Journal of the European Ceramic Society 26 (2006) 1687–1693

Preparation and mechanical properties of

machinable alumina/mica composites
Seiichi Taruta ∗ , Ryuji Fujisawa, Kunio Kitajima
Department of Chemistry and Materials Engineering, Faculty of Engineering, Shinshu University,
4-17-1, Wakasato, Nagano-shi, Nagano 380-8553, Japan

Received 9 December 2004; received in revised form 16 March 2005; accepted 26 March 2005
Available online 17 May 2005

Abstract

Using a mica-crystallizing glass powder in which a large amount of mica crystal was precipitated and a larger amount of MgF2 component
was contained as the raw materials of mica, machinable alumina/mica composites were obtained at 1400 ◦ C. In the firing process, magnesia
component in the mica crystals reacted with alumina to form spinel at 1150–1200 ◦ C. The reaction made the mica crystals melt. However, the
mica crystals were precipitated again during the cooling. Because a larger amount of MgF2 component was contained in the mica-crystallizing
glass powder, the nucleation of the mica crystals was caused during the cooling by the residual magnesium and fluorine in the liquid phase
and succeedingly the mica crystals were precipitated. The precipitated mica crystals grew to anisotropicaly larger size than alumina grains,
which lowered the bending strength and Vickers hardness and little heightened the fracture toughness.
© 2005 Elsevier Ltd. All rights reserved.

Keywords: Sintering; Mechanical properties; Al2 O3 ; Mica; Composites

1. Introduction BN, the plate or layered shaped structure of Ti3 SiC2 and
the weak interface between oxide and phosphate, respec-
Alumina ceramics are well-known typical ceramics and tively, have been reported. They could be cut and drilled us-
show a favorable combination of physical and chemical prop- ing conventional machining tools. On the other hand, mica
erties, e.g. high strength and hardness, high heat resistance, glass-ceramics have been well-known machinable ceramics
excellent chemical durability and low electrical resistance, since Beal developed a glass ceramic containing mica by
so such alumina ceramics are applied in the various fields controlling crystallization of the base glass in 1971.6,7 The
as engineering materials, electrical insulators, biomaterials excellent machinability originates in the cleavage and the
and so on. However, the alumina ceramics are difficult to be interlocking microstructure of mica platelet crystals.6,7 Uti-
machined by conventional metal tools due to their hardness lizing the machinability of mica, we succeeded in fabricating
and brittleness as well as many other ceramics. Therefore, the machinable cordierite/mica8 and spinel/mica9 composites.
machining costs are very high, which limits the application These composites could be prepared at low temperatures of
fields. The improvement of the machinability is very effective 1100–1200 ◦ C by the sintering of cordierite or spinel raw
in not only the reduction of the machining costs but also the materials and mica-composition (KMg3 AlSi3 O10 F2 ) glass
fabrication of complex shape ceramics, precision machining powder mixtures and the crystallization of mica from the
and machining efficiency. powder mixtures. While the machinable composites contain-
Machinable Al2 O3 /h-BN,1 Al2 O3 /Ti3 SiC2 2 and Al2 O3 / ing h-BN1,5,10–12 and Ti3 SiC2 2 are fabricated by hot pressing
LaPO4 composites,3–5 which utilize the machinability of h- and spark plasma sintering, our machinable composites con-
taining mica8,9 can be fabricated without the special sintering
∗ Corresponding author. Tel.: +81 26 269 5416; fax: +81 26 269 5424. apparatuses. Moreover, comparing with machinable compos-
E-mail address: staruta@gipwc.shinshu-u.ac.jp (S. Taruta). ite containing phosphates,3–5,13 our machinable composites

0955-2219/$ – see front matter © 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jeurceramsoc.2005.03.258
1688 S. Taruta et al. / Journal of the European Ceramic Society 26 (2006) 1687–1693

containing mica8,9 have a possibility of low-temperature sin-

tering due to sintering through the liquid phase formed by
melting of the additive glass. Thus, the fabrication at low
temperatures using conventional apparatuses is the merit of
our machinable composites. However, alumina/mica com-
posites had been never prepared by the sintering of alumina
and mica-composition glass powder mixtures. Because the
mica-composition glass powder reacted with alumina to form
spinel, mica was not crystallized.14
In this study, our aim was to fabricate machinable alu-
mina/mica composites at low temperatures. So not only
the mica-composition glass powder but also the mica-
crystallizing glass powder which contained a large amount
of mica crystals and an excess of MgF2 component over the
mica-composition glass powder was used as the raw mate-
rials of mica. Both or either of these powders were mixed
with alumina powder and sintered. In consequence, machin-
able alumina/mica composites were obtained at 1400 ◦ C. In
this paper, the sintering behavior of the powder mixtures and
the mechanical properties of the obtained composites are re-
ported.

2. Experimental procedure
Fig. 1. SEM photographs of (a) the mica-composition glass powder and (b)
The reagents of K2 CO3 , MgO, Al2 O3 , SiO2 and MgF2
the mica-crystallizing glass powder.
were mixed in the chemical composition corresponding
stoichiometric fluorophlogopite (KMg3 AlSi3 O10 F2 ) com-
position, calcined at 900 ◦ C, melted in a sealed platinum
container at 1450 ◦ C and then quenched. The obtained glass
was pulverized by a ball milling for 48 h. In this way, the
mica-composition glass powder was prepared. The above-
mentioned reagents were mixed in the chemical compo-
sition which was an excess of 10 mass% MgF2 over the
mica-composition glass powder, calcined, melted in a sealed
platinum container at 1450 ◦ C and then cooled in the fur-
nace. Mica was crystallized in the product. The product
was pulverized by a ball milling for 48 h. In this way, the
mica-crystallizing glass powder was obtained. Such mica-
composition glass and mica-crystallizing glass powders were
characterized using a field-emission type scanning elec-
tron microscopy (FE-SEM; S-4100, Hitachi, Japan), an X- Fig. 2. XRD patterns of (a) the mica-composition glass powder and (b) the
mica-crystallizing glass powder: (䊉) mica, (
) sellaite (MgF2 ).
ray diffractometry (XRD-6000, Shimadzu, Japan) and a
differential thermal analyzer (DTA-40, Shimadzu, Japan).
The SEM photographs, X-ray diffraction (XRD) patterns
and differential thermal analysis (DTA) curves of the both
powders are shown in Figs. 1–3, respectively. The SEM
photographs indicate that most particles in both powders
were less than 1 ␮m and a few particles were 2–4 ␮m. It
was obvious in the XRD patterns that the mica-composition
glass powder did not contain any crystals while a large
amount of mica crystal was precipitated and a small amount
of glass remained in the mica-crystallizing glass powder.
In the DTA curve of the mica-composition glass pow-
der, two exothermic peaks appeared at 730 ◦ C (Tc1 ) and Fig. 3. DTA curves of (a) the mica-composition glass powder and (b) the
970 ◦ C (Tc2 ). The Tc1 was attributed to the nucleus for- mica-crystallizing glass powder.
 S. Taruta et al. / Journal of the European Ceramic Society 26 (2006) 1687–1693 1689

Table 1
The mixing rations of starting powders
Specimen Alumina Mica-composition Mica-crystallizing
powder glass powder glass powder
G20 80 20 0
C20 80 0 20
G10C10 80 10 10
G20C20 60 20 20
Weight ratio.

mation which might be corresponding to the precipitation

of chondorodite (4MgO2 ·2SiO2 ·MgF2 ) and/or norbergite
(2MgO·SiO2 ·MgF2 ),6,7 and the Tc2 was to the crystalliza-
tion of mica. And endothermic transformation started at
about 1050 ◦ C (Tm1 ), which was attributed to the melt of
the residual glass. In the DTA curve of the mica-crystallizing
glass powder, any exothermic peaks of the crystallization Fig. 4. XRD patterns of (a) the green compact of the G20 specimen and the
were not observed and the glass included in the mica- sintered G20 specimens which were fired at (b) 1250 ◦ C, (c) 1300 ◦ C and
(d) 1350 ◦ C. (䊉) Mica, () spinel and () alumina.
crystallizing glass powder started to melt at about 1000 ◦ C
(Tm2 ).
The alumina powder (TM-DAR, Taimei Chemicals, 3. Results and discussion
Japan) was mixed by a ball milling with the mica-composition
glass powder and/or the mica-crystallizing glass powder. The 3.1. Phase change and sintering
particle size of the alumina powder was less than 0.1 ␮m,
which was much smaller than the particle size of the mica- XRD patterns of the G20 and G10C10 specimens are
composition glass and mica-crystallizing glass powders. shown in Figs. 4 and 5, respectively. In the G20 specimen,
The weight ratios of alumina/mica-composition glass/mica- very small peaks of mica were observed at 1300 and 1350 ◦ C
crystallizing glass were 80/20/0, 80/0/20, 80/10/10, and while relatively large peaks of spinel appeared at ≥1250 ◦ C.
60/20/20. These four specimens are denoted by G20, C20, On the other hand, in the G10C10 specimen, distinct peaks
G10C10 and G20C20, respectively, as shown in Table 1. of mica appeared at ≥1300 ◦ C, and simultaneously the peaks
The powder mixtures were calcined at 600 ◦ C for 1 h, passed of spinel were observed. Also, in the C20 and G20C20 speci-
through a 100-mesh sieve, compacted by a cold isostatic mens, mica and spinel were observed, of which XRD patterns
pressing at 98 MPa and fired in a sealed platinum container are not shown in this paper. These XRD results indicate that
at 1200–1450 ◦ C for 2 h. Both heating and cooling rates of
the firing were 5 ◦ C/min.
Crystalline phases in the specimens were determined us-
ing the X-ray diffractometry. The bulk densities and the true
densities were measured by Archimedes method and pyc-
nometer method, respectively. The fracture surfaces of the
sintered specimens were observed using the FE-SEM. The
three point bending strength was measured using a univer-
sal strength testing machine (AUTOGRAPH AG-100KNG,
Shimadzu, Japan). The crosshead speed for the bending test
was 0.5 mm/min. The hardness and fracture toughness were
measured using a Vickers diamond indenter (Model-AVK,
Akashi Seisakusho, Japan). The Vickers diamond was in-
dented on the polished surface of specimens at load of 98 N
for 10 s. The fracture toughness was determined by indenta-
tion microfracture method (IM method). For the measure-
ment of these mechanical properties, five test pieces per
specimen were used. The machinability was qualitatively
evaluated using a bench-drilling machine (DP-200, Takagi,
Japan). The drill with a diameter of 3 mm, which was made Fig. 5. XRD patterns of (a) the green compact of the G10C10 specimen and
of hard metal, was used and the rotational frequency was the sintered G10C10 specimens which were fired at (b) 1300 ◦ C, (c) 1350 ◦ C
620 rpm. and (d) 1400 ◦ C. (䊉) Mica, () spinel and () alumina.
1690 S. Taruta et al. / Journal of the European Ceramic Society 26 (2006) 1687–1693

crystallizing glass powder was alone fired at 1200 ◦ C or when

the mica-composition glass, alumina and magnesia powder
mixtures were fired at 1200 ◦ C, the mica crystals remained
in the specimens even after quenching.
Above results mean that magnesia component in the mica
crystals reacted with alumina to form spinel at 1150–1200 ◦ C,
the reaction made the mica crystals melt at ≥1200 ◦ C and
the mica crystals were precipitated again during the cooling.
And the excess of MgF2 component in the mica-crystallizing
glass powder played an important role in the crystallization of
mica during the cooling. That is, using the mica-crystallizing
glass powder which contained an excess of MgF2 compo-
nent over the stoichiometric composition of mica, after the
melting of the mica crystals, the residual magnesium and
fluorine in the liquid phase must form chondorodite and
norbergite which are known as the nuclei for the crystal-
Fig. 6. XRD patterns of the G10C10 specimen fired at (a) 1150 ◦ C and (b) lization of mica in the glass-ceramics6,7 during the cool-
1200 ◦ C for 2 h and then quenched. (䊉) Mica, () spinel and () alumina. ing and succeedingly the mica crystals were precipitated.
On the other hand, if almost magnesia component in the
the excess MgF2 component in the mica-crystallizing glass mica crystals and glassy phase react with alumina to form
powder was very effective in the crystallization of mica. spinel, mica crystals are not precipitated again during the
Incidentally, melting point of mica (fluorophlogopite) is cooling. Fig. 3 shows that mica was crystallized at <1000 ◦ C
about 1340 ◦ C, so mica should melt at ≥1350 ◦ C. Then, in in the mica-composition glass powder. Therefore, if the mica-
order to examine the phase changes during firing, after firing composition glass powder contains an excess of MgF2 com-
at holding temperatures, the specimens were quenched im- ponent, a larger amount of mica crystal is precipitated even
mediately. The XRD patterns of the G10C10 specimen fired in the G20 specimen.
at 1150 and 1200 ◦ C for 2 h and then quenched are shown The bulk densities of each specimen fired and then cooled
in Fig. 6. At ≤1150 ◦ C, mica was observed but spinel did at 5 ◦ C/min and those of the C20 and G10C10 specimens
not almost appear. On the contrary, spinel was observed at fired and then quenched are shown in Fig. 8. It is known that
≥1200 ◦ C but mica was not even at 1200 ◦ C, which is lower the alumina powder used in this study is densified at low
than melting point of mica. The same results were observed temperatures of 1200–1300 ◦ C because the alumina powder
in the C20 and G20C20 specimens. The XRD patterns of the has high purity of >99.99% and very fine particle size of
mica-crystallizing glass powder and spinel/mica composite,9 <0.1 ␮m. The G20 specimen was densified at low temper-
which were fired at 1200 ◦ C for 2 h and then quenched are atures of 1200–1300 ◦ C, too. The bulk density of the G20
shown in Fig. 7. This figure indicates that when the mica- specimen showed the maximum at 1250 ◦ C. The relative
density was 97%. The densification of the C20, G10C10
and G20C20 specimens was impeded by the addition of
the mica-crystallizing glass composition. The densification
of the G20C20 specimen was not almost progressed. The

Fig. 8. Bulk densities of the (
) G20, (䊉) C20, () G10C10 and () G20C20
Fig. 7. XRD patterns of (a) the mica-crystallizing glass powder fired at specimens fired at 1200–1450 ◦ C for 2 h and then cooled at 5 ◦ C/min and the
1200 ◦ C for 2 h and then quenched and (b) the spinel/mica composite fired () C20 and () G10C10 specimens quenched after firing at 1250–1400 ◦ C
at 1200 ◦ C for 2 h and then quenched. (䊉): mica and (): spinel. for 2 h.
 S. Taruta et al. / Journal of the European Ceramic Society 26 (2006) 1687–1693 1691

Fig. 9. SEM photographs of the fracture surfaces of (a) the G20 specimen fired at 1250 ◦ C for 2 h, (b) the C20 specimen fired at 1400 ◦ C for 2 h, (c) the G10C10
specimen fired at 1400 ◦ C for 2 h and (d) the G20C20 specimen fired at 1250 ◦ C for 2 h.

maximum bulk densities of the C20 and G10C10 specimens crystals grew to the size of more than 15 ␮m. In this way,
were obtained at 1400 ◦ C. The relative densities were 94 and using mica-crystallizing glass powder, the anisotropic mica
95%, respectively. In this way, dense alumina/mica compos- crystals grew to larger size than alumina grains during the
ites were obtained at 1400 ◦ C. The quenched specimens had cooling. This remarkable anisotropic growth of mica crystals
larger bulk densities than the specimens cooled at 5 ◦ C/min. was the main factor in the extreme deterioration of the densi-
The difference was large conspicuously for the C20 speci- fication especially at lower firing temperatures. And it limited
men fired at lower temperatures. At 1400 ◦ C, the bulk den- the relative density to the maximum 95%. Consequently, the
sities of the specimens cooled at 5 ◦ C/min were almost the C20 and G10C10 specimens did not reach full density.
same with those of the quenched specimens. The densifi-
cation was progressed by the melting of the mica crystals 3.2. Mechanical properties
during the heating but was deteriorated by the crystallization
of mica during the cooling. A larger number of nuclei should The photograph of drilling test for the C20 and G10C10
be formed at the same time in the C20 specimen because specimens fired at 1400 ◦ C is shown in Fig. 10. The drill
the C20 specimen contained a larger amount of MgF2 com- penetrated into these specimens with the thickness of about
ponent than the G10C10 specimen. Consequently, a larger
number of mica crystals should be precipitated during the
cooling, which resulted in the extreme deterioration of the
densification of the C20 specimen fired especially at lower
temperatures.
SEM photographs of the fractured surfaces of the sintered
specimens are shown in Fig. 9. In all specimens in this Figure,
isotropic grains with size of ≤5 ␮m, which were alumina or
spinel, were observed. In the G20 specimen fired at 1250 ◦ C,
flake-like mica crystals were not observed. In the C20 and
G10C10 specimens fired at 1400 ◦ C, flake-like mica crys-
tals with size of ≤8 ␮m were precipitated uniformly among
isotropic grains and formed the interlocking microstructure. Fig. 10. Photograph of drilling test for the (a) C20 and (b) G10C10 speci-
In the G20C20 specimen fired at 1250 ◦ C, flake-like mica mens fired at 1400 ◦ C for 2 h.
1692 S. Taruta et al. / Journal of the European Ceramic Society 26 (2006) 1687–1693

Table 2
Mechanical properties of each specimen
Specimen Firing temperature (◦ C) Bending strength (MPa) Vickers hardness (GPa) Fracture toughness (MPa m1/2 )
G20 1250 646 ± 20 17.9 ± 0.2 2.9 ± 0.2
C20 1400 405 ± 13 11.6 ± 0.6 3.9 ± 0.1
G10C10 1400 443 ± 5 13.8 ± 0.2 3.7 ± 0.1

3 mm. Glass-ceramics composed of greater than two-thirds tals. During the cooling, however, residual magnesium and
mica by volume are normally machinable, regardless of the fluorine in the liquid phase formed the nuclei for the crys-
morphology of the mica crystals, and those containing as lit- tallization of mica and succeedingly the mica crystals were
tle as one-third by volume of mica may be machinable if precipitated again. If almost magnesia component in the mica
the aspect ratio of the crystals is large enough to cause a crystals and glassy phase react with alumina to form spinel,
high degree of interlocking of the crystals.6,7 However, the mica crystals are not precipitated during the cooling. And
C20 and G10C10 specimens contain mica crystal of only if the mica-composition glass powder contains an excess of
about 26 vol.% even if the mica-crystallizing glass and the MgF2 component, a dense machinable alumina/mica com-
mica-composition glass powders completely crystallize into posite is obtained even by the single addition of the glass
mica. Practically, the content of the precipitated mica crys- powder. The densification was progressed by the melting of
tal must be lower than 26 vol.%. However, the interlocking mica crystals, but the anisotropic mica crystals grew to larger
microstructure of the flake-like mica crystals was observed size than alumina grains during the cooling, which deterio-
throughout the C20 and G10C10 specimens as shown in Fig. 9 rated the densification.
though the degree of the interlocking of mica crystals might The dense alumina/mica composites obtained at 1400 ◦ C
be low. Therefore, the C20 and G10C10 specimens could be could be machined by the conventional hard metallic tool.
machined with the drill made of hard metal but could not The precipitation of anisotropic large mica crystals low-
be sufficiently machined with conventional high-speed steel ered the bending strength and Vickers hardness but little
tools. In addition, the large chippings were observed in the heightened the fracture toughness. The bending strength was
bottom side of the specimens by the machining. While one 400–450 MPa, which were the same level as that of the con-
factor of the generation of the chippings was the technical ventional monolithic alumina ceramics while the fracture
problem of drilling, the low degree of the interlocking mi- toughness was 3.7–3.9 MPa m0.5 , which were little higher
crostructure of mica crystals might contribute to the genera- than that of the conventional monolithic alumina ceramics.
tion of the large chippings. The Vickers hardness was 11–14 GPa, which was the same
The mechanical properties of each specimen are shown level as that of zirconia ceramics.
in Table 2. The bending strength of the machinable C20 and
G10C10 specimens was lower than that of the G20 specimen.
The degradation of bending strength resulted from the precip-
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