing, the gas medium affects the reactions of defect
formation in the ceramics and hence affects the sintering
process. Brauer diagrams [8, 9, 11] give a visual picture of
the effect of the partial pressure of the components of the gas
medium on defect formation reactions. The correctness of the
diagrams can be proved by plotting the dependence of a de-
fect-sensitive property, for example, electrical conductivity,
on the partial pressure of the volatile component in logarith-
mic coordinates. Transparent ceramics are usually fired in a
vacuum, hydrogen, or gaseous medium which forms anions
in compounds. The anions are usually a volatile component.
Oxide ceramics are fired in oxygen, nitride ceramics in nitro-
gen, fluoride ceramics in fluorine, and so on. If we use other
gaseous media, they will penetrate the intracrystalline and
closed intercrystalline pores and impede their removal.
Gases consisting of the same atoms as the anions of the
main phase reduce the volatility of the anions in reactions of
defect formation that are analogous to (1) and (2) and the
concentration of vacancies in the anion sublattice. Such me-
dia require smaller amounts of additives for compensating
the perturbed Schottky equilibrium (Eq. (3)). In additive, the
diffusion coefficient of these gases in regions close to crystal
boundaries is rather high because these regions are enriched
by anion vacancies (reaction (1)). This stimulates the elimi-