Materials Science and Engineering A 527 (2010) 5400–5404

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Materials Science and Engineering A

journal homepage: www.elsevier.com/locate/msea

The high temperature strength of SiC ceramics based on SiO2 nano-colloidal

employed
Ki Woo Nam a,∗ , Jong Soon Kim b , Seung Won Park c,1
a
Pukyong National University, Materials Science and Engineering, 100 Yongdang-dong, Nam-gu, Busan, 608-739, Republic of Korea
b
NGE Tech, 1545-5 Songjeong-dong, Gangseo-gu, Busan, 618-818, Republic of Korea
c
Graduate School, Pukyong National University, Busan, 608-739, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: This study was carried out on the crack-healing behavior of two types of SiC ceramics based on a SiO2
Received 17 February 2010 additive, and mainly on the high temperature strength of crack-healed specimens. The mean particle sizes
Received in revised form 12 April 2010 of the SiC, Al2 O3 and Y2 O3 powders used in this study were 0.27 ␮m, 0.1 ␮m and 33 nm, respectively.
Accepted 20 May 2010
The SiO2 employed was a nano-colloidal (SiO2 12% solid solution). The SiC ceramics were prepared using
a mixture of 85 or 90 wt.%. SiC powder and sintering additives (Al2 O3 :Y2 O3 = 6:4 and SiO2 = 0 or 3 wt.%).
The mixtures were subsequently hot-pressed in N2 gas for 1 h via hot-pressing conducted under 35 MPa
Keywords:
at 2053 K. In both specimens, the optimized crack-healing condition was 1373 K for 1 h in air. The crack-
Crack-healing
High temperature strength
healing material of the crack part was the glassy phase of SiO2 by oxidation reaction of SiC and O2 .
Sintering additive The limiting temperatures for bending strength of smooth and crack-healed specimens of two types of
SiC ceramics specimens of SAY and SAYS were 1373 K and 1273 K, respectively. That is, the crack-healed specimens
SiO2 nano-colloidal had good high temperature strength in spite of the fact that the crack-healing material is the glassy phase
of SiO2 .
© 2010 Elsevier B.V. All rights reserved.

1. Introduction 2. Experiment

Ceramic materials have mechanical properties superior to metal
at high temperatures. However, they are very brittle and suscepti-
ble to cracks. As a result, the structural reliability is very low, and
the application in engineering has been limited. To overcome this
weakness, crack-healing of ceramics is a very useful method with
many advantages. Previous investigation has shown that silicon
carbide (SiC) ceramics have a very good crack-healing ability [1–7].
In addition, SiC has very good mechanical properties at high tem-
peratures with corrosion and radioactivity resistance. As a result,
SiC ceramics are one of the leading candidates for high tempera-
ture structural application, such as future generation gas turbines
and the inner containment of nuclear fusion reactors, etc. [8,9]. SiC
has a high potential for crack-healing; however, very few studies
have been conducted on its crack-healing behavior according to
sintering additive.
Therefore, this study focuses on the crack-healing behaviors of
two kinds of SiC ceramics based on SiO2 additive, and mainly on
the high temperature strength of crack-healed specimens.
∗ Corresponding author. Tel.: +82 51 629 6358; fax: +82 51 629 6353.
E-mail address: namkw@pknu.ac.kr (K.W. Nam).
1
Present address: Graduate School of Energy Science, Kyoto University,
Kyoto, 606-8501, Japan.
Two kinds of hot-pressed SiC ceramics with different sintering
additives were used in this study. The details of materials used are
as follows: the mean particle sizes of the SiC (Ibiden Co., Japan),
Al2 O3 (Sumitomo Chemical Co., Japan) and Y2 O3 (CI Chemical Co.,
Japan) powders used in this study were 0.27 ␮m, 0.1 ␮m and 33 nm,
respectively. The SiO2 employed was a nano-colloidal (SiO2 12%
solid solution, NGE Tech, Korea), not nano-powder. This was used
as an additive because SiO2 nano-colloidal is much cheaper than
SiO2 nano-powder with the same properties.
Table 1 shows the batch compositions. The SiC ceramics were
prepared using a mixture of 85 or 90 wt.%. SiC powder and sintering
additives (Al2 O3 :Y2 O3 = 6:4 and SiO2 = 0 or 3 wt.%). Each batch was
milled in isopropanol for 24 h using a Si3 N4 ball (␸5). The mixture
was placed in a 363 K furnace to extract solvent and to make a
dry powder mixture. The dry powder was then passed through a
106 ␮m sieve. The mixtures were subsequently hot-pressed in N2
gas for 1 h via hot-pressing conducted under 35 MPa at 2053 K.
The sintered plate was cut into test specimens measuring
3 mm × 4 mm × 18 mm. A semi-elliptical surface crack of about
125 ␮m in surface length was introduced at the center of the ten-
sile surface of the specimens with a Vickers indenter, using a load of
24.5 N. To evaluate the effect of crack-healing temperature on the
bending strength, the polished and cracked specimens were heated
at various temperatures ranging from 1173 K to 1573 K for 1 h. Cool-

0921-5093/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2010.05.055
 K.W. Nam et al. / Materials Science and Engineering A 527 (2010) 5400–5404
Table 1
Batch compositions of specimen (wt.%).
Specimen SiC Sintering additive
Al2 O3
SAY 90 6 4
SAYS 85 7.2
Fig. 1. Effect of healing temperature on the strength of crack-healed specimen.
ing was spontaneous in the furnace. The heat-treated specimen was
subsequently tested in three-point bending at a crosshead speed of
0.5 mm/min, using a fixture with a span of 16 mm. After testing,
all specimens were inspected to identify fracture origin by optical
microscope. To know the softening temperature of the intergranu-
lar phase in each material, high temperature bending strength was
measured at temperatures ranging from 1073 K to 1473 K in air,
after a dwell time of 10 min at the testing temperature. To investi-
gate the mechanism of crack-healing, the specimen surfaces were
analyzed by EPMA (electron probe microanalysis) and EDX (energy
dispersed X-ray) line analysis by FESEM and X-ray diffraction.
3. Test results and discussion
3.1. Effect of crack-healing temperature on the bending strength
Fig. 1 shows the bending strength of two types of specimens
that have been crack-healed for 1 h at various temperatures from
1173 K to 1573 K. The average strengths of smooth specimens were
674 MPa for SAY and 720 MPa for SAYS. The average strengths
Fig. 2. SEM images of the SAYS specimen surface (a) before and (b) after healing.
5401
Relative density (%)
Y2 O3 SiO2
0 98.3
4.8 3 98.9
of heat-treated smooth specimens were 1320 MPa for SAY and
1466 MPa for SAYS. In case of specimens using a SiO2 additive, both
strengths are higher than those of a SiO2 non-employed specimen.
This is because the liquid phase is generated at a lower temperature
in the case of using a SiO2 additive, and this results in much denser
microstructure. This is also consistent with the results of density
as shown in Table 1. On the other hand, the strength of the cracked
specimens was shown to be about half of the smooth strength.
After healing from 1173 K to 1573 K, the specimen recovered to the
strength similar to that of the smooth specimens, and in most cases
surpassed it. Based on the room temperature strength and smooth
heat-treated strength, the optimum healing temperature of cracked
specimens was found to be 1373 K for all specimens. It is similar
in strength to the heat-treated smooth specimen. The strengths
of the specimen healed at 1373 K represented a 200% increase
in the strengths of the smooth specimen non-healed because of
re-sintering and healing of surface cracks from machining and pol-
ishing etc by action of SiO2 additive, and this indicates that these
specimens with SiO2 additive have superior crack-healing ability.
However, the sintering additive for crack-healing had nothing to
do with whether SiO2 was employed.
3.2. Crack-healing mechanism
As a result of the strength test after crack-healing at various
temperatures, it was revealed that SiC ceramics have a good crack-
healing ability and that crack-healing is complete at the optimum
crack-healing temperature of 1373 K. Fig. 2 shows the image of the
SAYS specimen surface after crack-healing at 1373 K for 1 h. It was
covered with certain kinds of materials and the Vickers indentation
crack was not seen.
To identify the crack-healing material, EPMA, FESEM (EDX) and
XRD analysis were conducted. Fig. 3 shows elemental mapping
images of Si, O and C on the SAYS specimen surface by EPMA. In
the case of the crack-non-healed specimen, a large amount of Si, C
and little O was detected. However, on the crack-healed specimen
at 1373 K for 1 h, a large amount of Si, O and little C was detected.
Thus, it was assumed that Si-oxide was produced on the surface by
the crack-healing treatment.
5402 K.W. Nam et al. / Materials Science and Engineering A 527 (2010) 5400–5404
Fig. 3. The elemental mapping of the SAYS specimen surface before and after healing
by EPMA.
To investigate crack-healing material in detail, EDX analysis on
crack part of the SAYS specimen was conducted as shown in Fig. 4.
Fig. 4(a) is the crack-non-healed specimen, and Fig. 4(b) is crack-
healed specimen at 1173 K for 1 h. Intensity of cracked specimen
has little O and 70 Si on crack. But, crack-healed specimen has 23
Fig. 4. EDX line analysis on crack of the SAYS specimen before and after crack-healing. (a) Crack-non-healed specimen and (b) crack-healed specimen at 1173 K for 1 h.
O and 90 Si. That is, the crack-healed specimen abounds in oxygen
content. Silicon content was also increased by crack-healing pro-
cess. These results indicate that crack-healing material is silica and
oxygen. There is no doubt that the silica was produced by the oxi-
dation of silicon carbide. The SAY and SAYS specimen had the same
healing material, but that of the SAYS specimen had a little more
than SAY specimen.
The SiO2 has two phases: a glassy and a crystal phase. To inves-
tigate the crack-healing phase of SiO2 , XRD analysis was conducted
with crack-healing time increased. These results are shown in Fig. 5,
that is, (a) is crack-non-healed specimen, (b) is crack-healed speci-
men at 1373 K for 1 h, (c) is crack-healed specimen at 1373 K for 3 h
and (d) is crack-healed specimen at 1373 K for 10 h. As the crack-
healing time increased from 1 h to 3 h, the crystal phase of SiO2
also increased. This indicates that this SiC ceramic recovered its
bending strength through the glassy phase of SiO2 . However, in
case of the crack-healed specimen for 10 h, the SiO2 was reduced. It
was assumed that SiO2 was evaporated with the crack-healing time
increased or made Y2 Si2 O7 crystal by reaction with SiC and Y2 O3
[11,12]. The crack-healing reaction of this specimen was estimated
 K.W. Nam et al. / Materials Science and Engineering A 527 (2010) 5400–5404 5403

Fig. 5. Results of X-ray diffraction from the SAYS specimen surfaces: (a) crack-non-healed specimen, (b) crack-healed specimen at 1373 K for 1 h, (c) crack-healed specimen
at 1373 K for 3 h and (d) crack-healed specimen at 1373 K for 10 h.

as follows: the smooth specimens and the crack-healed specimens of SAY and
SAYS exhibited a high bending strength up to 1373 K and 1273 K,
SiC(s) + O2 (g) → 3SiO2 (s) + CO2 (CO)(g) respectively. These results indicate that crack-healed specimens
have a very good high temperature strength property. Therefore,
the limiting temperature for bending strength of SAY specimens is
SiC(s) + SiO2 (s) + Y 2 O3 (s) + 4O2 (g) about 100 K higher than the SAYS specimen. This seemed to be the
effect of an amount of sintering additive SiO2 . An amount of additive
→ Y 2 Si2 O7 (s) + CO2 (CO)(g)
SiO2 remained at the glassy phase at grain boundaries after sinter-
ing, and it seemed to be the weak point as temperature increased.
(5/2)Al2 O3 (s) + (3/2)Y 2 O3 (s) → Al5 Y 3 O12 (s) As a result, the additive SiO2 was able to densify SiC ceramics.
However, this seems to have a negative effect on high tempera-
SiC(s) + 2SiO2 (s) → 3SiO(g) + CO(g) ture strength. The symbol (*) indicates a crack initiated outside of
the crack-healed zone.
Fig. 7 shows the effect of testing temperature on the bend-
3.3. Effect of the test temperature on the bending strength of the
ing strength of crack-healed structural ceramics [1,10]. Monolithic
crack-healed specimen
SiC shows a very low limiting temperature for bending strength
(873 K). However, the SiC ceramics developed in this study
Fig. 6 shows the effect of test temperature on the bending
exhibited very high limiting temperature property even though
strength of a crack-healed specimen. The smooth specimen was
crack-healing material is the glassy phase of SiO2 .
also investigated for the sake of comparison. As shown in Fig. 6,

Fig. 7. Effect of testing temperature on the bending strength of crack-healed struc-

Fig. 6. Effect of testing temperature on bending strength of crack-healed specimen. tural ceramics.
5404 K.W. Nam et al. / Materials Science and Engineering A 527 (2010) 5400–5404
4. Conclusion
This study was carried out on the crack-healing behavior of two
types of SiC ceramics based on a SiO2 additive, and mainly on the
high temperature strength of crack-healed specimens. The main
conclusions obtained were as follows:
(1) In both specimens, the optimized crack-healing condition was
1373 K for 1 h in air.
(2) The crack-healing material of the crack part was the glassy
phase of SiO2 by oxidation reaction of SiC and O2 . The SiO2
additive has contributed re-sintering and healing of surface
cracks from machining and polishing etc by action of SiO2
additive.
(3) The limiting temperatures for bending strength of smooth and
crack-healed specimens of two types of SAY and SAYS specimen
were 1373 K and 1273 K, respectively. That is, the crack-healed
specimens had good high temperature strength in spite of
the fact that the crack-healing material is the glassy phase of
SiO2 .
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