Current Advances in Materials Sciences Research (CAMSR)

CAMSR Volume 1, Issue 1 Jan. 2014 PP. 12-16 www.vkingpub.com American V-King Scientific Publishing
12
The fracture toughness of the casted hydraulically
Yttria Zirconia-Mullite-Magnesia system
Budi L. Hakim
*1
, Syoni Soepriyanto
2
, Akhmad A. Korda
3
, Bambang Sunendar
4
*1, 2, 3
Department of Metallurgical Engineering-Faculty of Mining and Petroleum, Indonesia
4
Laboratory of Material Science and Engineering- Faculty of Industrial Technology, Indonesia
Bandung Institute of Technology, Jl. Ganesha 10 Bandung 40132, Indonesia
*1
bhakim8@gmail.com;
2
syonis@mining.itb.ac.id;
3
akhmad@mining.itb.ac.id;
4
purwa@tf.itb.ac.id


Abstract-This experiment intended to study the properties of
the casted hydraulically Yttria Zirconia-Mullite-Magnesia
system. The specimens were prepared containing 3% Yttria
into Tetragonal Zirconia Polycrystalline compound or 3Y-TZP.
The additional Mullite was synthesized from alumina and silica
with excessive silica content at about 15 to 25%. It can be said
that the Mullite or likely Mullite content tend to reduce the
values of hardness and fracture toughness parameters. High
concentration of Mullite may decrease the mechanical
properties of the ternary system. However, the optimization of
magnesia concentration has not been reached completely and
may influence directly to Mullite-Magnesia performance and
also whole mechanical properties of the 3Y-TZP-Mullite-
Magnesia system.
Keywords-Yttria Zirconia; Mullite; Magnesia; Vikers Hard-
ness; Fracture toughness.
I. INTRODUCTION
Cracking is a detectable response of the ceramic to
indentation even at small loads, may either be localized or,
at higher loads, massive to the extent that crushing follows.
The ceramics product mostly specifies the minimum
hardness requirement. ASTM F1873-98, the zirconia
specification for surgical implants stipulates that Vickers
hardness (HV) shall be no less than 11.8 GPa (1200 kgf/
mm
2
) at a load of 9.8 N (1 kgf). Vickers hardness covers
approximately 60% of worldwide published ceramic
hardness values, with loads typically in the range of a few
newtons to 9.8 N (1 kgf) and occasional data for soft or
high-toughness ceramics as high as 98 N (10 kgf). Whereas,
Knoop hardness involves about 35% with loads from as low
as 0.98 N (100 gf) to 19.6 N (2 kgf) [1].
Many contemporary structural ceramics have hardnesses
in the range from 10 to 30 GPa. For the higher hardness,
Vickers indentations made at 9.8 N (1 kgf) load are 25
microns in size and Knoop indentations are 68 microns long.
The ASTM C1327 is a new standard for Vickers hardness of
advanced ceramics and recommends a load of 9.8 N (1 kgf).
Hardness was calculated from the standard formula for
force divided by contact area [2]:
HV = 1.8544 P / d
2
(1)
where HV is Vickers hardness, P is the applied indenter load,
and d is the average diagonal length for an individual
indentation.
An indentation fracture mechanics was applied as a
simple technique for evaluating mechanical properties of
ceramic materials. Evans and Charles uniquely
characterized the surface radial cracks in brittle materials
generated by Vickers indentation. Evans-Charles was
modified by Lawn et.al

[3-6], based on approach for median
or radial cracks. Recently Niihara et al modified the analysis
of Evans and Charles and Lawn by incorporating Palmqvist
cracks, rather than median cracks, at low crack to indent
ratio size (0.25<l/a<2.50), in which for the Palmqvist cracks
is expressed as [7]:
(K
IC
/Ha
1/2
)(H/E)
2/5
= 0.035(l/a)
-1/2
(2)
and for the median cracks is applied for (c/a)>2.50, as the
following:
(K
IC
/Ha
1/2
)(H/E)
2/5
= 0.129(c/a)
-3/2
(3)
where H is the hardness, a is the indent half diagonal, E is
Youngs modulus and c is the radial crack size (Fig.1.).
Whereas is the constraint factor as H/
y
or nearly equal to
3, in which
y
is the yield stress, and l is the Palmqvist crack
length.

Fig.1. Palmqvist and median cracks around Vickers Indentation
Source: Nihaara (1983) [7]
A fracture mechanics model for the median cracks has
been provided by Lawn and Fuller, and Evans and Charles;
however there is no corresponding analysis for Palmqvist
cracks. Recently, numerous studies about the indentation
fracture on brittle materials have shown that the initially
cracks are the Palmqvist cracks. They extend radially along
median planes of indentation and remain close to the
specimen surface.
Current Advances in Materials Sciences Research (CAMSR)
CAMSR Volume 1, Issue 1 Jan. 2014 PP. 12-16 www.vkingpub.com American V-King Scientific Publishing
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This study analyzed the transition point and related it to
a new index of ceramic brittleness, which is defined as
B=HE/(K
IC
)
2
. The brittleness index will be important for
predicting mechanical properties such as for the
characterization of machinability, wear or erosion resistance.
The additive application in the ceramic system has being
examined. For instance, additional titania in the zirconia-
mullite-alumina system showed the increase in hardness and
density and the decrease of abrasion loss properties [8]. As
3Y-TZP presented the higher relative densities which
contributed to a better mechanical and thermal behaviour
rather than 8Y-TZP [9], this experiment preferably focused
on application 3Y-TZP as the basic substance of ternary
system.
The synthesis of Mullite compound should be based on
the reaction molarity composition, instead of the weight
basis. The difference between two perspectives implied an
occurrence of an excess of unreacted silica substances.
However the physical mechanical testing may still obtain a
reasonable trend of data to explain the parameter of Vikers
hardness and fracture thickness of metal ceramics composite
system.
II. EXPERIMENTAL PROCEDURE
This experiment employed local source of Zirconia
(ZrO
2
) which was obtained through caustic fusion and
calcination process of zircon opacifier raw material (ZrSiO
4
),
Yttria (Y
2
O
3
). The other materials were Alumina (Al
2
O
3
),
Silica (SiO
2
), and Magnesia (MgO). The Zirconia synthesis
was performed in the Ceramic Technology laboratory of
Metallurgy Department - Bandung Institute of Technology.
The 3Y-TZP powder was synthesized through mixing of
local Zirconia (ZrO
2
) powder with 3% mole of Yttria (Y
2
O
3
)
and poly vinyl butyrate. The blend was mixed
homogeneously, calcinated, dried and finally grinded to
obtain 3Y-TZP powder. The 3Y-TZP powder was then
casted hydraulically with applied maximum load at about 4
ton/cm
2
, and then sintered at temperature of 1500
o
C during
4 hours. All other powders of Al
2
O
3
, SiO
2
, and MgO were
commercially available.
This experiment prepared vary of samples, included: (a)
Mullite system with more silica proportion to study the
excess impact of this substance, (b) Synthesis of local
Zirconia from raw material, and (c) Binary and ternary
system involved 3Y-TZP-Mullite-Magnesia.The specimens
were prepared in pellet and plate shapes. The pellet
specimen has diameter of 8 mm, and 3 mm thickness.
Whereas the plate specimens referred to ASTM C1161
requirement of size with 4 mm width, 3 mm thickness, and
45 mm length as a three point bending test specimen.
In this experiment, the specimens were analyzed using
X-ray diffraction (XRD) to examine the crystal structure
and phase of ceramic 3Y-TZP- Mullite - MgO. Whereas the
ceramics morphology was analyzed using SEM. The
fracture toughness (K
IC
) was calculated based on Vikers
indentation.
III. RESULT AND DISCUSSION
A. Silica Rich Mullite
Application of excessive silica in mullite synthesis was
evaluated in this experiment (Table.1.). Thermodynamically
each 72 grams of alumina should thermally combine with 28
grams of silica to form alumina silica (mullite) compound
system. The benefit of Mullite addition was relatively
complex to be evaluated independently due to silica rich
impact in the system, in which not all of silica molecule can
be absorbed to form new complex molecule name YTZP-
Mullite system.
TABLE I SILICA RICH MULLITE INTO 3Y-TZP SYSTEM
Specimen
Code
Alumina,
gram
Silica,
gram
Silica
excess,
gram
Silica
excess, (%)
YZ00OS 72.0 28.0 0.0 0.0%
YZ00ES 66.0 25.9 6.1 24%
YZ10ES 60.0 23.5 4.5 19%
YZ15ES 57.0 22.4 3.6 16%
YZ20ES 53.0 20.8 4.2 20%
The excess of alumina was studied by Obal et.al (2012)
that it effects on the electrical conductivity of 3Y-TZP [10].
They assumed that the low grain boundary conductivity of
3Y-TZP is attributed to inter granular siliceous phases,
which wet the grain boundaries. The added alumina reacts
with silica, forming a stable Mullite:
3 Al
2
O
3
+ 2 SiO
2
3Al
2
O
3
.2SiO
2
(4)
According to thermodynamic calculations, reaction (4)
may occur when the activity of silica is at least 0.03 at
1600
o
C. On the other hand, the reaction between zirconia
and silica yields the unstable silicate ZrSiO
4
, which
dissociates above 1540
o
C. However, this compound is not
stable in the presence of alumina. So the occurrence of
Mullite may contribute to reduce possible formation of
unstable silicate ZrSiO
4
.
In this experiment, the remaining silica was occurred
caused from silica rich mullite composition. Fig.2 and 3
show examples of the XRD patterns of silica rich mullite
without 3Y-TZP, and 3Y-TZP-Mullite-Magnesia system. In
the 3Y-TZP system, the unstable ZrSiO
4
may be formed at
the interfacial region via a reaction between the excess SiO
2

and the ZrO
2
substrate.


Fig.2. XRD pattern of the Mullite (3Al2O3.2SiO2)
Al
Al
Al
Al
Al
Intensity (%)
Position (2)
Al
Al
Al
Al
Si
Si
Si
Si
Si
Si
Si
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CAMSR Volume 1, Issue 1 Jan. 2014 PP. 12-16 www.vkingpub.com American V-King Scientific Publishing
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Fig.3. XRD pattern of the (10% 3Y-TZP-19% silica rich Mullite- 10%MgO)
The XRD pattern of the silica rich Mullite indicates
alumina and silica compounds. The mullite reacted with the
zirconia to form 3YTZP-Mullite. The occurrence of
magnesia promotes to form 3YTZP-Mullite-Magnesia. It
indicated that there were some shifts of the peak positions
for both the zirconia phase and the mullite phase. The peak
shifts indicated some solubilities between mullite, zirconia,
and Yttria present in the metal composites.
As the 3Y-TZP specimens were placed in the excess
SiO
2
concentration, some of the SiO
2
may deposit on the
substrate. Initially, the SiO
2
that was involved in the 3Y-
TZP apparently reacted with the substrate to form combined
molecule such as ZrSiO
4
. However, as the reaction
continued, the diffusion path for zirconium or silicon
increased such that the formation of ZrSiO
4
was restricted,
and crystallized into the other molecule e.g. cristobalite

[11].
The additional data of XRD analysis of other content of
3Y-TZP shows similar trend of peak location with slightly
different of magnitudes. It implied that both of Mullite or
likely Mullite components of alumina and silica may
thermally combine rather chemically combines into the new
ceramic composite system.
B. Grain Sizes
Through a controlled crystallization, it was reported that
zirconia co-reinforced mullite composite micro structure can
be synthesized [12]. The tetragonal zirconia (t-ZrO
2
) grains
with the average diameter at about 0.1 to 2 m, were
observed in spherical and bar-like shape that were observed
in the mullite lattice (Fig.4.a). Further, it is shown in Fig.4.b
that the spherical objects of zirconia with the average
diameter at about 0.1 to 2 m were embedded in the mullite-
magnesia system. In this system, mullite incorporated with
or without magnesia, roles as a matrix medium for the
zirconia. The mechanical strength depends on the proportion
of zirconia, whereas mullite penetrates into the available
space between the grains mixture. The benefit of magnesia
occurrence may correlate with the possible crack resistance
during sintering cycle.
The influence of additives may correlate with the grain
sizes. X.Miao, et.al (2004) observed the SEM micrographs
of the thermally etched surfaces of the YZrO
2
TiO
2

composites sintered at 1300
o
C with TiO
2
content varied
from 0 vol.% to 30 vol.% [13]. They found that the increase
of an additive content in Y-TZP system tends to result the
bigger grain sizes.

(a) 3Y-TZP-Mullite

(b) 3Y-TZP-Mullite-Magnesia
Fig.4. The 3Y-TZP-Mullite with and without magnesia
The modified 3Y-TZP by additional Mullite will reduce
its hardness, modulus of elasticity, and stress concentration.
Practically, it was recommended that an additional Mullite
should be no more than 10% to 20%, due to reduction of
mechanical properties tendency, although it may be
compensated through smoother grain and better sintering
technique [14].
C. Vikers Hardness
In indentation testing, it is usually desired to avoid
cracking that interferes with the hardness measurement.
However, a simple method to estimate fracture toughness
(K
IC
) of ceramic employs the length of the cracks that
propagates from the corners of a Vickers indentation. The
lengths of the cracks and the indentation half-diagonal size
are related to the hardness, elastic modulus, and fracture
toughness by an analytical expression.
An example of indentation testing was shown in the
following figure (Fig.5.). This figure identifies crack length
(L) as 0.015mm (15m) both on the left and the right side of
the Vickers indentation, whereas the blue line, at the
bottom-right side, represents 0.050 mm length as a reference
of cracks length (l).
Position (2)
Intensity (%)
Al
Al
Al
Al
Al
Al
Al
Zr
Al Al
Zr
Al
Al Zr
Zr
Y
Zr
Zr
Zr
Zr
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Fig.5. Vikers micro hardness and crack measurement
It was revealed that the correlation between the crack
lengths (l) to the indentation half-diagonal size (a) is related
to the hardness. Fig.6 configures the Palmqvist cracks
criterion that prevails if the value of indent ratio (l/a) is in
the range of 0.25 to 2.50. However, if the value of (c/a) ratio
may exceed 2.5, the harness value should be considered as
the Median crack. The variable of c is defined as the crack
lengths (l) plus the indentation half-diagonal size (a).
Through the Vickers hardness testing, it was obtained that
the shorter the crack, the harder the ceramic material.

Fig.6. Vikers hardness curve of (Y-TZP + Mullite + MgO) system
It is shown that Mullite or likely Mullite shows lower
hardness than pure 3Y-TZP system, in which gradually
additional of Y-TZP into the Mullite system tend to increase
its hardness properties. In this case, the experiment tended
to comply with the Palmqvist crack criteria, in which the
length of crack conformed to Palmqvist curve in the range
of 19 microns to 31 microns.
In this experiment, the laboratory testing of rich silica
mullite (specimen A) achieved the mean hardness value
(HV) of 27.78 GPa. Actually, the sample contains 24%
silica rich in mullite compound system. The previous study
(Bodhak, et.al. 2011) measured the hardness value of 92%
densified mullite with 1 wt% MgO and 10 wt%
ZrO
2
composites and sintered at 1500C in microwave
furnace, exhibited a hardness value of 10.24 GPa. They
observed additional 1% weight of magnesia as a sintering
aid for Mullite proved an increase of compressive strength
typically from 128 to become 387 MPa [15].
The pure Mullite system has the lowest hardness while
compared among the other experiment data. Meanwhile,
Mullite performance may be influenced by occurrence of
magnesia (MgO) additive. S.Prutty, et.al (2012) observed
that mullite Zirconia not only stabilizes the cubic zirconia
phase but also acts as a sintering aid for the formation of
cross-linked mullite grains [16]. However it requires
further study about the role of magnesia into the ternary
system characteristics.
The specimen B represented the 3Y-TZP containing
10% Mullite and MgO having Vikers hardness (HV) value
of 35.27 GPa. By additional Mullite composition at about
15% (specimen C), it increased the hardness up to 42.73
GPa. As comparison, the pure 3Y-TZP in the similar testing
condition resulted the the average hardness (HV) value up to
60.36 GPa.
D. Fracture Toughness
The fracture toughness parameter was expressed
employing Vickers hardness indentation measurement.
Fracture toughness of silica rich Mullite shows the lowest
fracture toughness among data of YttriaZirconia-Mullite
system. In this experiment, the Mullite (specimen A)
showed the fracture toughness value of 3.69, whereas the
3Y-TZP reached the highest fracture toughness value at 4.32.
It seems that mullite or likely-mullite occurrence in the 3Y-
TZP-Mullite system may reduce fracture toughness
properties. The rest of silica was mixed in the ceramic
composite system to cause heterogeneous system.
The Yttria-TZP content tends to increase HV and
fracture toughness of the Mullite system. As a comparison,
the specific density of tetragonal zirconia is 6.13, whereas
the Mullite is 3.05 and zircon (ZrSiO
4
) is 4.65. Meanwhile
the hardness of tetragonal zirconia, in Mohs unit, is 6.5,
whereas the Mullite is 6 to 7 and zircon (ZrSiO
4
) is 7.5 [17].
In similar testing condition with the equal load of
indentation, the additional 10% 3Y-TZP in the Mullite
system increased the fracture toughness up to 4.26 MPa.m
1/2
.
At the higher 3Y-TZP content as much as 15% in the
Mullite and Magnesia system, the fracture toughness value
increased at 4.56 MPa.m
1/2
. In the case of the magnesia
occurrence, it may positively contribute in the increase of
this metal ceramic properties.
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CAMSR Volume 1, Issue 1 Jan. 2014 PP. 12-16 www.vkingpub.com American V-King Scientific Publishing
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Fig.7 represented the correlation between fracture
toughness and the Vikers hardness parameters. The brown
line in the figure acts as a reference line that represents
fracture toughness values based on Vikers hardness. With an
average crack length of 3Y-TZP equal to 22 microns, it
complies with Palmqvist crack hardness curve criterion, in
which the parameter of indent ratio (l/a) was equal to 1.87.

Fig.7. Fracture toughness of Mullite into 3Y-TZP system
The excessive content of silica in a Mullite compound
may increase gap of coefficient of thermal expansion
between Y-TZP, Mullite and the rest of silica. This case can
be identified by crack phenomenon of the system during
cooling after ternary system formation. Beside this reduce
the K
IC
and hardness of the ceramic system, it can be
visually observed through SEM analysis that the unreacted
silica component seems unable to completely mix into the
alumina-silica system.
IV. CONCLUSION
The influence of additional Mullite (or likely Mullite)
content into casted hydraulically Y-TZP ternary system was
reviewed. This experiment employed 3% Yttria content into
Tetragonal Zirconia Polycrystalline compound or 3Y-TZP.
The experiment utilized Mullite that was synthesized from
alumina and silica in high content at about 15 to 25%.
Although the test analysis unable not focused on pure
mullite due to an excessive silica content, however it can be
concluded that the Mullite or likely Mullite occurrence
tended to reduce the values of hardness and fracture
toughness parameters. High concentration of Mullite tends
to decrease the mechanical properties of the ternary system.
The optimization of magnesia concentration may correlate
directly to the true Mullite performance in the ceramic
composite system.
ACKNOWLEDGMENTS
The authors would like to thank Indonesian Aerospace-
Bandung, for contributing the silica and alumina materials.
The authors are grateful to H.Subawi from Indonesian
Aerospace for discussion and helpful suggestions. The
authors also appreciate National Atomic Power Council-
Bandung for facilitating specimen preparation.
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