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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Shrinkage and exural strength improvement of silica-based

composites for ceramic cores by colloidal alumina inltration
Young-Hwan Kim a,b, Jeong-gu Yeo a,n, Sung-Churl Choi b,n
a
b

Advanced Materials and Devices Laboratory, Korea Institute of Energy Research, 152 Gajeong-ro, Yuseong-gu, Daejeon 34129, Republic of Korea
Division of Materials Science and Engineering, Hanyang University, 222 Wangsimni-ro, Seongdong-gu, Seoul 04763, Republic of Korea

art ic l e i nf o

a b s t r a c t

Article history:
Received 5 January 2016
Received in revised form
16 February 2016
Accepted 23 February 2016

The effects of colloidal alumina inltration on porous silica-based composites for complex designed
ceramic cores were investigated. The specimens pre-sintered at 1100 C for 2 h were immersed into
colloidal alumina and were sintered at 1300 C for 2 h. Inltrated alumina particles were coagulated on
the surface of fused silica via their opposite electrical charges in the inltrating solution. The inltrated
alumina was reacted with the surface of fused silica, and mullite was formed thereafter. The shrinkage
and microcracking induced by surface crystallization of fused silica to cristobalite was prevented by
mullitization. As a result, the formation of mullite by alumina inltration for 150 min dramatically improved the exural strength (3.3 MPa to 9.6 MPa) and reduced the linear shrinkage (2% to 1%) of the
silica-based composites. However, longer inltration time over 150 min has no signicant effects on
exural strength and linear shrinkage.
& 2016 Published by Elsevier Ltd.

Keywords:
Fused silica
Colloidal alumina
Inltration
Flexural strength
Shrinkage

1. Introduction
Complex designed ceramic cores fabricated by injection
molding have been widely used to form internal cooling passages
in hollow gas turbine blades [13]. During investment casting of
the gas turbine blades, the ceramic core undergoes thermal stress
at high temperature. Ceramic cores have been manufactured using
a mixture of ceramic powders based on fused silica (SiO2) and
zircon (ZrSiO4) due to their excellent high temperature properties,
such as thermal shock resistance and chemical inertness against
molten metal [4]. Fused silica is mainly used to produce refractory
materials, as well as ceramic cores, because of its low thermal
expansion coefcient (0.55
10  6 K  1 between 25 C and
1000 C) and excellent chemical inertness against molten metal. To
provide optimal exural strength for enduring severe circumstances during investment casting, high temperature sintering is
required to manufacture the ceramic cores [5]. However, high
sintering temperature (Z 1300 C) leads to crystallization of fused
silica to cristobalite, thereby inducing shrinkage and microcracking of the ceramic cores. Volume contraction during - to -phase
transformation of cristobalite leads to shrinkage of the silica-based
ceramic cores. In addition, microcracks formed by volume contraction of cristobalite decrease the exural strength of ceramic
n

Corresponding authors.
E-mail addresses: jgyeo@kier.re.kr (J.-g. Yeo),
choi0505@hanyang.ac.kr (S.-C. Choi).

cores [6,7]. Consequently, the existence of cristobalite causes dimensional inaccuracy and deteriorative strength on silica-based
ceramic cores. Many studies have investigated the effect of cristobalite on mechanical properties of silica-based ceramics
[2,810]. Huseby et al. studied the shrinkage of silica-based composites with various compositions [1]. Their report indicated that
the volume contraction of cristobalite during its phase transformation leads to shrinkage on silica-based composites. In addition,
Breneman et al. investigated the effect of cristobalite phase on the
exural strength of fused silica [6]. They reported that the cristobalite improved exural strength of fused silica based ceramics at
350 C because of the existence of cristobalite for the -phase.
However, the exural strength at room temperature was reduced
due to microcracks formed by - to -phase transformation of
cristobalite. These results demonstrate that the cristobalite in silica-based ceramics gives rise to a decrease of exural strength and
an increase of the amount of shrinkage.
However, the cristobalite necessarily occurs at high sintering
temperature. Therefore, in the present study, colloidal alumina
was inltrated into a silica-based ceramic core to inhibit crystallization of fused silica for improvement of the exural strength
with low shrinkage. The inltration technique is a convenient
additional process applicable to the manufacturing of the ceramic
core. Preventing the crystallization of cristobalite through convenient alumina inltrating process ahead of sintering step denitely leads to minimization of its shrinkage and reduction of
the number of microcracks [9]. The present study is aimed at
improving the exural strength and reducing the amount of

http://dx.doi.org/10.1016/j.ceramint.2016.02.137
0272-8842/& 2016 Published by Elsevier Ltd.

Please cite this article as: Y.-H. Kim, et al., Shrinkage and exural strength improvement of silica-based composites for ceramic cores by
colloidal alumina inltration, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.02.137i

Y.-H. Kim et al. / Ceramics International ()

Fig. 1. SEM (1) and EDX mapping (2) images of (a) non-inltrated, (b) 30 min inltrated, and (c) 210 min inltrated specimens after drying.

shrinkage via inltration of colloidal alumina into silica-based

composites for complex ceramic cores.

2. Material and methods

Porous silica-based specimens for alumina inltration were
prepared using ceramic injection molding. The feedstocks for injection molding were composed of 63.75 wt% of fused silica
(amorphous SiO2, 325 mesh, Imerys, United States), 21.25 wt% of
zircon (ZrSiO4, 1 m, Cenotec, Korea) and 15 wt% of thermoplastic
binders (parafn wax, microcrystalline wax, stearic acid and oleic
acid). The ceramic powders of fused silica and zircon our were
ball milled for 6 hours at room temperature using a 6-mm diameter zirconia ball. After ball milling, the ceramic powders and
thermoplastic binders were mixed at 80 C for 6 h under vacuum
condition to produce the feedstocks.
The green bodies with dimensions of 6 mm
8 mm
90 mm
according to ASTM C1161-13 were injection molded using a
C-frame ceramic injection molding machine (CTM-CI-CF-35100HT, Cleveland Tools and Machines, United States) with a
nozzle temperature of 80 C, a ow rate of 400 cc/s and an injection pressure of 60 bar. After a slow heating step (0.2 K/min) to
burn out the thermoplastic binders, the specimens were presintered at 1100 C for 2 h with heating rate of 5 K/min using box
furnace (UAF-15-27-LHE, Lenton, England). During pre-sintering,
the specimens were positioned in alumina crucible with fused
silica backll powders. The measured apparent porosity and
linear shrinkage of pre-sintered specimen were 30.1% and 0.6%,
respectively.
The pre-sintered specimens were inltrated by colloidal alumina suspension (Aluminum oxide, 20% in H2O, colloidal dispersion, 50 nm, Alfa-aesar) with various inltration times of 30 min to
300 min under vacuum condition. For evaporation of solvent, the
inltrated specimens were dried at 110 C for 5 h. The dried specimen was sintered at 1300 C for 2 h, along with pre-sintered
(non-inltrated) specimen for comparison.
The dimensional change and inltrated alumina content of

specimens were measured after sintering.Field-emission scanning

electron microscopy (FE-SEM, S-4800, Hitachi, Japan) and EDX
mapping (Link Pentafet, Oxford) were used to identify the microstructures and alumina inltration of each specimen. The
exural strength of the specimens was measured through a
3-point bending test using a universal testing machine (UTM,
H10SK, Hounseeld, England) with span size of 80 mm and
crosshead speed of 1.0 mm/min. The crystallization of fused silica
to cristobalite and the existence of alumina and mullite were
analyzed using a X-ray diffractometer (XRD, D/Max-2200, Rigaku,
Japan) using Cu K radiation ( 1.54178 ). In addition, EDX line
analysis (Link Pentafet, Oxford) was used to determine the existence of mullite on the surface of fused silica and the residual
alumina in the specimens.

3. Results and discussion

It is well-known that the isoelectric point (IEP) of fused silica
and alumina are pH 2 and pH 9, respectively [1116]. In the range
of pH 2 to pH 9, fused silica has a negative electrical charge,
whereas alumina exhibits a positive electrical charge [17]. It is well
known that the IEP of alumina particle is near pH 9.0. However,
the colloidal alumina used in this study is alumina dispersed
suspension, and the described pH on the specication is 4.0. In this
study, the measured pH of the colloidal alumina solution was 3.92.
The fused silica and alumina were attracted each other via their
opposite electrical charges. Because fused silica had been long
necked via pre-sintering at 1100 C, alumina powder was coagulated onto the fused silica. The alumina powder already coagulated
onto the fused silica via electrical attraction force, therefore, it can
remain on the specimen after the solvent was pulled out via
drying after inltration [17]. EDX analysis data demonstrated the
existence of inltrated alumina in the specimens (Fig. 1). No aluminum peak was observed in the non-inltrated specimen (Fig. 1
(a)). In contrast, aluminum was detected in the inltrated specimens (Fig. 1(b) and (c)). The EDX data indicates that the alumina
coagulated homogeneously in silica-based porous specimen via

Please cite this article as: Y.-H. Kim, et al., Shrinkage and exural strength improvement of silica-based composites for ceramic cores by
colloidal alumina inltration, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.02.137i

Y.-H. Kim et al. / Ceramics International ()

Fig. 2. Inltrated alumina content and apparent porosity as a function of inltration time.

Fig. 3. XRD patterns of the sintered specimens as a variation of inltration time (:

zircon, : cristobalite, : alumina, : mullite).

inltration, exclusive of the fractured large fused silica particles

(black area). In addition, the result shows that the increase of the
alumina content depends on the inltration time.
The content of alumina (qth) on silica-based porous composites
while the pores were lled completely with the colloidal alumina
is calculated using the following equation [17].

qth=1+c

100 P
P

)( ) (
1
1w

1
a

100 ti
w ti

c is the pre-sintered silica-based composite density (2.51 g/cm3),

P is the apparent porosity of the pre-sintered specimen (30.1%), w
is the weight loss of the dried colloidal alumina between 110 C
and 1100 C (w 0.3), ti is the weight percent of alumina in the
colloidal suspension (20 wt%), and a and w are the density of
alumina (3.95 g/cm3) and liquid (1.00 g/cm3), respectively. The
weight loss of the dried colloidal alumina was measured using a
thermogravity/differential thermal analyzer (TG/DTA, SDT 2960
Simultaneous, TA instruments, United States). The dispersant was
completely eliminated at 500 C and weight of inltrated specimen did not change at a temperature range of 500 C to 1300 C.
The calculated content of inltrated alumina using the above
equation is 2.54%. The measured content of alumina and the apparent porosity of specimens are shown in Fig. 2. The alumina
content in the specimen continually increased with inltration
time. The alumina content reached near the calculated value
(2.54%) in the specimen inltrated for 150 min. The apparent
porosity reduces gradually with an increase of the inltration time.
The change rate of alumina content and the apparent porosity
start decreasing after 210 min. The increasing concentration of
alumina in the specimen observed in the saturated state at
150 min shows that most of the fused silica was coagulated with
alumina. Therefore, the inltrated alumina after 150 min of inltration time appeared to be coagulated alumina that is already
attached with silica.
As shown in Fig. 3, X-ray diffraction analysis revealed the phase
transformation of fused silica on silica-based composites for alumina inltration after sintering at 1300 C. All specimens contain
zircon (JCPDS 6-266) and cristobalite (JCPDS 39-1425) phases. The
cristobalite is formed by crystallization of fused silica at a temperature above 1300 C [1,2]. Due to a low content of alumina
(0.7%), the XRD pattern of the specimens inltrated for 30 and
90 min contain only zircon and cristobalite. Alternatively, the respective mullite peaks (JCPDS 15-0776) are found in the specimens

Fig. 4. Flexural strength (s3pt) and linear shrinkage (L/L0) as a function of inltration time.

inltrated above 150 min because the ne alumina particles coagulated on fused silica were transformed into mullite during sintering at 1300 C, according to the following reaction [1820]:
3Al2O3 2SiO2-3Al2O32SiO2 (Al6Si2O13)
In particular, the specimen inltrated for 210 min shows the existence of alumina (JCPDS 46-1212) as well as mullite. This result
reveals the existence of unreacted excessive alumina in the
specimen.
Fig. 4 shows the exural strength and the linear shrinkage of
the specimens. The existence of cristobalite has a decisive effect on
the shrinkage and exural strength of silica-based composites
because of its phase transformation [6,21,22]. As cristobalite
changes from - to -phase, it contracts 5 vol%; accordingly, microcracks are formed [23]. The volume contraction during the
phase change of cristobalite accompanied with microcracking
caused a reduction of the exural strength of the silica-based
ceramics [24]. Therefore, compared with inltrated specimens, the
lower exural strength and higher amount of shrinkage of noninltrated specimen (3.3 MPa and 2%, respectively) are caused by
volume contraction via phase transformation of cristobalite.
The formation of mullite via alumina inltration on the silicabased composites leads to exural strength enhancement and

Please cite this article as: Y.-H. Kim, et al., Shrinkage and exural strength improvement of silica-based composites for ceramic cores by
colloidal alumina inltration, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.02.137i

Y.-H. Kim et al. / Ceramics International ()

Table 1
The peak ratio of cristobalite to zircon of specimens with inltration time.
Inltration time

Cristobalite/Zircon peak ratio

0 min (non-inltrated)
30 min
90 min
150 min
210 min

1.081
0.880
0.692
0.501
0.491

reduction of the amount of linear shrinkage. As shown in Fig. 4,

the exural strength is gradually improved up to 10 MPa until
150 min of inltration time. It is considered that the exural
strength is enhanced by formation of mullite (i.e., mullitization).
However, no signicant changes are revealed on the exural
strength of the specimen inltrated above 210 min. This result
shows the mullitization of fused silica surface specically affect
the exural strength.
The mullitization by alumina inltration can prevent crystallization to cristobalite and the resulting generation of microcracks.
In this study, the inltrated alumina on the surface of fused silica
became mullite instead of undergoing surface crystallization to
produce cristobalite. Table 1 shows the main peak ratio of cristobalite (21.68, corresponding to (110) plane) to the zircon (26.86,
corresponding to (200) plane) in the XRD patterns of the specimens. It is possible to assume that the relative degree of crystallization of fused silica in specimens by comparing the main peak
intensity between cristobalite and zircon because all specimens
have same content of zircon [7,9]. In addition, zircon does not
react with fused silica or alumina at temperatures under 1600 C
[25,26]. As shown in Table 1, the relative content of cristobalite
reduces with the increase of inltrating time (or alumina content).
The exural strength (Fig. 4) and crystallization rate of cristobalite
(Table 1) are consistent with the behavior that mullitization via
alumina coagulated on fused silica inhibits surface crystallization,
thereby increasing the exural strength of silica-based ceramics. In
addition, the change of the crystallization rate reduces relative to

the specimen inltrated for 150 min, following the trend of the
alumina content. This result is related to the content of inltrated
alumina in the specimens because the excessive alumina does not
affect the mullitization.
Changes of the shrinkage with inltrating time showed exactly
the opposite tendency with that of the exural strength. The
shrinkage of a specimen is decreased in half with the inltrating
time of 150 min. However, the shrinkage does not change when
the specimen has excessive residual alumina; nor does the exural
strength. Consequently, mullitization on the surface of fused silica
via alumina inltration leads to exural strength enhancement
and shrinkage restraint due to inhibition of the crystallization of
fused silica.
Fig. 5 shows that the mullitization effect of reducing microcracks is accompanied by phase transformation of cristobalite.
Many microcracks are shown in the microstructure of the noninltrated specimen (Fig. 5(a)). In spite of the alumina inltration,
the specimen inltrated for 30 min still exhibits microcracks on
fused silica (Fig. 5(b)), whereas the specimens inltrated for over
150 min do not indicate microcracks (Fig. 5(c) and (d)). In addition,
the existence of alumina (or mullite) particles on fused silica is
revealed on the specimens inltrated for greater than 150 min.
These results demonstrate the inhibition effect of microcrack
generation by inltration of alumina in silica-based composites.
Based on high resolution SEM and EDX measurements of the
specimens, it was established that the mullitization occurred on
surface of silica. Fig. 6 shows the microstructures of the specimen
inltrated for 150 min. Although the alumina was not revealed in
the XRD patterns of the specimen, the excessive unreacted alumina is found in its microstructures. It is considered that the
content of residual alumina is too low to detect using the X-ray
diffractometer. As shown in EDX result, three zones (alumina,
mullite and silica) are developed between coagulated alumina and
fused silica, as shown in the SEM image of Fig. 6. The EDX analysis
data shows the mullite was formed on the surface of fused silica
due to the reaction between coagulated alumina and fused silica.
In addition, excessive alumina formed in the alumina zone. These

Fig. 5. The SEM images of the sintered specimens with various inltration time; (a) 0 min (non-inltrated), (b) 30 min, (c) 150 min, and (d) 210 min.

Please cite this article as: Y.-H. Kim, et al., Shrinkage and exural strength improvement of silica-based composites for ceramic cores by
colloidal alumina inltration, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.02.137i

Y.-H. Kim et al. / Ceramics International ()

Fig. 6. SEM and EDX analysis results of the specimen inltrated for 210 min.

results demonstrate that the alumina inltration leads to mullitization on the surface of fused silica instead of the crystallization to
cristobalite that is accompanied by microcracks. Consequently, the
enhanced exural strength and reduced shrinkage were obtained
due to mullitization on the surface of fused silica.

4. Conclusions
The presence of cristobalite reduces the mechanical properties,
such as exural strength and linear shrinkage, due to the volume
contraction during its - to -phase transformation. Therefore, in
the present study, the colloidal alumina was inltrated on a presintered specimen to prevent the surface crystallization of fused
silica to cristobalite. The inltrated particles were coagulated in
the specimens due to the opposite electrical charges between
alumina and fused silica. The alumina inltration improved the
exural strength and shrinkage of the silicazircon composites
because mullitization reduced the crystallization of fused silica to
cristobalite. Due to inhibition of the crystallization to cristobalite,
the improvement of the mechanical properties (i.e., the enhancement of exural strength and the reduction of the linear shrinkage) was revealed with increase of the inltration time up to
150 min. These signicant mechanical properties are considered to
rely on the cristobalite content in the specimens. Consequently,
the mullitization via alumina inltration improved the mechanical
properties of silicazircon composites. However, in the case of
inltration time of over 210 min, the strength and the shrinkage
did not change. The excessive alumina had no signicant effects on
mechanical properties of silicazircon composites because it did
not inuenced on inhibition of crystallization of fused silica to
cristobalite.

Acknowledgments
This work was supported by the Power Generation and Electricity Delivery Core Technology Program of the Korea Institute
of Energy Technology Evaluation and Planning (KETEP), granted
nancial resource from the Ministry of Trade, Industry and Energy,

Republic of Korea (20141020102460).

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colloidal alumina inltration, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.02.137i

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Please cite this article as: Y.-H. Kim, et al., Shrinkage and exural strength improvement of silica-based composites for ceramic cores by
colloidal alumina inltration, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.02.137i