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Article history: The dielectric, piezoelectric, and electromechanical properties of B-site cobalt-modied sodium lan-
Received 26 August 2009 thanum bismuth titanate (Na0.5 La0.5 Bi4 Ti4 O15 , NLBT) piezoelectric ceramics were investigated. The
Received in revised form 19 March 2010 piezoelectric properties of NLBT ceramics can be enhanced by cobalt modications. The NLBT ceramics
Accepted 31 March 2010
modied with 0.2 wt.% cobalt trioxide (NLBT-C4) possess good piezoelectric properties, with piezoelectric
coefcient d33 of 27 pC/N, electromechanical coupling factors (kp and kt ) of 6.5% and 28.5%, and mechan-
PACS:
ical quality factor Qm (kp mode) of 3400. The Curie temperature Tc of cobalt-modied NLBT ceramics
77.84.s
was found to slightly higher than that of pure NLBT ceramics. A large dielectric abnormity in dielectric
77.84.Dy
77.65.Bn
loss tan was observed in NLBT ceramics, which can be signicantly suppressed by cobalt modication.
77.80.Bh Thermal annealing studies presented the cobalt-modied NLBT ceramics possess stable piezoelectric
77.80.Dj properties.
2010 Elsevier B.V. All rights reserved.
Keywords:
Piezoelectric materials
Ferroelectrics
Dielectric properties
Sodium bismuth titanate
1. Introduction shows the crystal structure of four-layer BLSFs, for the NLBT, A-
site ions are Na, La, Bi ions, and B-site ions are Ti ions. The grain
High temperature technology is of major importance to growth rate in the direction perpendicular to the c-axis of the BLSFs
the automotive, aerospace, and power generation industries crystal is much higher than that in the direction parallel to the c-
[14]. Piezoelectric single crystals such as LiNbO3 , La3 Ga5 SiO14 , axis, so the grain growth is structurally highly anisotropic, and the
Sr2 Nb2 O7 , and La2 Ti2 O7 , and GaPO4 are generally used as high grains are plate-like shape. The BLSF ceramics, due to their rela-
temperature sensing components, however, the crystal growth of tively high Curie temperature Tc , have received signicant attention
these materials needs expensive equipment and has low yield. The for their potential use in high-temperature piezoelectric devices,
important advantage of polycrystalline piezoelectric ceramics over such as high-temperature piezoelectric owmeter, actuator, and
single crystals is the ease with which composition and properties accelerometer [24]. However, the piezoelectric activities in pure
may be tailored. and modied BLSF ceramics were found to be very low, and it is
Aurivillius-type bismuth layer-structured ferroelectrics (BLSFs) difcult to achieve high piezoelectric activities in ordinary sintered
are widely known to possess a structure expressed by the gen- BLSF ceramics with randomly oriented grain structure, because of
eral formula of (Bi2 O2 )2+ (Am1 Bm O3m+1 )2 , where A is a mono-, the two-dimensional orientation restriction of the rotation of their
di-, and tri-valent ion or combination of them allowing dodec- spontaneous polarization (Ps ) and their high coercive elds (Ec ).
ahedral coordination, B is a transition element or combination Generally, among the material properties determining device
of cations well suited to octahedral coordination, and m is performance, the piezoelectric activities of piezoelectric materials
an integer which represents the number of BO6 octahedra in are very important. For example, for a charge mode accelerometer,
(Am1 Bm O3m+1 )2 between the (Bi2 O2 )2+ layers, usually in the this can be demonstrated by the charge sensitivity which is a vital
range of 15. The pseudo-perovskite (Am1 Bm O3m+1 )2 layers inter- parameter used to scale the device sensitivity:
leave with (Bi2 O2 )2+ layers along the c-axis of the BLSFs. Fig. 1
Sq = d m (1)
0921-5107/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.mseb.2010.03.076
80 C.-M. Wang et al. / Materials Science and Engineering B 171 (2010) 7985
2. Experimental
The density of the sintered samples was determined by apply- For electrical and dielectric properties measurements, silver elec-
ing the Archimedes method. The X-ray diffraction (XRD) patterns trodes (1 cm2 ) were screen-printed on both surfaces of the polished
for the polished surface were obtained with an X-ray diffrac- pellets and red at 570 C for 20 min. The electrical resistivity
tometer (D8 Advance, Bruker AXS GmbH) using Cu K1 radiation. was calculated from the resistance, which was measured using
Fig. 3. Temperature dependence of dielectric permittivity and dielectric loss tan of the control and cobalt-modied NLBT piezoelectric ceramics (a) NLBT, (b) NLBT-C2, (b)
NLBT-C4, and (d) NLBT-C8.
82 C.-M. Wang et al. / Materials Science and Engineering B 171 (2010) 7985
Fig. 5. Scanning electron microscopy images for the surface of the pure and cobalt-modied NLBT piezoelectric ceramics (a) NLBT, (b) NLBT-C2, (c) NLBT-C4, (d) NLBT-C6,
and (e) NLBT-C8.
duce oxygen at elevated temperature, so the oxygen vacancies can bigger than the thickness t. It also can be seen, the cobalt-modied
be compensated by oxygen, and then the dielectric abnormity may NLBT ceramics exhibited the larger grain size compared to the pure
also be suppressed. Further work must be conducted to determine NLBT ceramics, indicating that the introduction of cobalt enhanced
the exact mechanism on the dielectric abnormity. The dielectric the grain growth of the ceramics. The increase in grain size resulted
loss tan was found to increase with the temperature increasing, in both the density and the shrinkage increasing, which are bene-
but with the temperature further increasing, the loss tan sharply cial to the piezoelectric properties of the ceramics.
drops at a specic temperature, which is corresponding to the Curie The detailed room temperature (RT) electrical properties of the
temperature Tc . That is, this dielectric loss valley is corresponding pure and cobalt-modied NLBT ceramics are characterized and
to the dielectric permittivity peak. From Fig. 4, it is also found that listed in Table 1. The RT relative dielectric permittivity of the
the cobalt-modied NLBT ceramics, especially NLBT-C2 and NLBT- NLBT ceramics does not change signicantly with cobalt modi-
C4, presented reduced loss tan in the temperature range from RT cation, varying between 180 and 210. The RT dielectric loss tan
to 500 C, compared to the pure NLBT ceramics. for the pure and cobalt-modied NLBT was found to be very low,
Fig. 5 shows the scanning electron microscopy images for the less than 0.5%. The loss tan of the cobalt-modied NLBT ceram-
surface of the pure and cobalt-modied NLBT piezoelectric ceram- ics was found to be lower than that of the pure NLBT ceramics,
ics. Due to the high grain growth rate in the direction perpendicular and the dielectric loss for the NLBT-C4 ceramics was found to be
to the c-axis of the BLSFs crystal, the grain growth is structurally only 0.2%. The piezoelectric properties of the cobalt-modied NLBT
highly anisotropic and the length l of the plate-like grain is much ceramics were obviously enhanced compared to that of the pure
84 C.-M. Wang et al. / Materials Science and Engineering B 171 (2010) 7985
Table 1
Electrical properties of cobalt-modied sodium lanthanum bismuth titanate ceramics.
Fig. 6. Frequency dependence of impedance |Z| and phase angle of the NLBT-C4 Fig. 8. Effect of annealing temperature for 1 h on the piezoelectric coefcient d33 of
piezoelectric ceramics in a planar mode. the NLBT-C4 piezoelectric ceramics.
C.-M. Wang et al. / Materials Science and Engineering B 171 (2010) 7985 85
The thermal annealing behaviors of the NLBT-C4 ceramics are entist Research Foundation of Shandong Province of China under
shown in Fig. 8, where the piezoelectric coefcient d33 is plot- Grant No. 2008BS04002, the Specialized Research Fund for the
ted against the annealing temperature. The value of piezoelectric Doctoral Program of Higher Education of China under Grant Nos.
coefcient d33 shows no obvious drop, when the annealing tem- 20070422059 and 20080422003.
perature is lower than 500 C, and it retains 25 pC/N, even if the
annealing temperature reaches 500 C. This reveals that the four- References
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