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Sintering of slip cast composite Al2O3-ZrO2 ceramics

Conference Paper · October 2018

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Ivana Sever Lidija Ćurković

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 Sintering of slip cast composite Al2O3-
ZrO2 ceramics
I. Sever, L. Ćurković, I. Žmak

Faculty of mechanical engineering and naval architecture, 10000 Zagreb, Croatia,

ivana.sever@fsb.hr

Abstract
Slip casting method can be used for forming monolithic and composite ceramics, in which a
stable aqueous suspension of ceramic particles is poured into a plaster mould. Zirconia-toughened
alumina composite ceramics possess many attractive properties such as high-temperature mechanical
strength, wear resistance, low thermal conductivity and good thermal shock resistance. Compared to
monolithic alumina ceramics, composite Al2O3-ZrO2 ceramics have enhanced fracture toughness and
flexural strength due to the embedded zirconia grains in the alumina matrix.
In this paper, water-based suspensions with a total of 70 wt. % solid phase content (monolithic Al2O3
and composite Al2O3-ZrO2 ceramic suspensions) were prepared. The solid phase of composite
ceramic suspensions consisted of either 1 or 10 dry weight base (dwb) % addition of zirconia (ZrO2)
powder, and the rest was alumina powder. The used zirconia (ZrO2) powder was partially stabilized
with the 3 mol % yttria (Y2O3). A dispersant (Dolapix CE 64) and a binder (polyvinyl alcohol - PVA)
were added for the stabilization of water-based suspensions. The stability of 70 wt. % monolithic
(Al2O3) and composite (Al2O3-ZrO2) ceramic suspensions was evaluated by rheological
measurements and sedimentation tests. Suspensions were homogenized in a planetary ball mill and
green bodies were prepared by slip casting of stable suspensions in a plaster mould. After the
sintering, the density of the sintered monolithic and composite ceramic samples was measured and
compared.

Keywords: alumina - zirconia composite ceramics, slip casting, stability, rheology

1. INTRODUCTION alumina, ZTA ceramics are characterized with

high fracture toughness due to zirconia's
The demand for new and improved ceramic
transformation of the tetragonal phase to
materials is constantly growing, especially over
monoclinic phase [3]. These improved
the last few decades. Although monolithic
properties such as high mechanical strength,
ceramics have a wide application scope, some
wear resistance, high flexural strength and
features such as brittleness and a low damage
fracture toughness extend the application scope
tolerance make them inadequate for some
of ZTA ceramics [4]. It has been used for
applications. Better features can be achieved by
different cutting tools, biomedical implants,
embedding ceramic fibres or grains in a ceramic
dental ceramics, structural ceramic parts and
matrix to obtain a ceramic composite with
lately armour materials [5,6].
improved properties [1].
The transformation of the tetragonal phase to
The addition of zirconia grains (ZrO2) to
monoclinic phase in stabilized zirconia acts as a
alumina matrix forms zirconia-toughened-
dissipative mechanism for fracture energy. This
alumina (ZTA) ceramic. Engineering
dissipative fracture energy is due to volume
applications of zirconia were made possible by
expansion during the tetragonal to monoclinic
the discovery of the stabilization of the
phase transformation [7]. When a crack appears
tetragonal phase using either magnesium oxide
in the material, the grains next to the crack
(MgO) or yttrium oxide (Y2O3) [2]. In addition
transform into monoclinic phase. The changes in
to high hardness and chemical stability of
volume and in shape of the crystal cells take
place on account of the elastic stresses during
the propagation of the crack. All these processes
lead to an increase in toughness of the ceramic
material [2].
Different technologies, such as dry-pressing,
tape casting, pressure casting, slip casting or
spraying can be used to produce composite
ceramics. All of these forming methods start
with a suspension of ceramic powder, water and
additives [8]. Slip casting is a colloidal
technique used for the consolidation of the
ceramic powder from an aqueous suspension.
The slip, i.e. the suspension, is poured into a
porous mould which withdraws water from the
slip producing a green body ready for sintering.
Slip casting is a widely used inexpensive
process suitable for producing both monolithic
and composite ceramics even for complex
geometries. However simple this technique may
be, it requires adequate understanding of colloid
suspensions and their behaviour [9,10]. In order
to obtain a material with high green density and
microstructural homogeneity, different casting
parameters must be properly adjusted such as
suspension viscosity and stability, as well as the
suspension composition. To achieve low
suspension viscosity, but also high green and
sintered density, various additives are added to
the suspensions, such as the dispersants and
binders [11]. The addition of dispersants
eliminates the powder’s tendency to
agglomerate due to the attractive intra-particle
van der Waals forces. The obtained slip has low
viscosity with high solid loading to ensure high
green density and homogeneous microstructure
[12].
In this paper, water-based suspensions with a
total of 70 wt. % solid phase pure Al2O3 as well
as mixture of Al2O3 and ZrO2 powder were
studied. Two composite ceramics were prepared
with 1 and 10 dwb % of the 3 mol % yttria-
partially stabilized zirconia (ZrO2) powder. A
dispersant (Dolapix CE 64) and a binder (PVA)
were added for the stabilization of water-based
suspensions. The stability of 70 wt. %
monolithic Al2O3 and composite Al2O3 - ZrO2
ceramic suspensions was evaluated by
rheological measurements and sedimentation
tests. Suspensions were homogenized in a
planetary ball mill and green bodies were
prepared by slip casting of stable suspensions in
a plaster mould. After the sintering at 1600 °C,
the density of the sintered monolithic and
composite ceramic samples was measured and
compared.
2. MATERIALS AND METHODS
USED FOR RESEARCH
2.1. Preparation of monolithic
alumina and composite alumina -
zirconia ceramic suspensions
Monolithic alumina suspensions were
prepared with a total of 70 wt. % solid phase,
and composite alumina - zirconia suspensions
with 1 and 10 dwb % addition of the 3 mol %
yttria-partially stabilized zirconia (ZrO2) powder
(SkySpring Nanomaterials, Inc., USA). High-
purity Al2O3 powder was used, with the average
particle size 300-400 nm (Alcan Chemicals,
USA). A commercial carbonic acid based
polyelectrolyte dispersant Dolapix CE 64
(Zschimmer & Schwarz Chemie GmbH,
Germany) and binder PVA (polyvinyl alcohol,
Sigma Aldrich, USA) were used to stabilize
highly concentrated alumina and alumina -
zirconia suspensions. The optimal amounts of
the dispersant (Table 1) were determined in
preliminary experiments.
The binder (PVA) was dissolved in deionised
water at a temperature of 60 °C. The optimal
amounts of the dispersant (Table 1) were added
to the solution of the binder and water and added
into the grinding jar of the planetary ball mill.
After that, 70 wt. % of dry ceramic powder was
added into the grinding jar. Ten alumina balls
were used for the mixture homogenization,
which lasted for 90 minutes at a speed of 300
rpm. Alumina balls were separated from the
suspension after the homogenization using a
sieve. The suspension underwent an ultrasonic
treatment for 15 min in an ultrasonic bath –
Bransonic 220 (Branson Ultrasonics Corp.,
USA) to remove the air bubbles and achieve
better homogeneity.
2.2. Rheological analysis of ceramic
suspensions
Rheological properties of ceramic
(monolithic and composite) suspensions were
determined using a rotational viscometer DV-III
Ultra (Brookfield Engineering Laboratories,
Inc., USA) in a small sample chamber with
spindle SC4-18. Pre-shearing lasted for 2 min at
a shear rate of 100 s-1. The shear rate was
gradually increased from 0.1 to 180 s-1, and then
reduced back to 0.1 s-1. The shear rate
increase/decrease interval was divided in 50
equal time frames, which lasted for 3 seconds
each. Rheological measurements were
conducted just before each shear rate change.
Table 1. Composition of prepared ceramic suspensions
Suspension Dry powder Composition of ceramic
content, wt.% powder
1 70 100 % Al2O3
2 70 99 % Al2O3 + 1 % ZrO2
3 70 90 % Al2O3 + 10 % ZrO2
2.4. Preparation and sintering of
ceramic green bodies
Production of ceramics by slip casting
method involves pouring of highly concentrated
water-based slip (suspension) into a plaster
mould. To produce ceramic green bodies, water
is absorbed by the mould through capillary
action. This way, dense cast form is obtained
which minimizes shrinkage in the final sintering
process.
After 24 hours, green bodies were removed from
plaster moulds and dried at 100 °C for 1 hour.
Finally, dried green bodies were grinded and
polished to form the desirable shape. Shaped
green bodies were then sintered at 1600 °C in an
electric furnace (Nabertherm P310, Germany).
Sintering process was carried out as follows:
1 °C min-1 to 600 °C, with holding time of 1
2.3. Sedimentation tests
Aqueous ceramic suspensions (monolithic
and composite) with 20 wt. % of dry solid phase
were prepared with the corresponding amounts
of the dispersant and the binder (Table 1). The
pH value was adjusted using 0.1 M HCl, 0.1 M
NaOH and the pH-meter FE20/EL20 (Mettler
Toledo GmbH, Switzerland). 14 ml of
suspensions, each with a different pH value
(from 2 to 12) were poured into test tubes and
set aside on a stand. The ceramic powder will
remain dispersed in a stable suspension, while in
an unstable suspension the ceramic powder will
settle on the bottom of the test tube. Sediment
volume was recorded after 1 h, 24 h, 72 h and 7
days for each suspension.
Dispersant Binder content,
content, wt.% wt.%
0.2 0.5
0.3 0.5
1 0.5
hour; then 3 °C min-1 to 1600 °C. To complete
the sintering process, samples were held for 2
hours at a temperature of 1600 °C after which
they were furnace cooled to room temperature.
Monolithic alumina ceramics and composite
alumina – zirconia ceramics prepared by above
described process are shown in Figure 1.
Fig. 1. Sintered ceramic samples: (A) 100%
Al2O3, (B) 99% Al2O3 + 1% ZrO2, (C) 90% Al2O3 +
10% ZrO2
2.5. Density measurements suspensions, which also confirms the previous
The density of the sintered samples was statement. The addition of zirconia powder
measured using a laboratory scale with Density increases the viscosity and the shear stress.
Kit MS-DNY-43 (Mettler Toledo GmbH,
Switzerland). Sintered samples were weighed,
first in the air and then in a liquid (distilled
water) of known temperature. The density is
calculated by a computer program according to
the ASTM C373-88 (Standard Test Method for
Water Absorption, Bulk Density, Apparent
Porosity, and Apparent Specific Gravity of Fired
Whiteware Products, Ceramic Tiles, and Glass
Tiles). The density is defined according to the
standard by the equation:

(1)
where:
V – sample volume, cm3,
α – correction factor (α =0.99985),
A – sample mass in air, g,
B – sample mass in liquid, g,
ρ0 – liquid density, g cm-3, Fig.2. Flow curves: (A) viscosity (η) vs. shear
rate (γ), and (B) shear stress (τ) vs. shear rate (γ)
ρL – air density, g cm-3 (ρL=0.0012 g cm-3).

3.2. Sedimentation tests results

3. RESULTS AND
ACHIEVEMENTS
3.1. Rheological flow curves
Rheological flow curves show the
dependence of shear stress (τ) on viscosity (η) as
well as on shear rate (γ), and can be used for
predicting the nature of interactions among
particles in the suspension. The alumina and
alumina - zirconia suspensions flow curves are
shown in Figure 2.
The obtained results show that the
suspension viscosity decreases with increasing
shear rate (Figure 2A), that is, all suspensions
show typical pseudoplastic behaviour,
characteristic for non-Newtonian fluids [13].
Figure 2B shows that the shear stress increases
with the increasing shear rate for all
Values of sediment volumes at different pH
after 1 h, 24 h, 72 h and 7 days of sedimentation
are shown in Figure 3A for the alumina
suspensions without the addition of zirconia
powder. It is visible that the alumina
suspensions are stable in acidic (2-5) and
alkaline (8-12) pH region during the first hour.
After 7 days phase separation is visible
throughout the studied pH values.
Values of sediment volumes at different pH
after 1 h, 24 h, 72 h and 7 days of sedimentation
for the alumina suspensions with the addition of
1 dwb % of zirconia powder are shown in Figure
3B. During the first few hours, alumina -
zirconia suspension is stable in the acidic (pH
2-4) and alkaline (pH 7-12) region. The pH
region of stability is shifted to the left with the
addition of zirconia powder. Phase separation is
also visible after 72 hours.
Values of sediment volumes at different pH
after 1 h, 24 h, 72 h and 7 days of sedimentation
for the alumina suspensions with the addition of
10 dwb % of zirconia powder are shown in
Figure 3C. It is noticeable that the alumina -
zirconia suspension is stable only in the neutral
and alkaline (6-12) pH region. The pH region of
stability is shifted even more to the left with the
increase in amount of the added zirconia
powder.
Fig.3. Values of sediment volume at different pH of
ceramic suspensions after 1 h, 24 h, 72 h and 7 days
of sedimentation: (A) 100% Al2O3, (B) 99% Al2O3 +
1% ZrO2, (C) 90% Al2O3 + 10% ZrO2
3.3. Density measurements results
The results of the density measurements
showed that the density of monolithic Al2O3
ceramic is 91.4 % of the theoretical alumina
density ( t = 3.986 g cm-3), Table 2. The
addition of the zirconia powder to alumina
significantly increased the density of the
sintered ceramic samples. The density of the
composite ceramic with 99% Al2O3 and 1%
ZrO2 was 94% of the theoretical density ( t =
3.999 g cm-3), whereas the composite ceramic
with 90% Al2O3 and 10% ZrO2 was only 89.4%
of the theoretical density ( t = 4.172 g cm-3).
Table 2. Density () of the sintered samples
Sample , g cm-3  t, %
100% Al2O3 3.637 91.4
99% Al2O3 + 1% ZrO2 3.759 94
90% Al2O3 + 10% ZrO2 3.729 89.4
4. CONCLUSIONS
In this paper, water-based suspensions with a
total of 70 wt. % solid phase (monolithic Al2O3
and composite Al2O3 - ZrO2 ceramic
suspensions) were prepared. Composite Al2O3-
ZrO2 ceramic suspensions were prepared with 1
and 10 dwb % addition of the 3 mol % yttria-
partially stabilized zirconia (ZrO2) powder to
investigate the effect of zirconia addition on
density of the sintered ceramic samples.
The stability of 70 wt. % monolithic Al2O3
and composite Al2O3-ZrO2 ceramic suspensions
was evaluated by the rheological measurements
and the sedimentation tests. The rheological
measurements showed that the addition of
zirconia powder increases the viscosity and the
shear stress of ceramic suspensions. The pH
region of the stability of the prepared
suspensions is shifted to the lower pH values
with the increasing amount of zirconia powder.
The density of the sintered monolithic and
composite ceramic samples was measured and
compared. The results of the density
measurements showed that the addition of
zirconia powder to alumina increases the density
of the sintered ceramic samples. The density
closest to the theoretical one was observed for
the composition of 99% Al2O3 + 1% ZrO2.
Although the addition of zirconia powder
 increased the density of ceramic samples, it is
still lower that the theoretical one. Therefore, it
must be considered to add various additives or
to modify the sintering process to further
increase the density.
5. ACKNOWLEDGEMENTS
This work has been fully supported by the
Croatian Science Foundation within the project
IP-2016-06-6000: Monolithic and Composite
Advanced Ceramics for Wear and Corrosion
Protection (WECOR).
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