J. Am. Ceram. Soc.
, 88 [4] 963–967 (2005)
Journal
The Effect of MgO Addition on Grain Growth in PMN–35PT
Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology, Daejeon
When Pb(Mg1/2Nb2/3)O3–35PbTiO3 (mol%) (PMN–35PT) is
sintered at 12001C after packing in PbZrO3 powder, the grains
show normal growth with time invariant normalized grain size
distributions. If 0.5 wt% MgO is added to PMN–35PT, ab-
normal grain growth occurs with the large abnormal grains de-
veloping nearly cubic shapes. The interfaces between grains and
PbO-rich liquid at grain triple junctions are flat, indicating that
they are singular. Many central segments of the liquid films and
possibly grain boundaries between the abnormal grains and the
small neighboring grains are also flat along the {100} planes of
the abnormal grains. The abnormal grain growth in the MgO-
doped specimens is likely to be caused by the presence of these
singular interfaces. Most of the large abnormal grains do not
contain any R 5 3 penetration twin boundaries unlike the pre-
vious observations in PbO-excess PMN–35PT.
I. Introduction
T HE solid solution of ferroelectric Pb(Mg1/3Nb2/3)O3 (PMN)
and PbTiO3 (PT) shows good piezoelectric property about
35 mol% PT.1–4 The grain growth is important in both process-
ing of polycrystalline PMN–PT and growing PMN–PT single
crystals in fine grain matrices. The specimens of PMN–35PT (by
mol%) composition were observed to show normal grain
growth,5–7 but addition of excess PbO was observed to induce
abnormal grain growth (AGG).5–6,8–10 This work shows that
addition of MgO to PMN–35PT also induces AGG. Addition of
MgO to PMN was previously observed to increase the grain size
without apparently changing the normal growth behavior.11
In single-phase polycrystalline materials and those with liquid
matrix phases, it was shown that the occurrence of AGG was
correlated with the presence of singular grain boundaries and
grain surfaces.12–19 It was proposed that AGG occurred because
the grains with singular surfaces and grain boundaries grew by
atom attachment to surface or boundary steps either produced
by two-dimensional nucleation or existing at screw disloca-
tions.12,15,20–22 Often, large abnormal grains surrounded by
fine grains were observed to have flat low index boundaries
that were suggested to consist of singular grain boundary or
surface segments.14,16,23 The PMN–35PT specimens with excess
MgO also show abnormal grains with nearly cubic shapes.
II. Experimental Procedure
PMN–35PT and 0.5 wt% MgO-doped PMN–35PT powders
were prepared by Columbite precursor method.24 MgNb2O6
precursor was prepared by ball milling appropriate amounts of
4MgCO3(Mg(OH)2)4H2O and Nb2O5 for 24 h, drying, crush-
L. C. Klein—contributing editor
Manuscript No. 11383. Received October 14, 2004; approved October 14, 2004.
Supported by the Korea Ministry of Science and Technology through the National
Research Laboratory (NRL) Program and Asian Office of Aerospace Research and De-
velopment (AOARD-00-403).
*Member, American Ceramic Society.
w
Author to whom correspondence should be addressed. e-mail: mylight@kaist.ac.kr
963
DOI: 10.1111/j.1551-2916.2005.00213.x
Chang Eui Seow and Duk Yong Yoon*
305-701, Korea
ing, sieving, and then calcining at 11001C for 4 h. For doping
with 0.5 wt% MgO, the excess amount of 4MgCO3(Mg
(OH)2)4H2O was calculated on the basis of MgO produced
after the calcination at 11001C. PMN–35PT and 0.5 wt% MgO-
doped PMN–35PT powders were prepared through ball milling
appropriate amounts of MgNb2O6, TiO2 and PbO for 24 h,
drying, crushing, sieving, and then calcining at 8501C. All ball
milling was done in ethyl alcohol with ZrO2 ball. The prepared
powder was pressed into cylinderical compacts and then pressed
isostatically at 200 MPa. The compacts were placed on a piece of
Pt foil and sintered at 12001C in a double alumina crucible with
lids surrounded by PbZrO3 (PZ) atmospheric powder, placed
at outer crucible to minimize PbO loss during sintering. They
were sintered in a flowing O2 atmosphere which was apparently
necessary for rapid sintering.25 The sintered specimens were
sectioned through the center perpendicular to the axes for
microscopic observations. The polished specimens were ther-
mally etched at 9001C for about 40 min for examinations under
optical and scanning electron microscopes (SEM; XL30 SFEG,
Philips, Eindhoven, Holland). The orientation relations between
grains of polished specimens were determined using electron
backscattered diffraction (EBSD; TexSEM Laboratories, Dra-
per, UT). The boundary and the triple junction regions between
the grains were examined with a transmission electron micro-
scope (TEM; JEM-310, JEOL, Tokyo, Japan). The grain diam-
eters were measured by digital analyzer. The sizes of more than
400 grains were measured in each specimen.
III. Results and Discussion
The PMN–35PT compacts packed in PbZrO3 powder sintered
very rapidly and were almost fully dense after sintering for 0
time (for the specimen heated to 12001C and cooled immedi-
ately) as shown in Fig. 1(a). The TEM observations of the
sintered PMN–35PT specimens showed that there were liquid
pockets at some of the grain triple junctions as exhibited in
Fig. 2. The dihedral angles appeared to be 0, indicating that
there were thin liquid films in the intergranular regions. The
TEM observations of the intergranular regions at higher mag-
nifications indeed showed thin amorphous layers as verified by
circular diffraction patterns. Such a liquid phase, which was
likely to be PbO-rich, probably formed because of slight com-
position inhomogeneity in the initial powder. It is also possible
that some PbO from the packing PbZrO3 powder transferred to
the PMN–35PT compacts during the sintering treatment be-
cause of its higher activity in PbZrO3.26 Previously, Khan et al.7
also observed PbO-rich liquid pockets at grain triple junctions
after sintering in PbZrO3 packing powder. It is thus likely that
the dark voids at the grain triple junctions in Fig. 1 (more clearly
visible in Fig. 1(d) with large grains) were formed by evapora-
tion of the PbO-rich liquid pockets during the thermal etching of
the polished specimen surface. The interfaces between the grains
and the liquid (or the void produced by the evaporation of the
liquid) at the triple junctions were mostly curved, indicating that
they were atomically rough. Similar curved grain–liquid inter-
faces at the triple junctions were also observed previously by
Khan et al.7 in a PMN–35PT specimen sintered at 11501C after
packing in PbZrO3 powder.
964 Journal of the American Ceramic Society—Seo and Yoon Vol. 88, No. 4

(a) (b)

1µm 1µm

(c) (d)

2µm 2µm

Fig. 1. The SEM microstructures of the PMN–35PT (mol%) specimens sintered at 12001C for (a) 0 min, (b) 1 h, (c)12 h, and (d) 24 h after packing in
PbZrO3 powder.

Because the energy of a grain boundary between two grains
will depend on their misorientation angle, the grain boundaries
(without any liquid layer) can be more stable than liquid films
between some grains. These grain boundaries will have finite di-
Fig. 2. The TEM image of a grain triple junction in a PMN–35PT
specimen sintered at 1200 C for 1 h.
hedral angles at the junctions with the liquid pockets. The TEM
observations indeed showed that there were no liquid films be-
tween some grains even at very high magnifications. It appeared,
therefore, that there were both (dry) grain boundaries and liquid
films between the grains in these PMN–35PT specimens.
The grain size distributions normalized to the average sizes
were relatively narrow and invariant, with the sintering time as
shown in Fig. 3(a). A plot of the cube of the average grain di-
ameters shown in Fig. 3(b) against the sintering time deviated
slightly upward from a straight line. Such a deviation could arise
from slow PbO transfer from the PbZrO3 packing powder to the
compacts at the early stages of sintering. Similar grain size dis-
tributions resembling those of normal grain growth were also
observed in this material.5–7 The grain growth in this material
can be normal and controlled by diffusion across the liquid
pockets at the triple junctions, because the grain–liquid inter-
faces are rough as suggested earlier.27–29
The specimens doped with 0.5 wt% MgO also sintered rap-
idly and were fully dense after sintering for 1 min with a micro-
structure which was similar to that shown in Fig. 4(a) for the
specimen sintered for 1 h. The grains grew slightly between 1
min and 1 h of sintering, but the grain size distributions re-
mained relatively narrow as shown in Fig. 4(a). After sintering
for 12 h, some large abnormal grains appeared with some
growth of the other grains as shown in Fig. 4(b). These ab-
normal grains subsequently grew to large sizes as shown in
Figs. 4(c) and (d), and the grain size distributions shown in
Fig. 5 confirmed a typical AGG behavior with very large grains
appearing after sintering for 12 h.
April 2005 Effect of MgO Addition on Grain Growth in PMN-PT 965

(a) (b) 25
20
0 min
18 20
1h

Relative Frequency [%]

16 4h
14 12 h 15
24 h

d 3 [µm3]
12
48 h
10 72 h 10
8
6 5
4
2 0
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0 10 20 30 40 50 60 70 80
Normalized Grain Size Sintering Time [h]
Fig. 3. The (a) normalized grain size distributions and the (b) cube of average grain sizes of the PMN–35PT (mol%) specimens sintered at 12001C for
various times.

The attempts to examine these MgO-doped specimens by
TEM failed because the TEM specimens broke during their
preparation. But the SEM observations of the voids at the grain
triple junctions that were formed by evaporation of the liquid
pockets during thermal etching often showed flat grain–liquid
interfaces indicating their singular structure. Furthermore, the
large abnormal grains developed nearly cubic shapes with some
flat boundaries which became more pronounced after long sin-
tering times as shown in Figs. 4(c) and (d). Typical morph-
ologies of the boundaries between the abnormal grains and the
fine grains are shown by a scanning electron micrograph in
Fig. 6 for the specimen sintered for 24 h (Fig. 4(d)).
Depending on the misorientation angle between grains, there
can be either liquid films or (dry) grain boundaries between the

Fig. 4. The microstructures of the 0.5wt.% MgO-doped PMN–35PT (mol%) specimens sintered at 12001C for (a) 1 h (SEM), (b) 12 h (optical), (c) 1 8 h
(optical), and (d) 24 h (optical).
966 Journal of the American Ceramic Society—Seo and Yoon
4h
1h
e rin
nt
1 min Si
0 2 4 6 8 10
Normalized Grain Diameter
Fig. 5. The normalized grain size distributions of the 0.5wt.% MgO-
doped PMN–35PT (mol%) specimens sintered at 12001C for various
times.
grain pairs. The liquid film and the grain boundary will be re-
ferred to as the intergranular boundary. The center region of the
boundary between the abnormal grain and each fine grain was
flat and appeared to be parallel to the (001) surface of the ab-
normal grain. These boundaries, however, were slightly curved
toward the fine grains at the triple junctions. Such a morphology
of the intergranular boundaries indicates that the equilibrium
shape of the grain in the liquid or embedded in another larger
grain with grain boundaries (the grain boundary Wulff shape)
will be a cube with flat {001} surfaces and curved edges (and
corners) without any discontinuity of the slopes. The flat {001}
interfaces will be singular corresponding to the cusps in the po-
Fig. 7. The (a) optical microstructure of the 0.5 wt% MgO-doped PMN–35PT (mol%) specimen sintered at 12001C for 24 h and an (b) EBSD image of
the same region.
Vol. 88, No. 4
Relative Frequency [%]
20
15
10
5
1
0
12 h
abnormal grain
e
m
Ti
g
Fig. 6. The SEM microstructure of a boundary region between an ab-
normal grain and small grains in the 0.5 wt% MgO-doped PMN–35PT
(mol%) specimen sintered at 12001C for 24 h.
lar (Wulff) plot of the interface energy against the orientation
and the curved edges will be atomically rough.30–32 If the grain
equilibrium shape was a cube with sharp edges and corners, a
surface of the abnormal grain would have been flat even at the
triple junctions. If, on the other hand, the equilibrium shape was
a sphere, the boundaries between the abnormal grains and the
fine grains would have been more convex (as seen from the small
grains) than those shown in Fig. 6. While the local shapes of the
interfaces at the triple junctions are determined by the equilib-
rium shape of the grains, the overall shapes of the abnormal
grains, which become cubic during their growth, are probably
determined by the anisotropy of the growth rates. If the grains
indeed have {001} singular surface segments, their intrinsic
migration rate is likely to be the lowest, and hence the growing
April 2005 Effect of MgO Addition on Grain Growth in PMN-PT
abnormal grains can develop cubic shapes. (In Fig. 6, the void at
a triple junction indicated by an arrow shows the flat grain–liq-
uid interfaces as described earlier, but the flat shapes were more
clearly visible at higher magnifications.)
When the grain boundaries or the grain–liquid interfaces are
singular, AGG can occur because the grains grow by a step
mechanism as proposed earlier.12,15,20–22 Although the PbO–
MgO–Nb2O5 phase diagram33 shows that the solubility of MgO
in liquid PbO and the excess MgO content in PMN at 10001C
are 0, it is possible that small amounts of MgO are dissolved in
the PbO-rich liquid or PMN–35PT at 12001C, and its segrega-
tion at the grain–liquid interface and grain boundary may have
made their step energies finite and hence made them sufficiently
singular to cause AGG. It was earlier observed that the addition
of MgO to alumina–anorthite17 and B to NbC–Co34 and NbC–
Fe35 caused partial or complete roughening of the interfaces, but
it is not presently possible to explain why the additives make the
interfaces of various materials more singular or rough.
These MgO-doped specimens showed pockets of a second
phase of about 5 mm in size (approximately same size as the fine
PMN–35PT grains) that were located between the fine PMN–
35PT grains with sometimes irregular shapes. This second phase
was determined to contain Mg and Ti at approximately equal
mole ratio by energy dispersive X-ray diffraction analysis. This
phase is likely to be the stable MgTiO3 according to the phase
diagram.36 No pyrochlore phase was found in these and un-
doped specimens by X-ray diffraction.
The orientations of the large abnormal grains in the MgO-
doped specimen sintered for 24 h were determined by EBSD as
shown in Fig. 7. Most of the neighboring abnormal grains had
high misorientation angles and only one boundary near the top
right corner of Fig. 7(b) was a S 5 3 type. In contrast, many
abnormal grains in PbO-excess PMN–26PT37 or PMN–35PT
(by mol%)8,9 were observed to contain S 5 3 penetration twins.
The present results show that AGG occurred in the MgO-doped
PMN–35PT without any penetration twins.
IV. Conclusions
It was confirmed in this work that normal grain growth occurred
in PMN–35PT without MgO doping. When 0.5 wt% MgO was
added, AGG occurred. The flat grain–liquid interfaces at the
grain triple junctions and the nearly flat boundary between the
abnormal and fine grains indicate that the grain–liquid interfac-
es and the grain boundaries become partially singular when
MgO is added. These singular interfaces should cause AGG as
in alumina with anorthite.
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