Effect of alumina-doping on grain boundary

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segregation-induced phase transformation in yttria-stabilized

tetragonal zirconia polycrystal
Koji Matsui,a) Nobukatsu Ohmichi, and Michiharu Ohgai
Synthetic Chemicals Production, Tosoh Corporation, Shunan, Yamaguchi 746-8501, Japan
Hidehiro Yoshida
National Institute for Materials Science, Tsukuba, Ibaraki 305-0047 Japan
Yuichi Ikuhara
Institute of Engineering Innovation, School of Engineering, The University of Tokyo, Bunkyo-ku,
Tokyo 113-8656, Japan

(Received 14 March 2006; accepted 3 May 2006)

The microstructure in a small amount of Al2O3-doped Y2O3-stabilized tetragonal

zirconia polycrystal (Y-TZP) sintered at 1100–1650 °C was examined to clarify the
effect of Al3+ ions segregated at grain boundaries on cubic-formation and grain-growth
processes. The sintering rate in Y-TZP was remarkably enhanced by Al2O3-doping. In
addition, at temperatures >1500 °C, grain growth remarkably proceeded, and the
fraction of the cubic phase increased in comparison with that of undoped Y-TZP.
High-resolution electron microscopy and nanoprobe x-ray energy dispersive
spectroscopy measurements revealed that no amorphous layer existed along the
grain-boundary faces in Al2O3-doped Y-TZP and that Y3+ and Al3+ ions segregated at
grain boundaries over widths of ∼10 and ∼6 nm, respectively. At 1100 °C, Al3+ ions
started to segregate at grain boundaries, and the segregation peak of Al3+ ions
increased as the sintering temperature increased. Cubic-formation and grain-growth
behaviors in Al2O3-doped Y-TZP were reasonably interpreted by taking into account
the effect of Al3+ ions segregating along grain boundaries.

I. INTRODUCTION found in Y-TZP in comparison to that in Y2O3-stabilized

Yttria-stabilized tetragonal zirconia polycrystal (Y-
TZP) is an important structural ceramic with excellent
mechanical properties, such as high fracture toughness,
strength, and hardness, and is used for products such as
optical fiber connectors, grinding media, and precision
mechanical parts. The hydrolysis process is the best in-
dustrial manufacture method for producing Y-TZP pow-
der. To develop new Y-TZP powder with forming and
sintering characteristics by the hydrolysis process, it is
particularly important to clarify the sintering mechanism
in Y-TZP.
So far, two models based on the solute-drag effect and
Zener’s pinning effect have been proposed to understand
the grain-growth behavior in Y-TZP. The model of the
solute-drag effect in Y-TZP was first proposed by Lee
and Chen1 to explain the slow grain-growth behavior
a)
Address all correspondence to this author.
e-mail: k_matui@tosoh.co.jp
DOI: 10.1557/JMR.2006.0274
cubic zirconia. The model of the Zener’s pinning effect
was firstly proposed by Lange.2 Subsequently, Sakuma
and Yoshizawa3,4 quantitatively analyzed the grain-
growth process using a rate equation based on Zener’s
pinning model to interpret the grain growth of dual-phase
ZrO2 generated after the equilibrium partitioning. Grain-
boundary characterization is a key to reveal the grain-
growth mechanism. The grain-boundary structure in Y-
TZP was intensively investigated by high-resolution
electron microscopy (HREM), and it had been concluded
that an amorphous phase existed in grain boundaries.5–10
However, Ikuhara et al.11 first reported that, from HREM
and nanoprobe x-ray energy dispersive spectroscopy
(EDS) measurements in Y-TZP, no amorphous phase is
observed along grain boundaries, but Y3+ ions segregate
at grain boundaries over a width of 4–6 nm. The grain-
boundary structure was clarified by their observation re-
sults. On the other hand, using the Rietveld analysis,
Ohmichi et al.12 investigated the formation behavior of
the cubic phase in Y-TZP and reported that the amount of
cubic phase increased and the Y2O3 concentration within

2278 J. Mater. Res., Vol. 21, No. 9, Sep 2006 © 2006 Materials Research Society
 K. Matsui et al.: Effect of alumina-doping on grain boundary segregation-induced phase transformation in Y-TZP
tetragonal phase decreased as the sintering temperature
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increased.12 We reported in-depth analysis of microstruc-
ture change in Y-TZP during the sintering process, using
HREM– and scanning transmission electron microscopy
(STEM)–nanoprobe EDS techniques, and the cubic-
formation and grain-growth mechanisms can be ex-
plained using the Grain Boundary Segregation-Induced
Phase Transformation (GBSIPT) model and the solute-
drag effect of Y3+ ions segregating along the grain
boundary, respectively.13,14
On the other hand, from the industrial standpoint, it is
particularly important to clarify the role of Al2O3, which
is one of the additives accelerating sintering. The role of
Al2O3 on the microstructure and properties of Y-TZP has
been reported previously by several researchers.15–17
However, the effect of Al2O3 on the microstructural for-
mation process in Y-TZP has not yet been clarified.
In the present study, we examined the microstructure
of grain boundaries and grain interiors in a small amount
of Al2O3-doped Y-TZP sintered at 1100–1650 °C to sys-
tematically investigate the effect of Al2O3-doping on
cubic-formation and grain-growth processes in detail.
The Al2O3-doping effect was discussed by comparing the
results of the present analysis with previous analysis for
undoped Y-TZP.14
II. EXPERIMENTAL PROCEDURES
A. Specimen preparation
A small amount of Al2O3-doped Y-TZP was prepared
as follows. Y-TZP powder containing 2.9 mol% (5.2
mass%) Y2O3 and 0.31 mol% (0.25 mass%) Al2O3, and
with a specific surface area of 15 m2/g (TZ-3YE grade,
Tosoh, Tokyo, Japan), manufactured by the hydrolysis
method was used as a starting raw material. This powder
was uniaxially pressed into a disk under 70 MPa pres-
sure. The resulting green compacts were sintered at
1100–1650 °C for 2 h at a constant heating rate of
100 °C/h in air. The specimens of the resulting Al2O3-
doped Y-TZPs are termed 3YE. The experimental con-
dition to prepare the specimens is the same as the con-
dition to sinter Y-TZP powder without Al2O3 described
in our previous paper.14 The Y-TZP powder without
Al2O3 (TZ-3Y grade, Tosoh, Tokyo, Japan) used in our
previous paper had a Y2O3 concentration of 2.9 mol%
(5.2 mass%) and a specific surface area of 15 m2/g.14 The
previous data (the undoped Y-TZPs) are termed 3Y.
B. Density and grain size measurements
The density of sintered bodies was measured by the
Archimedes method. In the case of the sintered bodies
with relative density of <80%, the density was calculated
from the weight and the size. Scanning electron micros-
copy (SEM; Model S-4500, Hitachi, Tokyo, Japan) was
J. Mater. Res., Vol. 21, No. 9, Sep 2006
used to measure the average grain sizes of the sintered
bodies. SEM specimens were polished with 3-␮m dia-
mond paste and then thermally etched for 1 h at a tem-
perature of 50 °C lower than sintering temperature of
each specimen in air. The average grain size was meas-
ured by the Planimetric method.18
C. XRD measurements
X-ray diffraction (XRD) profiles were measured at
room temperature using a powder diffractometer system
(Model MXP3, MAC Science Co. Ltd, Tokyo, Japan) and
recorded using Cu K␣ radiation, under 40 kV and 30 mA,
at a slit width of 1°. The fractions (mass%) of cubic (fc)
and tetragonal (ft) phases in the sintered bodies were
determined by the Rietveld method. The Rietveld calcu-
lation was conducted in a manner identical to those re-
ported by Ohmichi et al.14
D. Transmission electron microscopy and
nanoprobe EDS measurements
The microstructure was examined by field emission
transmission electron microscopy (TEM; Model 002BF,
Topcon, Tokyo, Japan). Specimens for TEM observa-
tions were mechanically ground to a thickness of
∼0.1 mm, further dimpled to a thickness of ∼10 ␮m, and
then ion-milled for electron transparency. Specimens sin-
tered at 1100 and 1200 °C were very porous and there-
fore were reinforced by permeating the epoxy resin be-
fore sample preparation. HREM observations were con-
ducted to examine the grain-boundary structure, using
Topcon 002BF (Tokyo, Japan) with a point-to-point
resolution of 0.17 nm. Nanoprobe EDS measurements
were performed to examine quantitatively segregation of
Y3+ and Al3+ ions at grain boundaries, using a Noran
Voyager System in the Topcon 002BF (Tokyo, Japan)
with a probe size of 0.5 nm. Four to six grain boundaries
in one specimen were analyzed. STEM and nanoprobe
EDS analyses were performed to examine the Y3+ ion
distribution within grains, using a Noran Voyager Sys-
tem in the Topcon 002BF with a probe size of 1 nm.
III. RESULTS
A. Densification, grain growth, and T → C
phase transformation
Figure 1 shows the relationship between relative den-
sity and sintering temperature for the 3YEs (Al2O3-
doped Y-TZPs) sintered at 1100–1650 °C. The relative
density of 3YE increased with increasing sintering tem-
perature and attained 99% at 1350 °C. The 3Y (undoped
Y-TZP) data reported in our previous paper14 are also
plotted in Fig. 1. The relative density of 3YE was higher
than that of 3Y at sintering temperatures of <1500 °C.
Figure 2 shows typical SEM images of 3YEs sintered at
2279
 K. Matsui et al.: Effect of alumina-doping on grain boundary segregation-induced phase transformation in Y-TZP
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FIG. 1. Dependence of relative density and average grain size in Y-
TZPs with sintering temperature. (䊉) and (䊏) indicate the relative
density and the average grain size of 3YE, respectively. (嘷) and (䊐)
indicate the relative density and the average grain size of 3Y, respec-
tively.14
(a) 1100 °C, (b) 1300 °C, (c) 1500 °C, and (d) 1650 °C.
The grain size of 3YE increased as the sintering tempera-
ture increased. To quantitatively examine the behavior of
grain growth with increasing temperature, the average
grain sizes of 3YE were determined by the Planimetric
method. The grain size of 3YE sintered at each tempera-
ture is also plotted in Fig. 1. The grain size increased
gradually up to 1400 °C and then rapidly above this tem-
perature. Comparing with previous 3Y data,14 it can be
seen that the grain-growth behavior of 3YE showed the
same tendency as that of 3Y up to 1500 °C, but when this
temperature was exceeded, the grain size of 3YE in-
creased more rapidly than that of 3Y as the sintering
temperature increased.
Figure 3 shows the relationship between the fc or ft
value and the sintering temperature for 3YEs sintered at
1100–1650 °C. The crystal phase in 3YE was monopha-
sic tetragonal zirconia (i.e., ft ⳱ 100 mass%) up to
1200 °C. At 1300 °C, the cubic phase appeared and the
value of fc was 12.7 mass%. The value of fc for 3YE
increased with increasing sintering temperature and
reached 22.9 mass% at 1650 °C. The value of ft de-
creased with increasing sintering temperature. In our pre-
vious paper, we reported that the amount of the cubic
phase formed by the tetragonal-to-cubic (T → C) phase
transformation increases with both decreasing ft value
and Y2O3 concentration within the tetragonal phase.13
Therefore, the present result can be also interpreted by
the same cubic-formation process. When 3YE data were
2280 J. Mater. Res., Vol. 21, No. 9, Sep 2006
compared with 3Y data,14 it was seen that the decreasing
ft of 3YE showed nearly the same tendency as that of 3Y,
whereas the increasing fc of 3YE exhibited nearly the
same tendency as that of 3Y up to 1500 °C, but when this
temperature was exceeded, the fc value of 3YE increased
more than that of 3Y as the sintering temperature in-
creased. If we make an analogy to our previous results,13
we can presume that the slight difference in fc is caused
primarily by the fact that the Y2O3 concentration within
the tetragonal phase of 3YE decreases more rapidly than
that of 3Y.
These experimental results revealed that when a small
amount of Al2O3 was doped to Y-TZP, the sintering rate
was remarkably enhanced, grain growth proceeded re-
markably, and the fc increased slightly at temperatures of
>1500 °C.
B. Internal structure
TEM measurements were performed to observe the
change in the internal structure in 3YE with an increase
in the sintering temperature. Figure 4 shows typical TEM
images of 3YEs sintered at (a) 1100 °C, (b) 1200 °C, (c)
1300 °C, (d) 1500 °C, and (e) 1650 °C. In the 3YE sin-
tered at 1100 °C, the network structure joined through
the neck parts among starting particles was observed.
When the sintering temperature attained 1200 °C, the
form of each particle and the network structure were no
longer seen, and grains and large pores were observed. At
1300 °C, the large pores disappeared. The grain-growth
behavior is thus consistent with the result shown in
Fig. 1.
C. Grain-interior microstructure
To examine the change in the microstructure with T →
C phase transformation in detail, the Y3+ ion distribution
of grain interiors in 3YE was analyzed using STEM and
element-mapping nanoprobe EDS techniques. Figure 5
shows typical STEM images and Y K␣ and Zr K␣ map-
ping images obtained by the STEM-nanoprobe EDS
method in 3YEs sintered at (a) 1100 °C, (b) 1200 °C, (c)
1300 °C, (d) 1500 °C, and (e) 1650 °C, respectively. Be-
cause the Zr K␣ maps of Figs. 5(a)–5(e) showed the same
homogeneous distribution, the distribution of Zr4+ ions is
almost the same irrespective of the sintering tempera-
tures. However, when the Y K␣ mapping patterns of
Figs. 5(a)–5(e) are compared, Y3+ ions are drastically
changed to heterogeneously distribute with the increas-
ing sintering temperature. In the specimens sintered at
1300 °C and below [Y K␣ maps in Figs. 5(a)–5(c)], most
of the grains were tetragonal phase because the distribu-
tion of Y3+ ions in grain interiors was nearly homoge-
neous. At 1500 °C [Y K␣ map, Fig. 5(d)], the regions
with high Y3+ ion concentrations were formed in grain
interiors, and the regions started to form from grain
 K. Matsui et al.: Effect of alumina-doping on grain boundary segregation-induced phase transformation in Y-TZP
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FIG. 2. SEM images of 3YEs sintered at (a) 1100 °C, (b) 1300 °C, (c) 1500 °C, and (d) 1650 °C.
boundaries and triple junctions. When the sintering tem-
perature increased to 1650 °C [Y K␣ map, Fig. 5(e)], the
regions with high Y3+ ion concentrations were further
partitioned. These observation results were nearly the
same as those of 3Y.14
According to Fig. 3, the fc increased with increasing
sintering temperature. Assuming that the high Y3+ ion
concentration regions are cubic phase, the present result
agrees qualitatively with the fc behavior in Fig. 3. It is
therefore concluded that the high Y3+ ion concentration
regions generated in grain interiors transform from te-
tragonal to cubic phases and the cubic phase regions are
partitioned as the sintering temperature increases. It is
presumed that this T → C phase transformation occurs by
redistribution of Y3+ ions in grain interiors and the re-
distribution process is related to the grain boundary.
D. Grain-boundary segregation
To probe the formation behavior of the grain-boundary
segregation of Y3+ ions with increasing sintering tem-
perature, grain-boundary structures and composition in
3YE were measured using HREM and nanoprobe EDS
techniques, which are very effective in analyzing a lo-
calized region. Figure 6 shows typical HREM images of
the grain-boundary faces in 3YE sintered at (a) 1100 °C,
(b) 1200 °C, (c) 1300 °C, (d) 1500 °C, and (e) 1650 °C.
The images have been taken with the boundary edge-on
to observe the grain-boundary structure directly. In
the HREM images of Figs. 6(a)–6(e), no amorphous or
second phase was observed along the grain-boundary
J. Mater. Res., Vol. 21, No. 9, Sep 2006
faces. This observation agrees with the previous
data.11,13,14,19,20 Taking into account the results of
HREM, Rietveld, and STEM-nanoprobe EDS analyses, it
can be concluded that 3YEs sintered at 1100 and 1200 °C
were composed of a single-crystal particle with mono-
phasic tetragonal.
Figure 7 shows typical Y-distribution profiles across
the grain in 3YEs sintered at (a) 1100 °C, (b) 1200 °C,
(c) 1300 °C, (d) 1500 °C, and (e) 1650 °C. The nano-
probe EDS measurements were performed with the probe
size of 0.5 nm at every 1 nm across the grain boundaries.
In the 3YE sintered at 1100 °C, Y3+ ions started to seg-
regate at grain boundaries. The Y2O3 concentration at the
grain boundary is ∼5 mol%, which is a little bit higher
than that in the grain interior. This segregation profile
represents the initial step of the segregation of Y3+ ions.
At 1300 °C, the segregation peak of Y3+ ions clearly
appeared. For the profiles in Figs. 7(a)–7(e), the Y2O3
concentrations in grain interiors were in the range of
1–4 mol%, which corresponds to that in the tetragonal
phase. It was therefore confirmed that Y3+ ions segre-
gated at grain boundaries over a width of ∼10 nm in all
grain boundaries between tetragonal and tetragonal
phases (T-T grain boundaries). The segregation behavior
of Y3+ ions obtained at the present experiments revealed
a tendency similar to that of 3Y.14
For the 3YEs sintered at 1300 °C and below, Y3+ ions
segregate at all grain boundaries, and the Y2O3 concen-
trations in grain interiors correspond to that in the te-
tragonal phase. Therefore, it is concluded that the cubic-
2281
 K. Matsui et al.: Effect of alumina-doping on grain boundary segregation-induced phase transformation in Y-TZP
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FIG. 3. Dependence of the fractions of cubic and tetragonal phases in
Y-TZPs with sintering temperature. (嘷) and (䊐) indicate 3YE and
3Y,14 respectively.
phase regions with high Y3+ ion concentration in grain
interiors shown in Figs. 5(d) and 5(e) started to form from
grain boundaries and the triple junctions in which Y3+
ions segregate. This mechanism can be reasonably inter-
preted using the GBSIPT model proposed in our previous
papers.13,14
Analogizing from the above conclusion, the region of
the segregation peak appearing clearly at 1300 °C is
2282 J. Mater. Res., Vol. 21, No. 9, Sep 2006
considered to be the possibility of transforming from
tetragonal to cubic phases. To examine this possibility,
the fraction of the cubic phase ( f⬘c) is determined by
assuming that the grain is a sphere with a diameter of D
and that the crystal structure of the grain-boundary vi-
cinity at which Y3+ ions segregate is the cubic phase. The
calculated value of f⬘c is given by Eq. (1)14:
D3 − 共D − ␻兲3
f⬘c共mass%兲 ≅ × 100 . (1)
D3
Here, ␻ is the width of the segregation of Y3+ ions.
Substituting the average grain size (D ≅ 200 nm) and the
width (␻ ≅ 6 nm) of the segregation of Y3+ ions at
1300 °C in Eq. (1), f ⬘c ≅ 9 mass% is obtained. This
calculated value is slightly smaller than the fc value
(12.7 mass%) at 1300 °C determined by the Rietveld
analysis. Therefore, this result reveals that most of the
grain boundaries at 1300 °C in which Y3+ ions segregate
have transformed from tetragonal to cubic phases, and
further, a part of cubic-phase regions formed in grain
boundaries and triple junctions may extend slightly in the
grain interior.
Because a small amount of Al2O3 was doped to 3YE,
not only Y3+ ions but also Al3+ ions were observed to
segregate at grain boundaries over a width of ∼6 nm in
T-T grain boundaries [Figs. 7(a)–7(e)]. In the 3YE sin-
tered at 1100 °C, the small segregation peak of Al3+ ions
was observed, and Al3+ ions started to segregate at grain
boundaries. At 1200 °C, the segregation peak of Al3+
ions clearly appeared. The segregation peak of Al3+ ions
increased as the sintering temperature increased. At
1650 °C, the segregation-peak height of Al3+ ions
reached ∼4.6 mol% Al2O3 and was ∼0.84 times that of
Y3+ ions (∼5.5 mol% Y2O3).
As can be seen in Figs. 5(d) and 5(e), the interfaces
between cubic and tetragonal phases are also formed in a
single domain in 3YEs sintered at 1500 °C and over. As
shown in Fig. 8, the different segregation profile of Y3+
ions from the T-T grain-boundaries was also observed at
1650 °C. The HREM image corresponding with Fig. 8
is also shown in Fig. 9. In the right side of the grain
interior, the Y2O3 concentration is over 6 mol%, which
indicates that the right side grain is a cubic phase. It was
therefore assigned to the grain boundary between cubic
and tetragonal phases (C-T grain boundary). In the C-T
grain boundary, Al3+ ions segregated at grain boundaries
over a width of ∼6 nm.
The present results reveal that though Al3+ ions seg-
regate in grain boundaries, the cubic-formation behavior
in 3YE can be explained using the GBSIPT mechanism
recognized for 3Y.14 It is therefore thought that the
Al2O3-doped in Y-TZP does not greatly influence the
GBSIPT mechanism.
 K. Matsui et al.: Effect of alumina-doping on grain boundary segregation-induced phase transformation in Y-TZP
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FIG. 4. Conventional bright-field TEM images of 3YEs sintered at (a) 1100 °C, (b) 1200 °C, (c) 1300 °C, (d) 1500 °C, and (e) 1650 °C.

IV. DISCUSSION boundary. As a result, Y3+ ions segregate slightly and a

Based on the present analytical results, the effect of
Al2O3-doping on cubic-formation and grain-growth
mechanisms in Y-TZP can be considered as follows. The
grain-boundary segregation process of Y3+ ions and the
cubic-formation mechanism from the initial to final sin-
tering stages in 3YE are summarized schematically in
Fig. 10. At 1100 °C classified as the initial sintering
stage, neck formation and growth between particles oc-
cur [Fig. 10(a)]. Each particle is the single crystal com-
posed of monophasic tetragonal and the distribution of
Y3+ ions in particle interiors is homogeneous. In the
grain-boundary faces formed in the neck parts, particles
are joined directly without amorphous or second phase.
When the grain boundary starts to form with neck
growth, Y3+ ions existing in the grain-boundary neigh-
borhood diffuse and start to segregate in the grain
segregation profile of Y3+ ions is formed in grain bound-
aries, as shown in Fig. 7(a). Subsequently, at the inter-
mediate sintering stage, neck growth between particles
completes and then grain formation and growth occur. At
the first step in the intermediate stage, neck growth con-
tinues to proceed, and as a result, the size of the single
crystal with monophasic tetragonal increases. The Y3+
ion distribution of particle interiors is homogeneous, but
the segregation peak of Y3+ ions starts to form in grain
boundaries. At 1200 °C, neck growth is completed as the
particle form originating in the starting powder disap-
pears and the grains are formed [Fig. 4(b)].
At 1300 °C, classified as the final sintering stage
[Fig. 10(b)], the Y3+ ion distribution of grain interiors is
almost homogeneous [Fig. 5(c)], but the well-defined
segregation peak of Y3+ ions is formed in grain bound-
aries [Fig. 7(c)]. Grain boundaries migrate with the

J. Mater. Res., Vol. 21, No. 9, Sep 2006 2283

 K. Matsui et al.: Effect of alumina-doping on grain boundary segregation-induced phase transformation in Y-TZP
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FIG. 5. STEM images and Y K␣ and Zr K␣ mapping images by STEM-nanoprobe EDS method, of 3YEs sintered at (a) 1100 °C, (b) 1200 °C,
(c) 1300 °C, (d) 1500 °C, and (e) 1650 °C. The white broken lines in the mapping images indicate the grain boundaries. Bright parts in the Y K␣
mapping images correspond to regions with high Y3+ ion concentrations.

2284 J. Mater. Res., Vol. 21, No. 9, Sep 2006

 K. Matsui et al.: Effect of alumina-doping on grain boundary segregation-induced phase transformation in Y-TZP
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FIG. 6. HREM images of the grain-boundary faces in 3YEs sintered at (a) 1100 °C, (b) 1200 °C, (c) 1300 °C, (d) 1500 °C, and (e) 1650 °C.

well-defined segregation peak of Y3+ ions as the sin- growth, but also the T → C phase transformation, occur
tering temperature increases (i.e., this behavior corre- at the final stage. A part of the crystal phase in Y-TZP
sponds to grain growth). On the other hand, not only becomes the cubic phase, which is thermodynamically
grain-boundary segregation of Y 3+ ions and grain stable as the sintering temperature increases. Because the

J. Mater. Res., Vol. 21, No. 9, Sep 2006 2285

 K. Matsui et al.: Effect of alumina-doping on grain boundary segregation-induced phase transformation in Y-TZP
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FIG. 7. Y- and Al-distribution profiles across the T-T grain boundaries in 3YEs sintered at (a) 1100 °C, (b) 1200 °C, (c) 1300 °C, (d) 1500 °C,
and (e) 1650 °C. (嘷) and (䊐) indicate Y and Al, respectively.

regions in which Y3+ ions segregate in grain boundaries
and triple junctions have a tendency to cause T → C
phase transformation, the cubic phase starts to form from
grain boundaries and triple junctions when the sintering
temperature at which the cubic phase is thermodynami-
cally stable is attained. We named such a new diffusive
transformation phenomenon from a grain boundary
GBSIPT.13 When this temperature is exceeded, to extend
regions of the cubic phase, which is thermodynamically
stable, Y3+ ions in grain interiors dominantly migrate in
the direction of grain boundaries and triple junctions with
grain growth (i.e., the GBSIPT structure is formed). As a
result of such behavior of Y3+ ions, cubic grains in Y-
TZP are formed via the GBSIPT structure.
This cubic-formation mechanism is applicable from a
certain step in the final stage where the segregation peak

2286 J. Mater. Res., Vol. 21, No. 9, Sep 2006

 K. Matsui et al.: Effect of alumina-doping on grain boundary segregation-induced phase transformation in Y-TZP
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FIG. 8. Y- and Al-distribution profiles across the C-T grain bound-
aries in 3YE sintered at 1650 °C. (嘷) and (䊐) indicate Y and Al,
respectively.
FIG. 9. HREM image of the grain-boundary face in 3YE sintered at
1650 °C.
of Y3+ ions clearly appears. At 1300 °C, most grain
boundaries in which Y3+ ions segregate have transformed
from tetragonal to cubic phases. In this step, when the
sintering temperature increases, the widths of Y3+ ions
segregating in grain boundaries and triple junctions in-
crease with grain growth, and then the regions with high
J. Mater. Res., Vol. 21, No. 9, Sep 2006
Y3+ ion concentrations are formed in the grain interior
[Figs. 10(b)–10(c)]. These regions with high Y3+ ion
concentrations immediately change into the cubic phase
by T → C phase transformation. When the cubic regions
increase, the Y2O3 concentrations of the tetragonal re-
gions further decrease by diffusion of Y3+ ions to the
cubic regions. When the sintering temperature increases
further, regions of the cubic phase proceed to the regions
of tetragonal phase with grain growth, and then grains
with only cubic phase are formed [Fig. 10(d)]. Thus, the
present results in 3YE are also reasonably interpreted
using the GBSIPT mechanism recognized for 3Y.14
Grain growth in Y-TZP proceeds in intermediate and
final stages of sintering. In particular, the grain size in-
creases rapidly at the final stage. We reported that since
Y3+ ions segregated at T-T and C-T grain-boundaries
during sintering, based on the theory of the impurity-drag
effect derived by Cahn,21 the grain-growth mechanism in
Y-TZP is reasonably interpreted by the solute-drag effect
of Y3+ ions segregating along grain boundaries.13,14
In the present experiments, it is revealed that when a
small amount of Al2O3 is doped to Y-TZP, the densifi-
cation rate is remarkably enhanced at initial and inter-
mediate stages, and the grain size increases with the same
tendency up to 1500 °C and rapidly at temperatures of
>1500 °C. Because the densification process occurring at
initial and intermediate stages is caused primarily by
pore shrinkage with neck growth, it is thought that the
densification behavior is determined by the characteris-
tics of the grain boundary relating directly to neck
growth. At 3YE sintered at 1100 °C, Al3+ ions slightly
segregate at grain boundaries over a width of ∼6 nm. In
this segregated amount, no difference in the relative den-
sities of 3YE and 3Y appears (i.e., the relative density of
3YE equals that of 3Y). However, at 1200 °C, in which
the segregation peak of Al3+ ions appears clearly, the
relative density of 3YE increases more rapidly than that
of 3Y. At 1300 °C, the segregation peak of Al3+ ions
grows further, and the relative density has already at-
tained in the range of the final stage. These results ap-
parently reveal that because the densification rate in the
initial and intermediate stages is enhanced as the segre-
gation peak of Al3+ ions grows, Al3+ ions segregated at
grain boundaries over a width of ∼6 nm relate directly to
acceleration of neck growth.
When the sintering temperature increases, the segre-
gation peak of Al3+ ions grows further and at 1650 °C,
segregation-peak heights of Al3+ ions are attained in the
range of about 4.6–5.9 mol% Al2O3. Because the grain
size of 3YE increases more rapidly than that of 3Y at
temperatures >1500 °C, it is thought that when the
amount of Al3+ ions segregated at grain boundaries ex-
ceeds a certain value, Al3+ ions accelerate grain growth.
According to the impurity-drag theory,21 when an impu-
rity exists in a grain boundary, grain growth is depressed
2287
 K. Matsui et al.: Effect of alumina-doping on grain boundary segregation-induced phase transformation in Y-TZP
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FIG. 10. Schematic illustration of the cubic-formation mechanism from the initial to final sintering stages for 3YE. The gray parts of the
grain-boundary indicate segregation of Y3+ ions. The white and gray regions of grain interior represent the tetragonal and cubic phases,
respectively. GB stands for grain boundary.

because the grain boundary migrates by dragging the
impurity segregated in the grain boundary. However, be-
cause the effect of Al3+ ions segregated at grain bound-
aries is different from the grain-growth behavior pre-
dicted from the impurity-drag theory, it cannot be inter-
preted using this theory. On the other hand, Yoshida
et al.22 have reported the small amount of dopant effect
on the grain-growth behavior in Y-TZP. They have ex-
perimentally revealed that the growth constant related to
the grain-boundary diffusivity increased as the ionic ra-
dius of dopant decreased and argued that the dopant cat-
ions segregated at grain boundaries change grain-
boundary diffusivity.22 Taking into account the present
results based on the result reported by Yoshida et al.,22 it
is concluded that Al3+ ions segregated at grain bound-
aries have the effect of enhancing grain-boundary diffu-
sion because the ionic radius of Al3+ ions (0.068 nm) is
smaller than that of Y3+ ions (0.104 nm).23 Therefore, it
is supposed that at temperatures >1500 °C, the predomi-
nant effect that enhances grain-boundary diffusion is
caused by Al3+ ions rather than the solute-drag effect of
Y3+ ions, and as a result, the grain-growth behavior of
3YE is enhanced more rapidly than that of 3Y.
Furthermore, Al3+ ions segregated at grain boundaries
also affect the formation behavior of the cubic phase,
which is formed by the GBSIPT mechanism. In the pres-
ent results, at temperatures >1500 °C, at which the dif-
ference in grain growth appears, the fc of 3YE also in-
creases more than that of 3Y. Therefore, it is thought that
Al3+ ions segregated at grain boundaries also accelerate
the formation of the cubic phase.
V. CONCLUSIONS
In the present study, the microstructure in a small
amount of Al2O3-doped Y-TZP at 1100–1650 °C was
measured to clarify the effect of Al2O3-doping on cubic-
formation and grain-growth processes. The following re-
sults were obtained.
When a small amount of Al2O3 was doped to Y-TZP,
the sintering rate was enhanced remarkably, grain growth
proceeded remarkably, and the fc slightly increased at
temperatures >1500 °C.
No amorphous or second phase existed along the
grain-boundary faces, but Y3+ and Al3+ ions segregated
at grain boundaries over widths of ∼10 and ∼6 nm, re-
spectively. The segregation peak of Al3+ ions at the grain
boundary increased as the sintering temperature in-
creased.
Al3+ ions segregated at grain boundaries relate directly

2288 J. Mater. Res., Vol. 21, No. 9, Sep 2006

 K. Matsui et al.: Effect of alumina-doping on grain boundary segregation-induced phase transformation in Y-TZP
to acceleration of the densification rate in the initial and
Downloaded from https://www.cambridge.org/core. Gadjah Mada University, on 28 Feb 2019 at 02:29:09, subject to the Cambridge Core terms of use, available at https://www.cambridge.org/core/terms. https://doi.org/10.1557/jmr.2006.0274
intermediate stage of sintering. Furthermore, at tempera-
tures >1500 °C, Al3+ ions segregated at grain boundaries
enhanced grain growth and the fc.
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