J. Am. Ceram. Soc.
, 85 [6] 1581– 84 (2002)
journal
Grain Growth and Twin Formation in 0.74PMN䡠0.26PT
Jay S. Wallace,* Jong-Moo Huh,* John E. Blendell,* and Carol A. Handwerker*
National Institute of Standards and Technology, Gaithersburg, Maryland
The mechanisms controlling normal and exaggerated grain
growth in lead magnesium niobate–lead titanate (PMN–PT)
ceramics have been investigated by varying the PbO-based
liquid-phase volume fraction from 0.03 to 0.6 and sintering
temperature from 900° to 1100°C. There is a transition in
matrix grain growth rate and matrix grain shape with liquid
fraction; samples with liquid volume fractions less than ⬃0.15
show relatively small equiaxed grains resulting from grain-to-
grain impingement. Samples with higher liquid fractions show
significantly larger, facetted, cube-shaped grains, whose size is
independent of liquid fraction, indicating that a surface nucle-
ation rate mechanism controls growth in this regime. Exagger-
ated grains were found in the high liquid fraction samples.
Electron backscatter diffraction showed that all of the exag-
gerated grains contained 60° 具111典 twins but none of the
normal matrix grains contained twins. The reentrant angles in
the twinned grains give them a growth advantage over un-
twinned grains, resulting in a population of exaggerated
grains.
I. Introduction
L EAD MAGNESIUM NIOBATE, Pb(Mg1/3Nb2/3)O3 (PMN), is a rel-
axor ferroelectric that shows excellent piezoelectric response
and is a good candidate for transducers.1 These properties can be
enhanced when lead titanate, PbTiO3 (PT), is present in solid
solution in amounts below that of the morphotropic phase bound-
ary, ⬇0.33 mol fraction.2 However, conventionally sintered poly-
crystalline PMN–PT ceramic materials exhibit inferior piezoelec-
tric properties compared with single crystals. This is due in part to
the anisotropy of the piezoelectric properties,3 requiring a high
degree of alignment to approach single-crystal properties. In
addition, polycrystalline materials have pores, cracks, and remnant
second phase inclusions, all of which degrade the properties.
To bridge the performance gap between single-crystal and
polycrystalline PMN, “in situ ” crystal growth of a single large
seed4 or from multiple, aligned “template” seeds5 that are larger
than the matrix grains has been applied. Initial growth of the
single-crystal seeds is dominated by growth in the 具111典 direction
until either impingement on large matrix grains occurs or the
growth surfaces become bounded by slow-growing (100) facets.4
In the case of templated growth,5 normal and exaggerated grain
growth in the matrix lowers the driving force of the template
grains, and impingement of growing grains occurs, resulting in a
further decrease in driving force. These effects create a practical
limit for the maximum crystal size achievable.
The present work focuses on the investigation of grain growth
mechanisms of PMN–PT grains in a PbO-rich liquid. Measure-
ments of growth rate with varying amounts of liquid phase were
used to determine the rate-limiting growth mechanism and the
M. P. Harmer—contributing editor
Manuscript No. 187543. Received August 3, 2001; approved March 8, 2002.
*Member, American Ceramic Society.
1581
20899
effect of grain-to-grain impingement. Improved understanding of
the grain growth mechanisms operating in this system can be used
to define the microstructural evolution paths and processing
parameters for increasing the size of PMN–PT single crystals.
II. Experimental Procedure
PMN–PT powders were formed from PbO, Nb2O5, MgCO3,
and PbTiO3 starting powders using a one-step process.6 Thermo-
gravimetric analysis was performed on each of the constituents to
assure a precise stoichiometry of 0.74PMN䡠0.26PT (mole fraction)
of the final body. The three oxides were attrition milled for 1 h
using 2 mm diameter Al2O3 media and isopropyl alcohol. MgCO3
was dissolved in 3M HNO3 and mixed with the isopropyl alcohol
slurry. The slurry was rotary evaporated to dryness and the
resulting powder was calcined in air for 0.5 h at 1050°C in a MgO
crucible to decompose the nitrate and form PMN–PT solid
solution. The calcined powder was attrition milled for 1 h to reduce
the PMN–PT particle size and dried. Finally, the powder was dry
mixed with PbO powder to obtain the desired quantity of liquid
phase. The liquid-phase volume fraction, Vᐉ, between 0.03 and 0.6,
was calculated using data for the equilibrium PMN–PbO liquid
composition,7 assuming that PbTiO3 partitions equally in the solid
and liquid and that the density of the liquid can be calculated from
the rule of mixtures. All samples were isostatically pressed at 350
MPa and sintered for 2 h in an oxygen atmosphere on MgO setter
plates using a double MgO crucible technique to minimize PbO
loss. Sample cross sections were polished with 0.05 ␮m silica
slurry for scanning electron microscopy (SEM) and electron
backscatter diffraction (EBSD). Etching, when needed, was per-
formed with a 5% HNO3 ⫹ 1% HF solution for 2 to 10 s. Grain
mean intercept length (L៮ ) was measured using line intercepts of
100 –300 grains on polished cross sections.8 The relative standard
deviation of L៮ between images of the same specimen was typically
between 5% and 10%. Individual grains were removed from the
sintered body by wicking the PbO liquid from the sintered sample
with a ZrO2 powder bed for 1 h at 1000°C followed by etching for
3 h with 3M HNO3, then sonication and filtration.
III. Results and Discussion
The matrix grains showed a shape transition with liquid frac-
tion. Samples sintered with low liquid fractions, Vᐉ ⬍ 0.15,
showed fine, equiaxed, space-filling grains (Fig. 1(A)) which
generally did not appear facetted. For these low liquid fractions,
shape accommodation occurred under the influence of the capil-
lary forces of the wetting liquid and the equilibrium shape of an
isolated grain surrounded by liquid was not observed. Samples
with high liquid fractions, Vᐉ ⬎ 0.15, had facetted, cube-shaped
matrix grains (Fig. 1(B)) which resulted from relieving the
constraint of shape accommodation with increasing liquid fraction.
This cube shape persisted to higher liquid fractions and long
sintering times, indicating that it is the equilibrium grain shape.
Accompanying the change in grain shape with increasing liquid
fraction was a transition to larger grain sizes, by a factor of
approximately 4 (Fig. 2) similar to those found in simulations.9 In
this regime the grain size for a given set of annealing conditions
was insensitive to liquid fraction. Since the average separation
1582 Journal of the American Ceramic Society—Wallace et al.
Fig. 1. Scanning electron microscope images of sintered PMN–PT samples: (A) rounded matrix grains result from shape accommodation in a sample with
0.1 liquid fraction; (B) facetted, cube-shaped matrix grains in a sample with 0.4 liquid fraction.
between grains, thus the length of the diffusion path, increased as
the liquid fraction increased, a smaller average grain size would
have resulted if diffusion were the growth-rate-limiting step.10,11
Therefore, the independence of L៮ with liquid fraction indicates that
diffusion is not the growth-rate-limiting step. Such behavior has
been observed in Si3N412,13 and other facetted ceramic systems.11
A further indication that diffusion was not rate limiting was
found in the matrix grain shape. As opposed to a rounded grain
morphology for rough surfaces and diffusion-controlled growth,14
facetted grain shapes at high liquid fractions (Fig. 1(B)) indicate
that interface attachment is the growth-limiting step.15 In this
Fig. 2. Mean intercept length of matrix grains was independent of liquid
fraction for Vᐉ ⬎ 0.2, indicating that growth is not diffusion controlled. For
Vᐉ ⬍ 0.15 impingement limits grain size. Note: the curves are drawn to aid
in visualizing the data groups.
Vol. 85, No. 6
regime, growth is limited by the nucleation of new ledges on
singular grain facets; once nucleated, the growth ledge moves
rapidly to complete the facet.
The apparent temperature dependence of the transition region
between low and high liquid fractions is an artifact of the
experimental conditions in which high and low liquid fraction
samples were sintered together in a single crucible. Samples with
high liquid fractions had sufficient liquid to fill all the pore
volume. Thus all liquid–vapor interfaces were flat. For lower
liquid fractions capillary pores with negative radii of curvature
existed, lowering the PbO vapor pressure above the liquid. This
activity difference resulted in transport of PbO from the high liquid
fraction to the low liquid fraction samples, with mass gain of up to
30% for low Vᐉ samples and mass loss of 40% for high Vᐉ samples
sintered at 1100°C. With further time at elevated temperature all of
the samples lost PbO by vaporization. Since vapor transport to and
from samples was transient and not readily quantifiable, no attempt
was made to correct for the changing liquid fractions; the value of
volume fraction for matrix grain size transition must be viewed as
approximate.
Accompanying the matrix grain size and shape transitions at
Vᐉ ⬇ 0.15 was the development of facetted exaggerated grains,
i.e., those larger than 2.25 times the average grain size16 (Figs. 3
and 4). The exaggerated grains did not have the cube shape of the
matrix grains and always contained reentrant edges in cross
section. EBSD determined that each exaggerated grain contained
one or more 60° 具111典 twins. The twin boundaries were not straight
and were not necessarily aligned with either of the adjacent crystal
orientations (Fig. 3(B)), indicative of low twin boundary energy.
Twinned matrix grains were not found by EBSD. The existence of
twins in the exaggerated grains, but not the matrix grains, indicates
that the exaggerated grains form a separate grain size population as
a result of a different grain growth mechanism, twin plane
reentrant edge (TPRE) growth.17 When a twin is present, there is
a significantly reduced nucleation barrier for the formation of a
stable new ledge at the twin site, compared with nucleation of a
stable ledge on a singular interface, resulting in a growth advan-
tage for the twinned grain. This grain growth behavior is well
known for BaTiO318,19 where it has been attributed to the
June 2002 Grain Growth and Twin Formation in 0.74PMN䡠0.26PT
Fig. 3. Scanning electron microscope images of sintered PMN–PT samples: (A) exaggerated grain with reentrant angles in a sample with 0.4 liquid fraction;
(B) EBSD image of an exaggerated grain and matrix grains. The dark lines within the exaggerated grain are 60° 具111典 twin boundaries.
formation of a double twin. The 60° 具111典 twins in PMN–PT create
a stable geometric configuration during growth, providing a
continuing source of ledges as the grains grow and a nearly linear
growth rate of the exaggerated grains until impingement on other
grains of similar or greater size occurs.11,13,20
Fig. 4. SEM image of a single exaggerated grain that was extracted from
a sintered body. The (100) faces, 60° 具111典 twin and reentrant angle of the
exaggerated grain are evident.
1583
Several possible mechanisms for twin formation have been
considered: twinning resulting from mechanical strains, grain
coalescence, and chemical effects. First, since the processing route
for the powders included mechanical comminution of the prere-
acted PMN–PT powders, mechanical twinning of some fraction of
the precursor grains could result in twinned “nuclei” for the
exaggerated grains. However, when PMN–PT was made from
starting oxides, PbO, MgCO3, Nb2O5, and TiO2 without a milling
step after the constituents were reacted and PMN formed, twinned
exaggerated grains were also found. Therefore, the twins do not
appear to form as a result of milling.
Coalescence of facetted grains in systems with an incompletely
wetting liquid to form twinned grains or grains with low-angle
boundaries has also been proposed,21,22 particularly for BaTiO3.
Calculations of the likelihood of forming single and double twins
based on geometric probabilities of twin formation seem plausible,
depending on the angular acceptance criteria chosen. Such a model
would predict a continuously increasing number of twinned grains
with time with the rate of coalescence highest for the smallest
grain sizes. However, the estimated number of exaggerated grains
per unit volume was nearly constant for samples annealed between
0.5 and 8 h at 1050°C, indicating that exaggerated grains did not
continuously nucleate during annealing. In addition, there is a
nucleation incubation time for formation of exaggerated grains
which depends on the PbTiO3 and MgO concentrations.23 During
this incubation period there can be significant grain growth
without exaggerated grain formation. These observations lead to
the tentative conclusion that nucleation of twins does not occur as
the result of grain coalescence.
Twin formation has also been shown to result from composi-
tional changes.24,25 In MgO, for example, 具111典 twins are stabi-
lized by a thin platelet of Mg(OH)2, formed in the presence of
water vapor, which serves as the template for the twin.26 Twinning
has also been found in crystals that were formed by solidification
from a binary liquid where compositional changes occurred during
cooling, but coalescence did not occur.27 The hypothesis that
compositional changes could affect twinning in this system is
supported by three observations. First, there are compositional
variations within the PMN–PT grains as a result of growth
conditions. The initially homogeneous PMN–PT solid solution
1584 Journal of the American Ceramic Society—Wallace et al.
particles dissolve in the PbO liquid phase and precipitate on the
growing grains. Depending on the partitioning coefficients of
PMN and PT, the PMN:PT composition of the precipitating
material will be initially different from the grain on which it is
being deposited. Qualitative SEM energy dispersive spectroscopy
measurements show that the Ti content of PMN–PT grains in
contact with 0.5 liquid fraction is significantly lower than that of
grains where no excess PbO is present. Second, when PMN
without PT is sintered for similar times, temperatures and liquid
fractions, exaggerated grains are not found. Finally, exaggerated
grains tend to nucleate in the PMN–PT samples where they contact
the MgO setter. Similar chemical gradients have been found in
other liquid-phase sintered systems in which facetted grains
exhibit nucleation of special boundaries and exaggerated grain
growth.22 Such chemical variations could affect the energetics of
stacking fault and twin formation, as in the case of MgO. While
these observations indicate that twin formation is affected by
composition, further examination of twinning in the PMN–PT
system is necessary to completely understand its origin.
IV. Summary
The grain growth of lead magnesium niobate–lead titanate has
been investigated by varying the amount of the PbO-based liquid
phase present during sintering. A change in the growth kinetics
was observed at Vᐉ ⬇ 0.15. For Vᐉ ⬍ 0.15 the matrix grain shapes
were rounded due to shape accommodation in response to the
capillary pressure. For Vᐉ ⬎ 0.2, the grains were facetted cubes
with growth rates much faster than for Vᐉ ⬍ 0.15 but independent
of Vᐉ. The matrix growth rate is controlled by a surface nucleation
mechanism rather than diffusion through the liquid as shown by
the independence of the growth rate on volume fraction liquid and
the faceted grain shape. In addition to faceting for Vᐉ ⱖ 0.15,
exaggerated grains (L ⬎ 2.25L៮ ) were observed. All the exagger-
ated grains contained 60° 具111典 twins and grain surfaces had twin
plane reentrant angles. These reentrant angles significantly low-
ered the ledge nucleation barrier, giving the twinned grains a
growth advantage over grains where ledge nucleation can only
occur on defect-free singular surfaces. The number of exaggerated
grains was constant with time, indicating that the twin formation
occurs at one time early in the growth process. Exaggerated grains
were not observed for PMN samples without PbTiO3, suggesting
that compositional changes during precipitation from the liquid
may control twin formation.
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