Materials Chemistry and Physics 59 (1999) 139±142

Densi®cation behavior and mechanical properties of pressureless-sintered

silicon carbide ceramics with alumina and yttria additions
J.H. She*, K. Ueno
Department of Energy Conversion, Osaka National Research Institute, Midorigaoka 1-8-31, Ikeda, Osaka 563-8577, Japan

Received 23 November 1998; received in revised form 8 January 1999; accepted 12 January 1999

Abstract

SiC powders were pressureless sintered to about 98% of the theoretical density by using 10 wt.% (Al2O3 ‡ Y2O3) as sintering additives.
The densi®cation mechanism was attributed to liquid-phase sintering due to the formation of a eutectic liquid between Al2O3 and Y2O3 at
sintering temperatures. SEM observation revealed that SiC exhibited a uniformly distributed ®ne-grained microstructure and a highly
intergranular fracture behavior. The maximum values of strength and toughness were up to 625 MPa and 7.5 MPa m1/2, respectively. The
improved toughness is considered to be mainly associated with the de¯ection of cracks along interphase boundaries due to a weak interface
as well as with the introduction of microcracks at the interface between SiC grains and the secondary phases due to a residual tensile stress
from thermal expansion mismatch. # 1999 Elsevier Science S.A. All rights reserved.

Keywords: Silicon carbide; Pressureless sintering; Mechanical properties; Residual stress; Interface; Microcrack

1. Introduction In the present work, the effects of Y2O3 contents in the

Pressureless sintering has been considered as the most
attractive manufacturing technology to obtain ceramic com-
ponents with complex shapes, volume production, and low
cost. In the early 1970s, pressureless-sintered SiC ceramics
were successfully developed by Prochazka [1], who found
that small additions of boron and carbon can drastically
enhance the densi®cation of SiC via a solid-state sintering
mechanism. However, the applications of this boron- and
carbon-doped SiC have been seriously limited by its low
mechanical properties and high sintering temperatures.
In order to improve the mechanical properties and lower
the sintering temperatures of pressureless-sintered SiC cera-
mics, many investigations have been focused on a variety of
other sintering additives over the past few years. Recently, it
has been shown [2±7] that either a- or b-SiC powders may
be pressureless-sintered to high density with the addition of
Al2O3 and Y2O3 at a relatively low temperature of
1850  20008C. The sintering mechanism in this system
is considered to be attributed to liquid-phase sintering via the
formation of a eutectic liquid between Al2O3 and Y2O3.
When compared with boron- and carbon-doped SiC, Al2O3-
and Y2O3-doped SiC exhibits a notably improved strength
and toughness.
*Corresponding author.
(Al2O3 ‡ Y2O3) additives on the densi®cation behavior and
mechanical properties of pressureless-sintered a-SiC cera-
mics are investigated and discussed.
2. Experimental procedure
The starting materials used in this experiment were a-
SiC, Al2O3 and Y2O3 powders, which have an average
particle size of 0.6, 0.5 and 0.8 mm, respectively. The
chemical composition of the a-SiC powder in wt.% was
Si (total) 69.35, Si (free) 0.22, C (total) 29.98, C (free) 0.37,
O (total) 0.42, Al2O3 0.18 and Fe2O3 0.12. To investigate the
in¯uences of Y2O3 contents in the (Al2O3 ‡ Y2O3) additives
on the densi®cation behavior and mechanical properties of
a-SiC, four compositions were made by keeping the total
amount of Al2O3 and Y2O3 at 10 wt.%. The theoretical
densities of these compositions were calculated according
to the rule of mixtures and are given in Table 1.
SiC powders and the (Al2O3 ‡ Y2O3) additives were
mixed in ethanol using high-purity a-SiC milling media.
After drying in air at 708C for about 8 h and sieving through
a 75-mesh screen, the powder mixtures were uniaxially
pressed into rectangular specimens of 45 mm
 8 mm  6.5 mm at 3 MPa in a carbon steel die. Subse-
quently, these green bodies were compacted in a cold

0254-0584/99/$ ± see front matter # 1999 Elsevier Science S.A. All rights reserved.
PII: S 0 2 5 4 - 0 5 8 4 ( 9 9 ) 0 0 0 3 9 - 5
140 J.H. She, K. Ueno / Materials Chemistry and Physics 59 (1999) 139±142
Table 1
Theoretical densities of SiC-10 wt.% (Al2O3 ‡ Y2O3)
Content of Y2O3 in Al2O3 ‡ Y2O3 (wt.%) Theoretical density (g/cm3)
25.0 3.2846
37.5 3.2907
50.0 3.2969
62.5 3.3031
isostatic press at 200 MPa, and sintered in a tightly-threaded
graphite crucible that was placed in a graphite resistance
furnace. Sintering was conducted in a ¯owing argon atmo-
sphere at a heating and cooling rate of 108C/min. Four
different sintering temperatures of 18508C, 19008C, 19508C
and 20008C were chosen, and the holding time was 1 h.
Dimensions and weights of all individual specimens
before and after sintering were determined to calculate
linear shrinkages and weight losses. Densities of the sin-
tered specimens were measured by a conventional water-
displacement method. Phase analysis was performed by
X-ray diffractometry (XRD) with Cu Ka radiation. Flexural
strength was measured by three-point bending tests with a
30 mm span at a cross-head speed of 0.5 mm/min. Fracture
toughness was determined using the single edge notch beam
(SENB) method with a notch width of 0.25 mm and a
support span of 20 mm. The microstructure of fracture
surfaces and polished surfaces was observed by scanning
electron microscopy (SEM).
3. Results and discussion
Fig. 1 presents the sintered densities of SiC-10 wt.%
(Al2O3 ‡ Y2O3) ceramics with different Y2O3 contents.
As shown, the highest densities were achieved at Y2O3
contents between 25 and 50 wt.% of the total additives. This
characteristic is quite important in conventional production
of sintered SiC ceramics, because it reduces the sensitivity
of properties to composition. Furthermore, X-ray diffraction
analysis revealed that these specimens were composed
primarily of a-SiC, Al2O3 and 3Y2O3
5Al2O3 (yttrium-
Fig. 1. Relative density as a function of Y2O3 content for SiC-10 wt.%
(Al2O3 ‡ Y2O3) ceramics sintered at 18508C (triangles), 19008C (circles),
19508C (diamonds) and 20008C (squares).
aluminum garnet, YAG). Thus, the formation of Al2O3-
YAG eutectic liquid should be responsible for the densi®ca-
tion of SiC ceramics. Since the eutectic temperature of
Al2O3-YAG liquid phase is approximately 17608C [8], it
is possible to obtain maximum sintered densities at tem-
peratures as low as 18508C. In this work, a high density up to
96.8% was attained for SiC-10 wt.% (Al2O3 ‡ Y2O3) cera-
mics at 18508C when the relative content of Y2O3 to
(Al2O3 ‡ Y2O3) was 37.5 wt.%. It must be pointed out that
the presence of SiO2 on the surface of SiC powders may
further enhance densi®cation through liquid-phase sinter-
ing, because it can decrease the melting point of Al2O3-YAG
eutectic phase and increase the amount of liquid [9].
On the other hand, it can be seen in Fig. 1 that sintered
densities deceased sharply when the content of Y2O3 in
(Al2O3 ‡ Y2O3) was 62.5 wt.%. According to the equili-
brium phase diagram [8] between Al2O3 and Y2O3, this
additive may form a eutectic liquid phase between
3Y2O3
5Al2O3 and 2Y2O3
Al2O3. Due to a relatively high
eutectic temperature of 3Y2O3
5Al2O3-2Y2O3
Al2O3 than
Al2O3-3Y2O3
5Al2O3, SiC grains cannot be fully wetted by
liquid phase, and thus the solution-precipitation process of
SiC in the liquid phase is inhibited, resulting in the
decreases in sintered density.
Fig. 2 shows the variation of sintering shrinkage with
Y2O3 addition for SiC containing 10 wt.% (Al2O3 ‡ Y2O3).
As expected, the dependence of sintering shrinkage on Y2O3
content correlates well with that of sintered density. How-
ever, the change of shrinkage with temperature is not fully
correlative to that of density. At 20008C, maximum shrink-
age values reached but the highest densities were not
achieved. This is believed to be mainly associated with
some reactions between SiC and additives. The most pos-
sible and important reactions are [4]
SiC s† ‡ Al2 O3 s† ! SiO g† ‡ Al2 O g† ‡ CO g† (1)
SiC s† ‡ 2Y2 O3 s† ! SiO g† ‡ 4YO g† ‡ CO g† (2)
The escape of gaseous reactants (SiO, Al2O, YO and CO)
during sintering may result in the formation of `new' pores
and thus the decrease in sintered density. Since high tem-
Fig. 2. Linear shrinkage as a function of Y2O3 content for SiC-10 wt.%
(Al2O3 ‡ Y2O3) ceramics sintered at 18508C (triangles), 19008C (circles),
19508C (diamonds) and 20008C (squares).
 J.H. She, K. Ueno / Materials Chemistry and Physics 59 (1999) 139±142
Fig. 3. Weight loss as a function of Y2O3 content for SiC-10 wt.%
(Al2O3 ‡ Y2O3) ceramics sintered at 18508C (triangles), 19008C (circles),
19508C (diamonds) and 20008C (squares).
peratures may enhance the evaporation of liquid phases and
the reactions between SiC and additives, maximum densi-
ties were not obtained at 20008C, where the sintering
shrinkage reached highest values.
During sintering, the volatilization of liquid phases as
well as the reactions between SiC and additives may also
cause the loss of weight. As shown in Fig. 3, the weight loss
of SiC-10 wt.% (Al2O3 ‡ Y2O3) ceramics increases with
increasing temperature. In addition, it can be seen in Fig. 3
that the weight loss is higher at lower Y2O3 contents, i.e.,
Al2O3-rich compositions have higher weight loss than
Y2O3-rich compositions.
Fig. 4 shows the fracture surfaces of SiC-10 wt.%
(Al2O3‡Y2O3) ceramics with different Y2O3 contents.
For the specimen with 25 wt.% Y2O3 in the additives, many
Fig. 4. Fracture surfaces of SiC-10 wt.% (Al2O3‡Y2O3) ceramics with
(A) 25 wt.% and (B) 62.5 wt.% Y2O3 in the additives.
141
Fig. 5. Flexural strength as a function of Y2O3 content for SiC-10 wt.%
(Al2O3 ‡ Y2O3) ceramics sintered at 19008C (circles), 19508C (dia-
monds) and 20008C (squares).
droplets can be seen on the surface of SiC grains due to a
relatively high amount of Al2O3, which is easy to volatilize
at high temperatures. In contrast, SiC-10 wt.%
(Al2O3 ‡ Y2O3) ceramic with 62.5 wt.% Y2O3 in the addi-
tives exhibited a `clean' surface. This phenomenon suggests
that an excessive addition of Al2O3 is needed to suppress the
evaporation of Al2O3 and therefore obtain high sintered
densities. As shown in Fig. 1, the sintered densities
increased with increasing Al2O3 addition.
The ¯exural strength of SiC-10 wt.% (Al2O3‡Y2O3)
ceramics is illustrated in Fig. 5 as a function of Y2O3
content. Over the whole range of Y2O3 contents, the
strengths were in excess of 500 MPa, which is at the upper
limit of boron- and carbon-doped SiC. Especially at a
sintering temperature of 19508C, a high strength up to
625 MPa was achieved for SiC-10 wt.% (Al2O3 ‡ Y2O3)
ceramics with 25 wt.% Y2O3 in the additives. This should be
attributed to a relatively homogeneous microstructure with-
out large abnormal grains, which may act as ¯aw origins. In
addition, the strength of SiC-10 wt.% (Al2O3 ‡ Y2O3) cera-
mics decreased with increasing Y2O3 content. The decrease
in strength is estimated to result from the increase in residual
pores, i.e., the decrease in sintered density. As can be seen in
Fig. 1, the sintered density decreased with increasing Y2O3
content.
It has been reported [10] that the fracture mode in boron-
and carbon-doped SiC is predominantly transgranular. How-
ever, it is interesting to note in Fig. 6 that SiC-10 wt.%
(Al2O3 ‡ Y2O3) ceramics exhibited a highly intergranular
fracture behavior. This phenomenon is considered to be
related to the characteristics of secondary phases. As shown
in Fig. 6, the secondary phase is primarily located as a
continuous ®lm at the grain boundaries. Since the major part
of the intergranular phase was YAG, which has a larger
thermal expansion coef®cient than SiC, a residual tensile
stress would be generated at the interface between SiC and
YAG upon cooling down from sintering temperatures. The
existence of such a stress may weaken the interphase
boundaries, leading to intergranular fracture.
Fig. 7 shows the fracture toughness of SiC-10 wt.%
(Al2O3 ‡ Y2O3) ceramics as a function of Y2O3 content.
142 J.H. She, K. Ueno / Materials Chemistry and Physics 59 (1999) 139±142
Fig. 6. SEM micrograph of a fracture surface for SiC-10 wt.%
(Al2O3 ‡ Y2O3) ceramics sintered at 19508C with 37.5 wt.% Y2O3 in
the additives.
When compared with boron- and carbon-doped SiC, Al2O3-
and Y2O3-doped SiC exhibited much higher toughness
values. Especially, a high fracture toughness in excess of
7.5 MPa m1/2 was attained for SiC-10 wt.% (Al2O3 ‡
Y2O3) ceramics sintered at 20008C with 37.5±50 wt.%
Y2O3 in the additives. The notably improved toughness is
considered to be mainly associated with the crack de¯ection
process. It can be seen in Fig. 8 that SiC-10 wt.%
(Al2O3 ‡ Y2O3) ceramics showed signi®cant crack de¯ec-
tion along interphase boundaries due to a weak interface. On
the other hand, the residual tensile stresses at the interface
between SiC and YAG, which were induced on cooling after
sintering, may result in microcracking at the SiC/YAG
interface ahead of a primary propagating crack. These
microcracks dissipate the strain energy and shield the main
crack, leading to the increase in fracture toughness.
Additionally, it can be seen in Fig. 7 that the toughness of
SiC-10 wt.% (Al2O3 ‡ Y2O3) ceramics increased with
increased sintering temperature. This phenomenon is con-
sidered to be related to the coarsening of SiC grains at a
relatively high sintering temperature, because an exagger-
ated grain may enhance the crack bridging and branching,
leading to the increase in fracture toughness.
Fig. 7. Fracture toughness as a function of Y2O3 content for SiC-10 wt.%
(Al2O3 ‡ Y2O3) ceramics sintered at 19008C (circles), 19508C (dia-
monds) and 20008C (squares).
Fig. 8. SEM micrograph of Vickers indentation cracks in SiC-10 wt.%
(Al2O3 ‡ Y2O3) ceramics sintered at 19508C with 37.5 wt.% Y2O3 in the
additives.
4. Conclusion
SiC ceramics with an addition of 10 wt.%
(Al2O3 ‡ Y2O3) were investigated by pressureless sintering
to determine the effects of Y2O3 content and sintering
temperature on the densi®cation behavior and mechanical
properties. A high sintered density up to 98% was achieved
at a sintering temperature of 19508C for SiC-10 wt.%
(Al2O3 ‡ Y2O3) with Y2O3 contents between 25 and
50 wt.% of the total additives. This is considered to be
attributed to the formation of a eutectic liquid between
Al2O3 and Y2O3 at sintering temperatures. Owing to a
homogeneous microstructure without exaggerated grains,
a high strength of about 625 MPa was achieved. SEM
observation revealed that SiC-10 wt.% (Al2O3 ‡ Y2O3)
ceramics showed a highly intergranular fracture behavior
due to a residual tensile stress at the interface between SiC
grains and the secondary phases. On the other hand, SiC
exhibited signi®cant crack de¯ection along interphase
boundaries. As a result, a high toughness in excess of
7.5 MPa m1/2 was attained.
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