J O U R N A L OF M A T E R I A L S S C I E N C E L E T T E R S 15 ( 1 9 9 6 ) 282 284
High temperature strength and oxidation behaviour of Er2Si207-Si3N4
ceramics
HEON-JIN CHOI, YOUNG-WOOK KIM, JUNE-GUNN LEE
Division of Ceramics, Korea Institute of Science and Technology, RO. Box 131 Cheongryang, Seoul, Korea
Silicon nitride (Si3N4) is a difficult material to sinter
because of the covalent nature of its bond. There-
fore, various sintering additives have been investi-
gated to promote ,liquid phase sintering. It is well
known that glassy phases always remained at the
grain boundary of Si3N4 due to liquid phase
sintering [1, 2]. Many observations have shown that
the sintering additives determine the characteristics
of the grain boundary, which influences high-
temperature properties such as high-temperature
flexural strength, creep property, and oxidation
resistance [3-6].
Work by Lange et al. [7] on the system Si3N4-
SIO2-Y203 has shown that the high-temperature
properties of Si3N4 can be improved by choosing the
compositions in the Si3N4-Si2N20-Y2Si207 com-
patibility triangle since Si2N20 and Y2Si207 phases
are in equilibrium with SiO2, the oxidation product
of Si3N4. On this basis, various RE203 (RE = cation
of rare-earth oxide) has been studied as sintering
additives since it is expected that the systems Si3N4-
SiO2-RE203 will exhibit similar behaviour [3, 8]. It
has also been reported that the high-temperature
properties of Si3N4 could be improved by adding
RE203 due to formation of RE2Si207 and Si2N20 as
well as highly refractory grain boundary glassy
phases [4, 5].
Among RE203, Er203 could be considered as one
of the most suitable additives for improving the
high-temperature properties of Si3N4 ceramics be-
cause the eutectic temperature of the Er203-SiO2
binary system is the highest (1680 °C) among the
RE203 SiOz binary systems [9], and because of the
good oxidation resistance of ErzSi2Oy-Si3N4 cera-
mics [5].
This letter reports the high-temperature strength
and oxidation resistance of hot-pressed ErzSizO7-
Si3N4 ceramics. For comparison, YzSi2OT-Si3N4
ceramics were also fabricated and their high-tem-
perature strength and oxidation resistance measured.
Commercially available Si3N4 powder (SN E-10,
Ube Industries, Tokyo, Japan) was mixed with SiQ
(99.9%, Aerosil 200, Degussa Corp., NJ, America)
and Er203 (99.9%, Johnson Matthey, Seabrook, NH,
America) and milled in methanol using Si3N4
milling media. The molar ratio of SiO2:Er203
(taking into account the SiQ content in Si3N4
powder as 2.6wt%) was kept as 2:1, which
corresponds to the ErzSi207 Si3N4 tie line. The
slurry was dried, sieved through a 60 mesh screen,
282
and hot-pressed at 1820 °C for 2 h with 25 MPa of
applied pressure under nitrogen atmosphere. Two
batches with different amount of additives (8 and
16vo1%) were prepared. Y2Si207-Si3N4 ceramics
containing 8 and 16 vol% of additives were also
prepared using the same procedures.
Densities were measured by the Archimedes
method. Theoretical densities were calculated based
on the rule of mixtures. Sintered samples were cut
into 3 × 2.5 × 20 mm bars and polished using an
800 grit diamond wheel. Three-point flexural
strengths were measured at room temperature and
1200 °C. The span for three-point bending was
15mm. The 18 × 18 × 2.5mm samples were cut
and polished for oxidation. The samples were placed
on platinum wire in a box furnace and heated to
1400 °C at a heating rate of 450 °C/h and then kept
for 192 h in air. The furnace was cooled and heated
at 12-72 h intervals to measure the weight change of
samples.
X-ray diffraction (XRD) of the samples showed/3-
Si3N4 as a major phase and Er2Si207 or Y2Si207 as
a minor phase, as expected. All samples showed
sintered densities higher than 99.8% of theoretical
density. Typical morphology of the microstructure
and grain size of each samples were similar, as
shown in Fig. 1. Flexural strengths of sintered
samples at room temperature and 1200 °C are shown
in Table I. The Er2Si207-Si3N4 ceramics showed
higher high-temperature strength than the Y2Si207-
Si3N4 ceramics with the same amount of additives.
The Er2Si207-Si3N4 ceramics also showed higher
retention of room-temperature strength and better
oxidation resistance than the Y2Si207-Si3N4 cera-
mics.
Fig. 2 shows the relation between the square of the
weight gain and oxidation time of sintered samples
at 1400°C. Oxidation behaviour of the sintered
samples obeyed a parabolic rate law as follows:
w 2 = kt (1)
where W is the weight gain per unit surface area, k is
the rate constant of parabolic oxidation, and t is the
exposure time. Parabolic behaviour of the Er2SizO7-
Si3N4 and YzSi2OT-Si3N4 ceramics indicates that
the rate-controlling step in the oxidation process is a
diffusional process, associated with the migration of
cations of additives and impurities along residual
grain boundary glassy phases to the interface
between ceramics and surface oxide [5].
0261-8028 © 1996 Chapman & Hall
Figure 1 Scanning electron micrographs of the polished and etched surfaces: (a) Y2Si207-Si3N4 ceramics with 8 vol % of additives; (b) Y2Si207-
Si3N4 ceramics with 16 vol % of additives; (c) Er2Si207-Si3N4 ceramics with 8 vol % of additives; and (d) Er2Si207-Si3N4 ceramics with 16 vol%
of additives.

TABLE I Room- and high-temperature strengths and weight gains of Er;Si207-Si3N4 and
Y2Si2OT-Si3N4 ceramics
Amount of Flexural strength Retention of room- Weight gain
additives temperature strength at 1400 °C
(vol%) room temperature/ at 1200 °C for 192 h
1200 °C (MPa) (%) (mg/cm2)

Er2Si207 8 1113 -+ 92/812 -+ 82 73.0 0.439

-Si3N4 16 1216 -+ 80/968 -+ 81 79.6 0.242
ceramics

Y2Si207 8 1112 -+ 132/771 +- 89 69.3 0.486

-Si3N4 16 1095 -+ 73/622 + 51 56.8 0.323
ceramics

High-temperature strength and oxidation resistance
of liquid phase sintered Si3N4 are mainly influenced
by the refractoriness of the grain boundary glassy
phases [3-6, 10]. The relationship between high-
temperature properties and the eutectic temperature
of a RE203-SiO2 binary system has also been
reported [4, 5]. Therefore, the present results indicate
that the high strength at 1200 °C and good oxidation
resistance at 1400 °C of the Er2Si207-Si3N4 cera-
mics might be attributed to the formation of highly
refractory grain boundary glassy phases.
Grain boundary glassy phases of Si3N4 ceramics
have a SiO2 glass structure, which contains nitrogen,
cations of the oxide additives, and impurities [11].
The properties of oxide additive-containing SiO2
glass are dominated by the strength of bond between
the cation and neighbouring anions, and the strength
of bond is proportional to the ionic charge and
reciprocal of the ionic radius. A study of SiO2
glasses containing RE203 showed that the bond
between the cation of RE203 and the surrounding
oxygen ion is the weakest link in the glass structure
since the additive cation radius is the largest [12].
The high-temperature properties of glass are be-
lieved to be determined by the weakest bond.
Therefore, the stability of glass might be increased
at high temperature by decreasing the cationic radius
of RE203. The grain boundary glassy phases in
RE2Si207-Si3N4 ceramics are expected to show
similar behaviour to glass because the basic structure
283
 0.25 I ' I ' I ' is higher than that of the Y203-SIO2 binary system
(1660 °C).
It can be summarized that the high strength at
1200 °C and good oxidation resistance at 1400 °C of
0.20 ErzSizO7-Si3N4 ceramics are due to the formation of
highly refractory grain boundary glassy phases, and
ErzO3 could be considered as a suitable sintering
additive for improving the high-temperature proper-
E
0.15 ties of Si3N4 ceramics.
%
g

.~ 0.10
0.05
0 . 0 0 , ~
0 50 100
Time (h)
Figure 2 Parabolic plot of specific weight gains as a function of time
at 1400 °C: [] Y2Si2Ov-Si3N4, 8 vol%; C)YzSi2Ov-Si3N4, 16 vol %;
/k Er2Si207-Si3N4, 8 vol%; V Er2SizOT-Si3N4, 16 vol%.
and structure role of constituent ions are the same.
Therefore, more highly refractory grain boundary
glassy phases could be expected in ErzSizOy-Si3N4
ceramics than in YzSizO7-Si3N4 ceramics since the
cationic radius of Er203 (0.1004 nm) is smaller than
Y203 (0.1011 nm). Furthermore, the eutectic tem-
perature of the Er203-SiO2 binary system (1680 °C)
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Received 9 August
and accepted 18 September 1995

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