J. Am. Ceram. Soc.
, 90 [5] 1420–1426 (2007)
Journal
Influence of CeO2 Reduction on the Microstructure and Mechanical
Properties of Pulsed Electric Current Sintered Y2O3–CeO2
Co-Stabilized ZrO2 Ceramics
S. G. Huang, K. Vanmeensel, O. Van der Biest, J. Vleugelsw
Department of Metallurgy and Materials Engineering, Katholieke Universiteit Leuven, Kasteelpark Arenberg 44,
The combination of yttria co-stabilization and pulsed electric
current sintering allowed full densification of CeO2-containing
ZrO2 ceramics in a graphite environment, while avoiding spon-
taneous catastrophic material degradation due to ceria reduc-
tion. Tetragonal ZrO2 ceramics were obtained by pulsed electric
current sintering (PECS) of 1 mol% Y2O316 mol% CeO2
(1Y6Ce) stabilizer-coated monoclinic ZrO2 powder with 2 wt%
Al2O3 as sintering additive for 2 min at 14501 or 15501C under a
maximum pressure of 60 MPa. In addition, a 2 mol% Y2O3
doped ZrO2 (2Y) ceramic was used as reference material to
elucidate the effect of CeO2 reduction in the densified 1Y6Ce
ceramics. The influence of the CeO2 reduction and sintering
temperature on the microstructure and mechanical properties of
the co-stabilized ZrO2 ceramics was investigated. A graded mi-
crostructure with a gradient in color and mechanical properties
were observed in the 1Y6Ce ceramic sintered at 14501C, where-
as the 1Y6Ce ZrO2 sintered at 15501C and the 2Y ceramic had
a uniform color and mechanical properties. Additionally, the
formation of an elongated CeAl11O18 (Ce2O3 . 11Al2O3) phase
was observed in the 1Y6Ce ceramic sintered at 15501C. The
formation of the graded color, the presence of the CeAl11O18
phase, as well as the graded fracture toughness profile were ex-
plained in terms of the gradual reduction of CeO2 to Ce2O3 in
the 1Y6Ce ceramic.
I. Introduction
T ETRAGONAL ZrO2 polycrystalline (TZP) ceramics have excel-
lent mechanical properties due to the effect of transforma-
tion toughening.1 Two to three mol% Y2O3-doped tetragonal
ZrO2 (Y-TZP) exhibits a high toughness and strength. The poor
thermal stability, however, largely limits its application in humid
atmosphere or hot aqueous solution.2,3 Doping CeO2 into
ZrO2–Y2O3 mixtures, on the other hand, has been reported to
significantly improve the hydrothermal stability and mechanical
properties of Y-TZP.4–6 ZrO2 ceramics are normally densified
by pressureless sintering in air or oxidizing atmosphere, resulting
in a long sintering cycle to obtain full densification. Extensive
grain coarsening usually occurs during sintering of fine-grained
ceramics.
Pulsed electric current sintering (PECS) or spark plasma sin-
tering is capable of fast sintering ceramic powder to a high den-
sity at a relatively lower temperature or shorter time compared
with conventional sintering.7 During PECS, the starting powder
is usually inserted in a graphite die/punch set-up and sintered in
vacuum or under inert atmosphere, generating a reducing sin-
R. Cutler—contributing editor
Manuscript No. 22105. Received August 11, 2006; approved December 22, 2006.
This work was financially supported by the GROWTH program of the Commission of
the European Communities under project contract No. G5RD-CT2002-0732.
w
Author to whom correspondence should be addressed. e-mail: Jozef.Vleugels@
mtm.kuleuven.be
1420
DOI: 10.1111/j.1551-2916.2007.01570.x
r 2007 The American Ceramic Society
B-3001 Heverlee, Belgium
tering environment or extremely low oxygen partial pressure.
When sintering CeO2-containing materials, the atmosphere
must be taken into account as CeO2 can be partially reduced
to Ce2O3 in vacuum or low oxygen partial pressure atmos-
pheres.
The main concern related to the reduction of Ce-TZP is its
effect on the stability of the tetragonal zirconia (t-ZrO2) phase at
room temperature. In fact, cracking is always observed due to
the destabilization and spontaneous transformation of the t-
ZrO2 phase as a result of the reduction of Ce–TZP, especially in
a graphite environment.8–10 The redox behavior of CeO2 and
CeO2–ZrO2 solid solutions was recently assessed from a ther-
modynamic point of view,11,12 revealing that Ce14 in CeO2 or
ZrO2–CeO2 solid solutions can be gradually reduced to Ce13 at
elevated temperature in vacuum of 10 1–10 2 Pa, inert atmos-
pheres (Ar, He), or under low oxygen partial pressures. The
fracture toughness on the surface layer of fully dense air-sintered
Ce–TZP could be improved from 8 up to 16 MPa
m1/2 by
means of an annealing process in Ar (5% N2, 1.2 ppm O2) at
14501C.13 Heussner et al.8 observed an improved bending
strength of 12 mol% Ce–TZP from 240 to 545 MPa after an-
nealing in N2 at 14001C for 2 h. The increased toughness and
strength were explained in terms of the partial reduction of Ce41
and segregation of Ce31, resulting in a TZP matrix with en-
hanced transformability. On the other hand, a heat treatment of
Ce–TZP in H2 for 8 h at 10001C was reported to increase the
hardness but decrease the fracture toughness.14
By a combinatorial approach of yttria co-stabilization and
PECS, this study aims to investigate the possibility to fully den-
sify CeO2-containing ZrO2 ceramics in a graphite environment,
while avoiding spontaneous catastrophic material degradation
due to ceria reduction. The effect of the sintering condition on
the phase composition, microstructure, and mechanical proper-
ties of as-sintered 1 mol% Y2O316 mol% CeO2 co-stabilized
TZP, PECS in vacuum in a graphite die-punch set-up is inves-
tigated. In particular, the possible formation of a graded micro-
structure and mechanical properties was examined and
correlated to the CeO2 reduction.
II. Experimental Procedure
(1) Materials Preparation
Based on literature data,5,6 the optimum (Y,Ce)-TZP compos-
ition contains 1.12–1.5 mol% Y2O3 and 6.5–7.0 mol% CeO2,
exhibiting a strength of 800–900 MPa in combination with a
fracture toughness of 10–15 MPa
m1/2 and high resistance to
low temperature degradation. The dispersion of fine Al2O3 par-
ticles in a TZP matrix was reported to enhance sintering, in-
crease the fracture toughness and improve the thermal
stability.1,15 Therefore, the selected ZrO2 powder was co-stabil-
ized with 1 mol% Y2O3 and 6 mol% CeO2 (1Y6Ce) with 2 wt%
Al2O3 as sintering additive. In addition, a 2 mol% Y2O3-stabil-
ized ZrO2 (2Y) with 2 wt% Al2O3 was prepared as reference
material as Y-TZP should be stable under reducing conditions.
 15512916, 2007, 5, Downloaded from https://ceramics.onlinelibrary.wiley.com/doi/10.1111/j.1551-2916.2007.01570.x by Indian Institute Of Technology, Wiley Online Library on [05/06/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
May 2007 Influence of CeO2 Reduction on Sintered Y2O3–CeO2 Co-Stabilized ZrO2 Ceramics 1421

Commercially available monoclinic ZrO2 with a crystallite size

of 27 nm and a specific surface area of 15.9 m2/g (grade TZ-0,
Tosoh, Tokyo, Japan), Y2O3 (grade YT-603, Atlantic Equip-
ment Engineers, Bergenfield, NJ), Ce(NO3)3
6H2O (Chempur,
Karlsruhe, Germany) and Al2O3 (grade SM8, Baikowski, La
Balme de Sillingy, France) powders were used as starting mate-
rials. The processing route to obtain Y2O3-coated and mixed
Y2O3–CeO2 coated ZrO2 powder is described elsewhere.6,16
PECS (Type HP D 25/1, FCT systeme, Rauenstein, Ger-
many) was performed in vacuum in a + 5 20 mm graphite die/
punch set-up at 14501 and 15501C under a pressure of 60 MPa
for 2 min. The heating and cooling rates were 1001 and 2001C/
min, respectively. The temperature was measured by a two-color
pyrometer (4001–23001C, Impac, Chesterfield, U.K.) focused at
the bottom of a central bore hole in the upper punch, about 2
mm from the top surface of sample. The applied pressure was
adjusted within 0.5 min from 16 to 30 MPa at 10501C and from
Fig. 1. Shrinkage behavior of the 1Y6Ce ceramic, pulsed electric cur-
30 to 60 MPa when reaching the sintering temperature. After
rent sintered for 2 min at 14501C and 60 MPa.
sintering, the samples had a diameter of 20 mm and thickness of
4 mm. The disc-shape samples were cross-sectioned and polished
to a mirror finish with 1 mm diamond paste.
Densification was completed when reaching the sintering
(2) Characterization temperature at a pressure of 60 MPa. Full densification of the
nanocrystalline Y–Ce–TZP powders is completed within 20 min,
The bulk density of the sintered samples was measured in eth- heating and cooling included. For the 2Y ceramic, the maximum
anol. The microstructure of the thermally etched (20 min in air densification rate was observed at 12981C.
at 13501C) and fractured surfaces was examined by scanning
electron microscopy (SEM, XL30-FEG, FEI, Eindhoven, the
Netherlands), equipped with an energy-dispersive analysis sys- (2) Microstructural Observation
tem (EDS, EDAX, Tilburg, the Netherlands) for compositional
A gradual color change along the axial direction from brown
analysis. The average grain size was determined from SEM mi-
at the edge to orange in the core was observed on the cross-
crographs using Image-pro Plus software,17 measuring the linear
sectioned 1Y6Ce ceramics sintered at 14501C, whereas a homo-
intercept length of at least 200 ZrO2 grains for each material
geneous chocolate color was observed for the ceramics sintered
grade. X-ray diffraction (XRD, 3003-TT, Seifert, Ahrensburg,
at 15501C, as shown in Fig. 2. The 2Y grade has a homogeneous
Germany) was used for phase identification on the polished
gray color. 1Y6Ce or 2Y ceramics obtained by pressureless sin-
cross-sectioned surfaces and fractured surfaces of the sintered
tering at 14501C in air have a pale yellow color.6 In this study,
ceramics. Phase analysis was performed by measuring the in-
the gradient color in the 1Y6Ce ceramic PECS at 14501C and
tensities of the (11–1) and (1 1 1) peaks of m-ZrO2 and the (1 1 1)
the darkening of the ceramic sintered at 15501C indicate the ex-
peak of the t-ZrO2 phase according to the formula proposed by
istence of a reduction from CeO2 to Ce2O3.
Toraya et al.18 The transformability of the t-ZrO2 phase that
A number of studies reported on the reduction-induced ef-
undergoes a stress-induced martensitic transformation during
fects in CeO2-containing ZrO2-based ceramics.21–23 The origin
fracture was determined from the m-ZrO2 phase vol% differ-
of coloration or darkening of 12 mol% CeO2–ZrO2 induced by
ence on the fractured and polished surfaces. The Vickers hard-
heat treatment in H2 and Ar above 10001C for 1 h was con-
ness, HV10, was measured (Model FV-700, Future-Tech Corp.,
firmed to be associated with the valence change from Ce41 to
Tokyo, Japan) with an indentation load of 98.1 N. The inden-
Ce31 by XPS and XRD.22 CeO2 is known to change color de-
tation toughness, KIC, was calculated from the length of the ra-
pending on the oxygen deficiency, such as pale yellow for CeO2,
dial cracks originating from the indentations according to the
blue for CeO1.84, and blue–black for CeO1.73.24 In the present
Anstis formula.19 The elastic modulus, E, of the 1Y6Ce and 2Y
experiments, the samples were in close contact with the graphite
ceramics was measured on the as-sintered PECS disks (30 mm
die and punch during sintering, resulting in a lower oxygen par-
diameter) by the resonance frequency method.20 The resonance
tial pressure at the sample surface compared with the core and a
frequency was measured by the impulse excitation technique
concomitant oxygen partial pressure gradient in the sample. The
(Grindo-Sonic, J. W. Lemmens N. V., Leuven, Belgium). The
presence of graphite surrounding the 1Y6Ce powder compact
reported mechanical properties are the mean and standard de-
accelerates the reduction process. After thermal etching in air,
viation of five measurements.
the color of the PECS 1Y6Ce ceramics changed back to the
normal pale yellow, indicating re-oxidization of some oxygen
III. Results and Discussion deficient CeO2 x to CeO2, whereas the reduction color remained
when thermal etching in a mixture of N2 and Ar. No micro-
(1) Densification Behavior of ZrO2 Ceramics
Despite the short sintering cycle of 2 min at 14501C under a
pressure of 60 MPa, the PECS processed ceramics reached full
density, as could be deduced from SEM investigation by the
absence of pores on cross-sectioned samples. The densification
and shrinkage rate of the ceramics was recorded by the dis-
placement of the upper piston of the PECS unit, as illustrated in
Fig. 1 for the 1Y6Ce ceramic. Densification started at 10501C
(peak 1 in Fig. 1) upon increasing the pressure from 16 to 30
MPa, resulting in particle rearrangement. A strong shrinkage
and rapid densification were observed around 12601C (peak 2
in Fig. 1). The presence of the densification rate peak 3 in Fig. 1
arises from the pressure increase up to 60 MPa when reaching
the sintering temperature and corresponds with the elimination Fig. 2. Overview of the cross-sectioned surface of the 1Y6Ce ceramics
of residual porosity and compaction of the graphite punches. sintered at 14501 (top) and 15501C (bottom).
 15512916, 2007, 5, Downloaded from https://ceramics.onlinelibrary.wiley.com/doi/10.1111/j.1551-2916.2007.01570.x by Indian Institute Of Technology, Wiley Online Library on [05/06/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
1422 Journal of the American Ceramic Society—Huang et al. Vol. 90, No. 5

structural differences were observed after thermal etching in air
or a mixture of N2 and Ar.
The 2Y ceramic has a homogeneous gray color after PECS,
which converted to white after thermal etching in air. The dark-
ening of hot pressed ZrO2-based ceramics is commonly attrib-
uted to carbon diffusion from the graphite die or punches into
the zirconia material. The carbon incorporated in TZPs was
identified as either an ether-type C–O or a carbonyl-type
C 5 O.25 Moreover, carbon was reported to enter the ZrO2 lat-
tice when carburizing in a graphite powder bed.26 The darkening
of the 1Y6Ce ceramic due to carbon diffusion is not so obvious
because of the superimposed color change due to the reduction
of the ceria stabilizer.
Representative micrographs at the surface and core of the
cross-sectioned thermally etched 1Y6Ce ceramic, PECS for 2
min at 14501C, are shown in Figs. 3(a) and (b), respectively. The
bright and dark contrast phases correspond to ZrO2 and Al2O3
grains. In contrast to the well-dispersed Al2O3 grains in the
1Y6Ce grade sintered at 14501C, elongated grains are uniformly
dispersed in the surface area of the 1Y6Ce ceramic sintered for 2
min at 15501C (see Fig. 3(c)), whereas equiaxed Al2O3 grains are
present in the core (see Fig. 3(d)). It should be noted that similar
microstructures were observed on the surface of the 1Y6Ce cer-
amics after thermal etching in air or N21Ar atmosphere, even
though the ceramics exhibited a different color after the thermal
treatment. A higher magnification image of such an elongated
particle along with the energy dispersive analysis by X-ray
(EDAX) point analysis results are shown in Figs. 3(e) and (f).
The elongated dark contrast phase contains Al, O, and Ce
atoms, whereas the presence of a weak Zr peak can be either
from neighboring ZrO2 grains or small ZrO2 grains incorporat-
ed into the dark crystals. On the other hand, Ce was not detected
in the equiaxed Al2O3 grains in the core area of the material. The
Ce/Al/O atomic ratio of the elongated phase was measured to be
3.49/35.67/60.85, which is in good agreement with the stoichio-
metric CeAl11O18 compound composition (3.45 at.% Ce, 37.93
at.% Al, 62.07 at.% O). The presence of this phase has to be
related to the reduction of CeO2 to Ce2O3, as it is only found in
the more reduced edge layer and it is only stable, beside CeAlO3,
in the Al2O3–Ce2O3 system.27,28
An identical elongated Al2O3-based phase was reported in
10Ce-TZP/30 vol% Al2O3 composites sintered at 15001C.29
More recently, Tsukuma reported that the CeAl11O18 phase
can be formed from a powder mixture containing 9.05 wt%

Fig. 3. Scanning electron micrographs of the surface (a) and core (b) area of the 1Y6Ce ceramic pulsed electric current sintered (PECS) at 14501C and
the surface (c) and core (d) area of the 1Y6Ce ceramic PECS at 15501C, together with a detail (e) and energy dispersive analysis by X-ray spectrum (f) of
an elongate CeAl11O18 grain in the surface area of the latter ceramic grade.

May 2007 Influence of CeO2 Reduction on Sintered Y2O3–CeO2 Co-Stabilized ZrO2 Ceramics
CeO2, 30.95 wt% Al2O3, and 60 wt% 2Y-TZP sintered at
15001C in an Ar stream in a carbon-lined tube furnace, where-
as it was not formed when annealing at 14001C. Annealing in
oxygen at 15001C caused complete conversion of the CeAl11O18
phase into Al2O3 and CeO2.30 This temperature and oxygen par-
tial pressure dependency also explain why the CeAl11O18 phase is
only present in the surface region of the 1Y6Ce ceramics PECS at
15001C and not at all in those PECS at 14501C. It should, how-
ever, be clear that Ce31 ions segregate to the grain boundaries at
14501C, forming a Ce-containing amorphous grain boundary
phase, as reported for the CeO21La2O3-doped TZP system.31
As shown in Fig. 3(e), the ZrO2 grain size in the vicinity of the
CeAl11O18 grains is substantially larger than in the matrix. As-
suming that the local ceria content is energetically more favor-
ably dissolved by the formation of CeAl11O18 grains rather than
into the contacting ZrO2 grains would imply that the stabilizer
content in these ZrO2 might be very low. The fact that m-ZrO2
grains are larger than t-ZrO2 grains,32 could explain their rela-
tively larger grain size.
The average ZrO2 grain size in the edge layer of the 1Y6Ce
ceramic sintered at 14501C is about 0.17 mm (Fig. 3(a)), which is
significantly smaller than the 0.44 mm in the core (Fig. 3(b)).
Moreover, the core shows a clearly bimodal grain size distribu-
tion with coarse 1.1 mm grains, while the finer grains are in the
0.1–0.4 mm range. When PECS at 15501C, the ZrO2 grains be-
come coarser and the average grain size increases to 0.56 mm at
the edge and 0.58 mm in the core area respectively, as indicated
in Figs. 3(c) and (d). An even more obvious bimodal grain size
distribution is present all over the sample, with coarse grains up
to 1.5–2.0 mm. In the 2Y ceramic PECS at 14501C, the Al2O3
particles are homogeneously distributed in the ZrO2 matrix, as
shown in Figs. 4(a) and (b). The average ZrO2 grain size is 0.53
and 0.54 mm in the surface and core region, respectively.
Besides the effect of CeO2 reduction, the graded microstruc-
ture can also arise from a graded temperature distribution inside
the sample. During PECS, the temperature distribution can be
very complicated and is determined by the geometry of the sin-
tering set-up, the die/punch materials and the thermo-electrical
properties of the sintering powder compact. Recently, Van-
meensel et al.33 investigated the temperature distribution in elec-
trical insulating ZrO2 and electrical conducting TiN samples
Fig. 4. Scanning electron microscope of the 2Y ceramic, pulsed electric
current sintered at 14501C, (a) surface area and (b) core area.
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1423
Fig. 5. Simulated temperature distribution in a Y2O3-doped tetragonal
ZrO2 ceramic during the 2 min dwell time when pulsed electric current
sintered at 14501C.
during PECS by a mixed experimental-theoretical approach, re-
vealing that the temperature distribution in the ZrO2 compact
was quite homogeneous. The simulated temperature distribution
in a 2Y–TZP ceramic with a final height of 4 mm and a diameter
of 20 mm is presented in Fig. 5. The axial temperature gradient
during the dwell time of 2 min at 14501C is o21C in the 2Y
ceramic. The radial temperature gradient in the bulk of the ma-
terial is homogeneous but reaches about 1001C in the outer 1
mm. The homogeneous temperature distribution along the axial
direction is confirmed by the homogeneous microstructure of
the 2Y ceramic, as illustrated in Fig. 4. As there is no reason to
believe that the temperature distribution in the 1Y6Ce ceramics
would be less homogeneous than in the 2Y ceramic, the ob-
served microstructural changes in the 1Y6Ce ceramics should be
completely attributed to the partial reduction of CeO2. Besides
the sintering temperature, the stabilizer type and content in the
ZrO2 solid solution strongly influence the ZrO2 grain size and
growth. The average ZrO2 grain size was reported to decrease
from 0.58 mm for a 1Y6Ce to 0.53 mm for a 1Y4Ce TZP ceramic
when conventional sintering in air for 1 h at 14501C,6 revealing
that the grain size decreases with decreasing CeO2 co-stabilizer
content. Moreover, solutes with a larger radius are correlated
with a smaller ZrO2 grain size.34
During PECS in vacuum and a graphite environment, a grad-
ed oxygen partial pressure is established across the sample re-
sulting in a reduction of CeO2 to Ce2O3 in the TZP, progressing
from the sample surface toward the interior. The reduction is
associated with an increase in the ionic radius from 0.101 nm for
Ce41 to 0.111 nm for Ce31. Ce2O3 is unstable in the ZrO2 lattice
because of an approximately 40% mismatch in ionic radii be-
tween Ce31 and Zr41, resulting in a decreased solubility of CeO2
in t-ZrO2 and a high elastic lattice strain.31,35 As a result of the
reduction, Ce31 ions diffuse out of the t-ZrO2 grains reducing
the intercrystalline stabilizer content and thereby increasing the
transformability of the remaining TZP matrix.31 The Ce31 ions
expelled from the t-ZrO2 grains recombine with the Al2O3 sin-
tering aid and formed the elongated CeAl11O18 grains in the
1Y6Ce ceramic sintered at 15501C. The much smaller grain size
in the surface layer compared with the core of the 1Y6Ce ce-
ramic sintered at 14501C can therefore be explained by the re-
duced CeO2 stabilizer content and the large radius of Ce31 ions.
At 15501C, the grains are coarser due to the increased sintering
temperature, whereas the grain size gradient diminished due to
the more homogeneous CeO2 reduction throughout the sample.
(3) Phase Analysis
Before sintering, the stabilizer-coated starting powders were
characterized as m-ZrO2.6 After densification, only a trace
amount of m-ZrO2 phase was observed on the polished

1424 Journal of the American Ceramic Society—Huang et al.
Fig. 6. X-ray diffraction patterns of the polished (a) and fractured (b)
cross-sectional surfaces of the 2Y and 1Y6Ce ceramics, obtained by
pulsed electric current sinterings at 14501 and 15501C.
surfaces, revealing that the stabilizer effectively dissolved into
the ZrO2 grains to stabilize the system despite the very short
sintering cycle, as indicated in Fig. 6 for the XRD patterns on
polished and fractured cross sections of the 2Y and 1Y6Ce cer-
amics. The 2Y starting powder is converted into a 2Y-TZP ce-
ramic. A shoulder peak was detected in the 1Y6Ce ceramics on
the left side of the (111) t peak, which increased with increasing
sintering temperature, whereas a symmetrical t-ZrO2 peak was
found in the 1Y6Ce ceramics sintered at 14501C for
1–4 h in air.6 Several interpretations on the shoulder peak, ob-
served in both partially and fully stabilized ZrO2, are report-
ed.36,37 Recently, Kondoh38 thoroughly examined the origin of
this peak and concluded that it was caused by lattice distortion
and disappears with aging. As described earlier, the CeO2 re-
duction is associated with a 40% mismatch in ionic radii be-
tween Ce31 and Zr41, resulting in a high elastic lattice strain and
Table I. Phase Constitution and Mechanical Properties of the PECS ZrO2 Ceramics
Grades Sintering T (1C) Phases E (GPa)
1Y6Ce 1450 t1m 19976
1Y6Ce 1550 t1m1CeAl11O18 20575
2Y 1450 t1m 20375
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Vol. 90, No. 5
therefore lattice distortion. After thermal etching for 20 min at
13501C in air, the shoulder peak completely disappeared and the
resulting t-ZrO2 peak becomes symmetrical, as shown in Fig
6(a). The experimental results indicated that the shoulder peak is
due to a lattice distortion, rather than the formation of c-ZrO2
phase. Despite the reduction of CeO2 to Ce2O3 and the accom-
panying diffusion of Ce31 from the grains, it should be clear that
enough Ce1Y ions are present in the TZP structure to stabilize
the t-ZrO2 phase as it was reported that ZrO2 ceramics with an
Y2O3 content below 1.4 mol% are fully m-ZrO2.39
Although the elongated dark atomic number contrast
CeAl11O18 grains can be clearly observed in the microstructure
of the 1Y6Ce grade sintered at 15501C, they could not be de-
tected by XRD due to its relatively low volume (3.5 vol% as
determined by image analysis).
The amount of m-ZrO2 phase increased dramatically on the
fracture surfaces of all the three samples, as shown in Fig. 6(b),
indicating high t-ZrO2 phase transformability. Comparing the
amount of m-ZrO2 phase on the polished and fractured surface
allows to calculate the average t-ZrO2 phase transformability as
48.5, 46.5, and 77.1 vol% for the 2Y, 1Y6Ce (at 14501C) and
1Y6Ce (at 15501C), respectively. The t-ZrO2 transformability of
the 1Y6Ce sintered at 15501C is much higher due to the higher
degree of CeO2 reduction and the larger ZrO2 grain size.
(4) Mechanical Properties
Representative Vickers indentations at different locations on the
cross-sectioned 1Y6Ce ceramics are presented in Fig. 7, reveal-
ing that the radial cracks are significantly shorter in the surface
region compared with the core when PECS at 14501C. When
sintering at 15501C, the length of the radial cracks at the surface
and the core is short and comparable. The corresponding E-
moduli, hardness, and fracture toughness are summarized in
Table 1, whereas the hardness and toughness profiles along the
axial direction of the sample (only half of the sample) are pre-
sented in Fig. 8.
A large gradient in toughness was observed in the 1Y6Ce
ceramic sintered at 14501C, decreasing dramatically from
10.370.2 MPa
m1/2 at the surface to 6.570.3 MPa
m1/2 in
the center, accompanied by a similar hardness value of
12.1070.15 and 11.9270.11 GPa. At 15501C, the toughness
was homogeneous, i.e., 9.570.2 MPa.m1/2 in the surface region
and 9.570.2 MPa.m1/2 in the core. A homogeneous toughness
of 6.8 MPa
m1/2 and hardness of 12.90 GPa was obtained for
the 2Y ceramic PECS at 14501C.
The toughness difference of the ceramics correlates well with
the measured overall t-ZrO2 phase transformability reported
above. Although the t-ZrO2 phase transformability and con-
comitant toughness of TZP ceramics increases with increasing t-
ZrO2 grain size up to the critical grain size for spontaneous
transformation,1,35 the surface region of the 1Y6Ce ceramic
PECS at 14501C with a smaller ZrO2 grain size of 0.17 mm
has a higher toughness than the larger grained core. Moreover,
the toughness of the surface region is even higher than that of
the larger grained (0.58 mm) 1Y6Ce grade conventionally sin-
tered in air for 1 h at 14501C.6 This can only be explained by a
higher t-ZrO2 phase transformability due to a reduced stabilizer
level caused by the reduction of CeO2 to Ce2O3 in the surface
region. The observed phenomena during PECS of the 1Y6Ce
ceramic are consistent with the toughening of Ce-TZP by re-
duction-induced phase transformation.10 When PECS for 2 min
HV10 (GPa) KIC (MPa.m1/2)
Edge Center Edge Center
12.1070.15 11.9170.11 10.370.2 6.570.2
11.8470.14 11.8070.17 9.570.2 9.470.2
12.9170.09 12.8970.19 6.870.3 6.770.2
 15512916, 2007, 5, Downloaded from https://ceramics.onlinelibrary.wiley.com/doi/10.1111/j.1551-2916.2007.01570.x by Indian Institute Of Technology, Wiley Online Library on [05/06/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
May 2007 Influence of CeO2 Reduction on Sintered Y2O3–CeO2 Co-Stabilized ZrO2 Ceramics 1425

Fig. 7. Optical micrographs of the Vickers indentation and radial crack pattern of the 1Y6Ce ceramics. Surface region (a) and core (b) when pulsed
electric current sintered (PECS) at 14501C and surface region (c) and core (d) when PECS at 15501C.

(a) 11 (b) 13.1

2Y,1450°C
13.0
Fracture toughness(MPa m1/2)

10 1Y6Ce,1550°C
12.9
Hardness (GPa)

9 12.8

12.7 1Y6Ce,1450°C
8 1Y6Ce,1450°C

2Y,1450°C 12.2
7 12.0

11.8
6
1Y6Ce,1550°C
11.6
0.0 0.4 0.8 1.2 1.6 2.0 2.4 0.0 0.4 0.8 1.2 1.6 2.0 2.4
Distance (mm) Distance (mm)
Fig. 8. Toughness (a) and Vickers hardness (b) profiles along the central axial direction of the cross-sectioned 1Y6Ce and 2Y ceramics, pulsed electric
current sintered at 14501 and 15501C.

at 15501C, the toughness difference at the edge and core de-
creased because of the more homogeneous CeO2 reduction
throughout the sample.
IV. Conclusions
1 mol% Y2O316 mol% CeO2 or 2 mol% Y2O3 stabilizer coated
m-ZrO2 powder with 2 wt% Al2O3 addition could be fully den-
sified into a (Y,Ce)-TZP or a Y-TZP by PECS in a graphite die/
punch set-up and vacuum for 2 min at 14501 or 15501C, without
spontaneous catastrophic material degradation due to ceria
reduction. A homogeneous 2Y-TZP was obtained at 14501C,
whereas a 1Y6Ce ceramic with graded and homogenous
properties was formed when PECS at 14501 and 15501C
respectively.
The 1Y6Ce ceramic sintered at 14501C was composed of a
high toughness (10.2 MPa
m1/2) surface region with a fine
grained t-ZrO2 microstructure and a lower toughness core (6.4

1426 Journal of the American Ceramic Society—Huang et al.
MPa
m1/2) with a bimodal ZrO2 grain size distribution. The
hardness was comparable throughout the material. At 15501C,
the 1Y6Ce ceramic had a homogeneous high toughness of 9.5
MPa
m1/2 in combination with a hardness of 11.80 GPa. The
relatively large elongated CeAl11O18 grains present in the surface
region did not change the hardness and toughness compared
with the core that contains Al2O3.
The microstructural gradient and enhanced toughness in the
1Y6Ce ceramic could be attributed to the partial reduction of
CeO2 to Ce2O3 during PECS resulting in an increased t-ZrO2
phase transformability as a result of the reduced CeO2 solubility
in the t-ZrO2 phase at lower oxygen partial pressure, which also
results in the formation of CeAl11O18 grains from the Al2O3
sintering aid and the excess CeO2 stabilizer.
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