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Mechanical Properties of xPMN-(1-x)PZT Ceramic Systems

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 ➔ CMU. Journal (2004) Vol. 3(2) 147

Mechanical Properties of xPMN-(1-x)PZT Ceramic Systems

Rattikorn Yimnirun*, Ekarat Meechoowas, Supon Ananta and Tawee Tunkasiri

Department of Physics, Faculty of Science, Chiang Mai University, Chiang Mai 50200,
Thailand
*Corresponding author. E-mail: [email protected]

ABSTRACT
Most of earlier work on PMN-PZT ceramic systems has been mainly focused on
processing and electrical properties, while knowledge on mechanical properties is scarce.
This article describes for the first time mechanical properties of the PMN-PZT ceramic
systems. The (x) Pb(Mg1/3Nb2/3)O3 - (1-x) Pb(Zr0.52Ti0.48)O3 (when x = 0, 0.1, 0.3, 0.5, 0.7,
0.9, and 1.0) ceramics are prepared from respective starting materials by a conventional
mixed-oxide method. A combination of the Knoop and Vickers indentation techniques is
employed to determine the mechanical properties of the ceramics. It is found that the Vickers
hardness of the ceramics varies between 5.28 and 7.75 GPa while the Young’s modulus
values range from 65.9 to 99.6 GPa. The fracture toughness of 2.03 to 3.42 MPa.m1/2 is
obtained from the ceramics tested. In general, it is observed that the mechanical properties
of the ceramic systems are largely controlled by those of PMN ceramics.

Key words: PMN-PZT ceramics, Mixed-oxide method, Mechanical properties

INTRODUCTION
With distinct characteristics, lead magnesium niobate (Pb(Mg1/3Nb2/3)O3 or PMN) and
lead zirconate titanate (Pb(Zr1-xTix)O3 or PZT) ceramics have been employed extensively in
different types of actuator and transducer applications (Cross, 1987; Xu, 1991). As a prototypic
relaxor ferroelectric, PMN has advantages of having very high dielectric constant and broader
operating temperature range, especially over the room temperature range, as a consequence
of the diffuse paraelectric-ferroelectric phase transition which takes place in the vicinity of
room temperature. In addition, as a result of their unique microstructural features, PMN
ceramics exhibit low loss and non-hysteretic characteristics. However, the PMN ceramics
have relatively low electromechanical coupling coefficients as compared to PZT. On the
contrary to PMN, PZT ceramics have been utilized more in actuator and transducer
applications due to their high electromechanical coupling coefficients near the morphotropic
phase boundary (MPB) (Cross, 1987; Xu, 1991; Abe et al., 2000). However, PZT ceramics
are fairly lossy as a result of their hysteretic behavior. This makes them unsuitable for
applications that require high delicacy and reliability. Furthermore, PZT ceramics normally
have very high Curie temperature (TC) in the vicinity of 400˚C. Usually, many applications
require that TC is close to ambient temperature. Therefore, there is a general interest to
reduce the TC of PZT ceramics to optimize their uses. Forming a solid-solution of PZT and
relaxor ferroelectrics has been one of the techniques employed to improve the properties of
148 ➔ CMU. Journal (2004) Vol. 3(2)

ferroelectric ceramics. With the complementary features of PMN and PZT, it is of special
interest to investigate a solid-solution of PMN-PZT ceramics which are expected to possess
more desirable features than single-phase PMN and PZT (Ouchi et al., 1965; Ouchi, 1968;
Xu, 1991).
However, most of earlier studies on PMN-PZT ceramics have been focused on
processing, dielectric and electrical properties of the system. It is then of interest to examine
the mechanical properties of the ceramic systems (Shilnikov et al., 1999; He et al., 2001;
Stringfellow et al., 2002). The mechanical properties of the PMN-PZT systems require a
special attention because these ceramics are usually used under an influence of stress in most
of the actuator and transducer applications (Murty et al., 1992; Yoo et al., 1998). Thus, this
study is undertaken to investigate for the first time the mechanical properties of the
PMN-PZT ceramic systems.

MATERIALS AND METHODS

The Pb(Mg1/3Nb2/3)O3 -Pb(Zr0.52Ti0.48)O3 ceramics are prepared from PMN and PZT
powders by a mixed-oxide method. Detailed procedures of each preparation step are
described elsewhere (Yimnirun et al., 2003). Perovskite-phase PMN powders are obtained
via a well-known columbite method (Swartz and Shrout, 1982). In this method, the
magnesium niobate powders are first prepared by mixing starting MgO and Nb2O5 powders
and then calcined to form a so-called columbite powder (MgNb2O6). The columbite powders
are subsequently ball-milled with PbO. After another calcination process, a perovskite-phase
PMN is formed. PZT powders, on the other hand, are prepared by a more conventional
mixed-oxide method. With a more conventional oxide-mixing route, PZT powders are
prepared from PbO, ZrO2, and TiO2 starting powders. These powders are ball-milled and
later calcined to yield the PZT powders. The (x) Pb(Mg1/3Nb2/3)O3 - (1-x) Pb(Zr0.52Ti0.48)O3
(when x = 0, 0.1, 0.3, 0.5, 0.7, 0.9, and 1.0) ceramic systems are prepared from the starting
PMN and PZT powders by a mixed-oxide method at various calcining conditions. The mixed
powders are pressed hydraulically to form disc-shaped pellets, 15 mm in diameter and 2 mm
thick. The pellets are sintered in a covered alumina crucible filled with PZ powders to
prevent lead loss. For optimization purpose, the sintering temperature is varied between 1000˚C
- 1300˚C, depending upon the compositions.
The densities of the sintered ceramics are measured by Archimedes method from
the specimens weighed in air, in water and the density of water. The phase formations of
the sintered specimens are studied by XRD technique. The microstructure analyses are
undertaken by a scanning electron microscopy (SEM: JEOL Model JSM 840A). Grain size
is determined from SEM micrographs by a linear intercept method. A combination of the
Knoop and the Vickers indentation techniques (Microhardness Testers: Model Matsuzawa
MXT-α and Model Galileo Microscan-2) is used to determine various mechanical properties
of the ceramics, such as the Vickers hardness (HV), the Young’s modulus (E) and the fracture
toughness (KIc).
With the indentation techniques used, the Vickers hardness (HV) is calculated from
(1.18185x1010 x P)/d2 relation, where P is the weight of the indenter used and d is the average
 ➔ CMU. Journal (2004) Vol. 3(2) 149

length of the indented surface. Using the Knoop indentation technique, the Young’s modulus
(E) is determined from α•HK•(0.1407-(b/a)) relation, where α is the constant (0.45), HK is
the Knoop hardness in GPa unit, and (b/a) is the ratio of the diagonal lengths of the indented
surface. Finally, the fracture toughness (KIc) is determined from the microhardness tester
(model Galileo Microscan-2) experiment and the KIc is then calculated from 0.016(E/HV)1/2
(P/C3/2) relation, where E and HV are the values obtained earlier, P is the indenter weight
(in a unit of MPa), and C is the length of the fracture (in a unit of meter) (Meechoowas, 2002).

RESULTS AND DISCUSSION

The phase formation behavior of the sintered ceramics is revealed by an XRD method.
The XRD patterns, shown in Figure 1, indicate that PZT ceramic is identified as a material
with a perovskite structure having tetragonal symmetry (JCPDS card no.33-784) while PMN
ceramic is a perovskite material with a cubic symmetry (JCPDS card no. 81-0861). All
PMN-PZT ceramic composites exhibit pseudocubic crystal structure, as reported in previous
investigations (Ouchi et al., 1965; Ouchi, 1968). However, some impurity phases (Pb2Nb2O7
and MgO) are also observed in the ceramics with x > 0.1. These impurities phases are
believed to precipitate mostly on the surface areas of the specimens (Park et al., 2001).
Further XRD investigation at different depths of the specimens reveals that the impurities
diminish in the interior areas of the specimens.
The SEM micrographs of x(PMN - (1-x)(PZT ceramics, sintered at 1150 ˚C, are shown
in Figure 2. Clearly, the morphology of the grains is composition-dependent and shows mixed
features of the two end-members. PZT and PMN ceramics exhibit more uniform microstructure
than those of the PMN-PZT ceramics. It should be noted that some of the grains are observed
to be in irregular shapes with some open pores. This is a result of a Pb-loss during the
sintering process. Grains of the PMN ceramics are mostly in spherical-like shape, while those
of the secondary pyrochlore phase (Pb2Nb2O7) exhibit a pyramidal morphology. The SEM
micrographs also reveal that the PMN-PZT ceramics with x = 0.1 and x = 0.3 contain very
small and loosely-bonded grains. This clearly suggests that the two compositions are not well
sintered.
150 ➔ CMU. Journal (2004) Vol. 3(2)

Pb2Nb2O7
MgO

PZT

0 . 9 P Z T- 0 . 1 P M N
Arbitrary Intensity

0 . 7 P Z T- 0 . 3 P M N

0 . 5 P Z T- 0 . 5 P M N

0 . 3 P Z T- 0 . 7 P M N

0 . 1 P Z T- 0 . 9 P M N

PMN

20 25 30 35 40 45 50 55 60
2θ (degree)
Figure 1. XRD patterns of x .PMN - (1-x) .PZT ceramics.
 ➔ CMU. Journal (2004) Vol. 3(2) 151

PMN

PMN

10 µm 1 µm
(a) (b)

Py

1 µm 1 µm
(c) (d)

PMN
Py
Py

PMN
Py
Py
Py

1 µm 1 µm
(e) (f)

Figure 2. SEM micrographs of ceramics sintered at 1150˚C: (a) PZT; (b) 0.1PMN-0.9PZT; (c) 0.3PMN-0.7PZT;
(d) 0.7PMN-0.3PZT; (e) 0.9PMN-0.1PZT; and (f) PMN (Py indicates Pyrochlore Phase).
152 ➔ CMU. Journal (2004) Vol. 3(2)

As listed in Table 1, the average grain size varies considerably from 1.40 µm to 5.23 µm.
It should also be noted that the average grain size of all mixed compositions is much smaller
than that of the end members. The reason for the smaller grain sizes is not clearly understood,
but this may be a result of PMN’s role as a grain-growth inhibitor in the PMN-PZT systems.

Table 1. Summary of physical data and optimum mechanical properties for a given
composition of x.PMN - (1-x).PZT ceramics.

Average Vickers Young’s Fracture

Composition Density Grain Hardness Modulus Toughness
Size (HV) (E) (KIc)
(g/cm3) (µm) (GPa) (GPa) (MPa.m1/2)
PZT 7.59 ± 0.11 5.23 5.28 ± 0.49 65.9 ± 2.6 2.48 ± 0.12
0.5PZT-0.5PMN 7.86 ± 0.05 1.90 7.16 ± 0.28 82.4 ± 9.4 3.42 ± 0.26

0.3PZT-0.7PMN 7.87 ± 0.07 1.40 7.28 ± 0.33 99.6 ± 6.1 3.03 ± 0.29

0.1PZT-0.9PMN 7.90 ± 0.09 1.50 7.13 ± 0.37 89.3 ± 9.4 2.03 ± 0.24

PMN 7.82 ± 0.06 3.25 7.75 ± 0.18 84.3 ± 5.6 2.84 ± 0.10

Table 1 also summarizes the optimum mechanical properties for a given composition
of x PMN - (1-x).PZT ceramics, evaluated by the Knoop and the Vickers indentation
.
techniques. It should be mentioned that the mechanical properties of 0.1PMN- 0.9PZT and
0.3PMN- 0.7PZT ceramics are not available. As a result of their low densities, the mechanical
properties of the 0.1PMN- 0.9PZT and 0.3PMN- 0.7PZT ceramics are not quantifiable. The
Vickers hardness (HV) of PMN is found to be highest (7.75 GPa) among the ceramics tested.
It is also of interest to observe that all the mixed compositions exhibit much larger hardness
value (7.13-7.16 GPa) than that of pure PZT (5.28 GPa). This clearly indicates that PMN
addition enhances the hardness of ceramics in PMN-PZT system, as the Vickers hardness
value increases from 5.28 GPa in PZT ceramic to 7.28 GPa in 0.7PMN-0.3PZT ceramic. This
could be attributed to the facts that hardness is a material’s surface property and that there are
some mechanically-hard materials (MgO and Pb2Nb2O7) precipitating on the surfaces of the
mixed compositions, as described in earlier discussions.
Similarly, the Young’s modulus (E) of the PMN and PMN-PZT ceramics (varying
between 82.4 GPa and 99.6 GPa) is significantly higher than that of PZT ceramic, which is
measured to be 65.9 GPa. However, an addition of PZT into PMN-PZT system results in an
increase in the Young’s modulus of the mixed compositions until the trace off is observed in
0.5PZT-0.5PMN ceramic when the density begins to drop due to loss of PbO during the
sintering process. The reason for this observation is somewhat linked to the density of these
ceramics. As seen in Table 1, ceramics with higher density possess comparatively higher
value of the Young’s modulus.
The fracture toughness (KIc) of these ceramics is more difficult to understand because it
depends on many factors, for instance grain size and morphology, crystal structure and phase
 ➔ CMU. Journal (2004) Vol. 3(2) 153

and pore size and distribution. However, it is generally observed that except for the
0.9PMN-0.1PZT composition, the fracture toughness of the mixed compositions (3.42 and
3.03 MPa.m1/2 for 0.5PMN-0.5PZT and 0.7PMN-0.3PZT, respectively) is higher than that of
PMN and PZT ceramics, reported as 2.84 and 2.48 MPa.m1/2). This could very well be a result
of a fracture-inhibition effect by the mechanically- and physically- different components in the
mixtures.
Generally, it can be stated that the mechanical properties of the ceramic systems are
largely controlled by those of PMN ceramics. It is also noticeable that PMN ceramics are
mechanically-superior to PZT ceramics. Finally, it is of interest to observe that some of the
ceramic systems exhibit better mechanical properties than those of the single-phase PMN or
PZT. Intuitively, this can be attributed to a composite nature of the mixtures, in which some
of the properties are enhanced by the presence of inclusions.

CONCLUSIONS
In this study, the (x) Pb(Mg1/3Nb2/3)O3 - (1-x) Pb(Zr0.52Ti0.48)O3 (when x = 0, 0.1, 0.3,
0.5, 0.7, 0.9, and 1.0) ceramic systems are prepared by a conventional mixed-oxide method at
various processing conditions. Perovskite-phase PMN and PZT powders, prepared by a
columbite route and a mixed-oxide route, respectively, are used as starting powders for the
PMN-PZT ceramic systems preparation. Density measurements, XRD and SEM studies and
mechanical properties tests indicate that PMN phase show very important roles in controlling
the properties of the ceramic systems. Finally, it is clearly shown that the mechanical
properties, e.g., Vickers hardness, Young’s modulus and fracture toughness of the ceramics
with mixed compositions are generally better than those of the end members.

ACKNOWLEDGEMENTS
The authors would like to express their gratitude for financial supports from the
Thailand Research Fund (TRF) and Professor Dr. Nuth Bhamornpravate’s Foundation,
Faculty of Science, Chiang Mai University.

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