Sintering-viscosity relation for mixed-alkali glass

powder compacts
Ki-Dong Kima)
Rheinisch-Westfdlische Technische Hochschule (RWTH), lnstitut fur Gesteinshiittenkunde,
Mauerstr. 5, D-52064 Aachen, Germany
(Received 13 June 1994; accepted 1 November 1994)
The sintering of glass powder compacts was studied by dilatometer in the (25 - x)
Na 2 O-xK 2 O-75SiO2 glass system. The dilatometrically determined sintering temperature
(r sin ) at constant heating rate decreases and the shrinkage at isothermal sintering
increases when Na 2 O is replaced by K 2 O up to the mole fraction of K 2 0 / ( N a 2 0 +
K2O) = 0.5. This is due to the decrease in viscosity and means that sintering can be
possibly accelerated by introduction of mixed alkali oxides in this system. According
to calculation using the VFT-equation, the viscosity value at r sin is almost independent
of glass composition. From these results it may be supposed that the dilatometrically
determined sintering begin temperature (Tsia) can be a characteristic point for the
sintering of glass.

I. INTRODUCTION mercially frequently used alkali oxides such as Na 2 O

In the last several years the preparation of glass by
sintering has received attention because of its advantages
compared with the conventional melting technology. The
sintering takes place at considerably lower temperature
than melting1 and gives a possibility for the manufacture
of glass phase contained composites2-3 or porous sin-
tered glasses and glass ceramics for the biotechnology.4
According to sintering theories,5'6 the sintering of glass
powders and amorphous powders proceeds by viscous
flow; this has been already experimentally supported by
many works.7"10 The viscosity is thus the decisive factor
for sintering of glass.
However, there is no denned viscosity fixed point
for sintering of glass. According to recent studies10"12
on the relationship between liquidus line and sintering
temperature of glass in binary eutectic systems, the so-
called minimal sintering temperature of glass powder
compacts decreases with a decrease of their liquidus
temperature and lies always between transformation and
the softening point of glass. On the basis of these results,
the concept of sintering aid material in glasses was
introduced. A sintering aid material must be selected as
a constituent of glass which improves the sintering; in
other words, it decreases the viscosity without bad effects
on the desired properties of glass. From the viewpoint of
the sintering aid, mixed alkali glasses exhibit interesting
characteristics. At an intermediate mixed-alkali compo-
sition, the glasses show not only a viscosity minimum,
particularly in the silicate systems13"15 containing com-
a)
Present address: Samsung-Corning Co., R&D Center, 445-970 Su-
won, Korea.
and K 2 O, but also improved properties, for example,
chemical durability and electrical resistance due to the
mixed alkali effect.16
In the present work the influence of mixed alkali
oxide on the sintering of glass powder compacts was
studied in the Na 2 O-K 2 O-SiO 2 system with 25 mol %
as total alkali content, and the correlation between the
observed results and the viscosity was discussed.
II. EXPERIMENTAL PROCEDURE
Mixed alkali glasses of mol % composition (25 - x)
Na 2 O-xK 2 O-75SiO 2 with x = 0, 6.25, and 12.5, in
which the K 2 0 / ( N a 2 0 + K2O) mole fraction takes the
value of 0, 0.25, and 0.5, were examined in this study.
All of the glasses studied lie beyond the composition
range for the metastable phase separation.17 The starting
materials, high purity quartz sand, commercial reagent
grade Na 2 CO 3 and K 2 CO 3 , were mixed thoroughly and
melted in a Pt5Au crucible at temperatures between 1450
and 1550 °C in an electric furnace, depending on the
given composition. Sufficient time (4-6 h) was allowed
for the melts to become visibly homogeneous. Wet
chemical analysis of the prepared glasses was carried out
to examine the possible compositional changes during
melting. The results indicate a deviation from batch
composition of less than 1 mol % of alkali oxide.
For the sintering experiment the glass was powdered
by crushing and grinding in a mechanical agate and
separated into the fraction of 120 - 100 /am by sieving.
A small amount of polyvinyl alcohol (5 wt. % solution)
was used as a temporary binder for the powder com-
pact. The glass powder was cold-uniaxially pressed at
135 MPa into a cylindrical compact (6 mm in diameter

1846 J. Mater. Res., Vol. 10, No. 7, Jul 1995 © 1995 Materials Research Society
 K-D. Kim: Sintering-viscosity relation for mixed-alkali glass powder compacts
and 25 mm in length). After drying at 120 °C, the
green densities were 0.7 ± 0.02 of theoreticals. Sintering
investigations were carried out in a calibrated vertical-
type dilatometer. One part of the investigation was
performed at a constant heating rate (5 K/min) and
the other isothermal at a constant temperature. The
specimens were heated in a tube furnace under a slightly
flowing oxygen atmosphere. Their length changes were
continuously measured. The relative linear shrinkage (%)
was calculated from the length changes.
The two viscosity fixed points, transformation point
(Tg, 7] = 10 133 dPas) and softening point (Ts, rj =
IQ7.6 j p a s ) ; w e r e measured by using dilatometer (Netz
Co., DIN 52324) and fiber extension method (ASTM
C338), respectively. The viscosities at high temperature,
especially the working point (Tw, 77 = 104 dPas), were
also determined by the rotating viscometer (Haake Co.,
DIN 53018) calibrated using DGG (Deutsche Glastech-
nische Gesellschaft) standard glass I.
III. RESULTS AND DISCUSSION
Shrinkage curves during constant rate of heating of
the three glasses are shown in Fig. 1. All the curves
show a typical shrinkage shape for the amorphous
compact. 1(M2 At the first stage negligible shrinkage
occurs, but after passing through a certain temperature
the shrinkage shows a steep increase. The minimal
sintering temperature (r sin ) at which the sintering begins
can be determined by the tangent line at the curve. It lies
approximately at 500 °C for the specimen with x = 0
and is higher than those of the mixed alkali containing
specimens (=460 °C for x = 6.25 and =440 °C for
x = 12.5). From those results it can be expected that
a decrease of sintering temperature is possible by the
introduction of mixed alkali oxides.
-0.5
100 200 300 400 500 600
Temperature (°C)
FIG. 1. Dilatometric shrinkage curves of (25 - x) Na 2 O-xK 2 O-
75SiO2 glasses with x = 0, 6.25, and 12.5 mol% at a heating rate
of 5 K/min.
J. Mater. Res., Vol. 10, No. 7, Jul 1995
30 60 90 120 150
Time (min)
FIG. 2. Isothermal dilatometric shrinkage curves of (25 — x) Na 2 O-
xK2O-75SiO2 glasses with x = 0, 6.25, and 12.5 mol% at 500 "C.
Figure 2 shows the shrinkage of three glasses in
dependence on sintering time at r sin (500 °C) corre-
sponding to the single alkali glass (x = 0). At the first
stage of sintering, the dependence of shrinkage on the
sintering time shows a good linearity, but with increasing
time the second stage of sintering due to glass particle
collapse takes place only in mixed alkali containing
specimens. This is more clearly observed in glass with
x = 12.5. The shrinkage at 120 min sintering time is
2.7% for x = 0, 9.7% for x = 6.25, and 19% for
x = 12.5. These results for shrinkage indicate a good
agreement with the tendency of sintering temperature
in Fig. 1.
Tg, r sin , and Ts of three glasses are given in Table I.
The dependence of these points on K 2 O content (x) is
presented in Fig. 3. r sin of each glass lies between Tg
and Ts, corresponding to glass, namely in viscosity range
10 1 3 3 -10 7 6 dPas. The behavior of 7 sin in Fig. 3 is the
same as that of Tg and Ts with replacement of Na 2 O
by K2O. The lower sintering temperature and the higher
shrinkage of mixed alkali glasses (Fig. 1 and Fig. 2) may
be due to their lower viscosity. According to studies that
investigated the effect of mixed alkali oxide on viscosity
at low temperature, 1314 the viscosity begins to increase if
the mole fraction of K 2 O/(Na2O + K2O) becomes more
than 0.5. Therefore, it may be expected that the sintering
temperature should also increase under the condition of
K 2 0 / ( N a 2 0 + K2O) > 0.5, or K 2 O > 12.5 mol % in
this case.
Although a viscosity minimum has been founded
in several mixed alkali glass systems.16 it is generally
agreed that the "mixed alkali effect" should be reserved
for properties relating to alkali ion mobility. In viscosity
that is not direct dependent on ionic transport, another
mechanism must be considered.15 The viscous flow
occurs via the movement of structure units, for example
1847
 K-D. Kim; Sintering-viscosity relation for mixed-alkali glass powder compacts

TABLE I. Two viscosity fixed points (Tg and Ts) and the sintering TABLE II. Three constants (A, B, and To) of the VFT equation in
begin temperature (r s i n ) of mixed alkali glasses, (25 - x) N a 2 O - the viscosity range 1 0 4 - 1 0 1 3 3 dPas and calculated viscosity values
x K 2 0 - 7 5 S i 0 2 , with x = 0, 6.25, and 12.5. corresponding to Tsin.

x (mol % of K 2 O) Tsm Ts VFT equation

0 473 500 626 x (mol % of A B To log 17 (in dPa s) at

6.25 437 460 606 K 2 O) * sin
12.5 424 440 600
0 -0.413 2949.2 257.9 11.8
6.25 -0.804 3514.7 187.8 12.1
12.5 -0.830 3678.0 163.7 12.5
Soda lime -2.868 5611.9 197.9 11.3
650 silicate
glass9
Borosilicate -2.087 7452.6 45.65 10.5
glassb
Quartz glass0 -2.49 15004 253 12.1
a
7 s i n = 595 °C.
b
7 s i n = 640 °C.
T s i n = 1280 °C.

that the dilatometrically determined sintering begin tem-

perature (7Sjn) has a constant viscosity value as same
as the transformation temperature, and hence can be a
characteristic point for the sintering of glass. However,
further experimental works are needed to investigate the
dependence of r sin on the heating rate, the particle size
400 of powder, and the green density of powder compact, as
12.5 well as the weight force applied by the detection rod of
dilatometer onto the specimen.
FIG. 3. Tg, r S i n , and r , in dependence of x in (25 - x) N a 2 O -
zK 2 O-75SiO 2 glasses.

100
SiO4, while the ion mobility takes place through the site
exchange between ions. According to the work of Sakka
and Mackenzie,18 it seems that liquidus temperature
plays an important role in determining the transformation
temperature (Tg) of glasses. The phase diagram19 corre-
sponding to the glasses studied in the present work also
shows a minimum of liquidus temperature in the vicinity
of K 2 0/(Na 2 0 + K2O) = 0.5. It is postulated that the
liquidus curve is latent in the viscosity characteristics of
glasses.
In order to express the temperature dependence
of the viscosity, the Vogel-Fulcher-Tammann (VFT)
equation, log r\ = A + B/(T — To), was used. The con-
stants A, B, and TQ of this equation were calculated
from Tg, Ts, and Tw. In Table II the three constants
corresponding to glass and viscosity values of each r sin
calculated using this equation are given, respectively.
In this table the results of several commercial glasses 400 600 800 1000 1200
(soda lime silicate, borosilicate, and quartz glasses)12 are Temperature (°C)
also presented. Figure 4 shows the relationship between
FIG. 4. Viscosity values (log 77) at Tsin of (25 - x) N a 2 O -
log 77 and Tsin. All the calculated viscosity values (17) xK 2 O-75SiO 2 glasses and three commercial glasses. ( • ) x = 0,
at r sin lie near at 10''~12 dPas, irrespective of glass (•) x = 6.25, (A) x = 12.5, ( • ) soda lime silicate glass, ( • )
composition. From these results it may be supposed borosilicate glass, and (O) quartz glass.

1848 J. Mater. Res., Vol. 10, No. 7, Jul 1995

 K-D. Kim: Sintering-viscosity relation for mixed-alkali glass powder compacts
ACKNOWLEDGMENTS
The author gratefully acknowledges the valuable
discussion of Professor G. Ondracek in Institut fuer
Gesteinshuettenkunde of RWTH Aachen and thanks the
Katholischer Akademischer Auslaender-Dienst (KAAD)
for their financial help.
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