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Ferroelectrics
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Electrical Properties of Low Temperature Sintered Piezoceramics

Tingting Wang , Feifei An & Jian Yu
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Functional Materials Research Laboratory, Tongji University, Shanghai, 200092, China Version of record first published: 01 Dec 2010.

To cite this article: Tingting Wang , Feifei An & Jian Yu (2010): Electrical Properties of Low Temperature Sintered Piezoceramics, Ferroelectrics, 408:1, 98-102 To link to this article: http://dx.doi.org/10.1080/00150193.2010.485540

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Ferroelectrics, 408:98102, 2010 Copyright Taylor & Francis Group, LLC ISSN: 0015-0193 print / 1563-5112 online DOI: 10.1080/00150193.2010.485540

Electrical Properties of Low Temperature Sintered Piezoceramics

TINGTING WANG, FEIFEI AN, AND JIAN YU
Functional Materials Research Laboratory, Tongji University, Shanghai 200092, China

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In general, commercial PZT piezoceramics are sintered at temperature above 1200 C. Here, one low-temperature sintering technology was developed for PZT piezoceramics by adding perovskite-type ferroelectrics with low sintering temperature, alternative to adding non-piezoelectric low-melting glass or eutectic oxides. Through solid state reaction mechanism, very densied piezoceramics of (Pb0.95 Sr0.05 )(Zr0.53 Ti0.47 )O3 with 0.6PbTiO3 0.3Bi(Zn0.5 Ti0.5 )O3 0.1BiFeO3 as sintering additive were obtained below 1050 C. The phase of (Pb,Bi,Sr)(Zr,Ti,Zn,Fe)O3 solid solution piezoceramics was demonstrated to be single-phased perovskite structure and the measurements of dielectric, ferroelectric and piezoelectric properties showed good piezoelectric performance equivalent to PZT-8.

I. Introduction
Driven by low driving electric force and large output displacements, multilayer-stacked transducers have been becoming dominant in the market. Till now, high-temperature sintering technology above 1200 C with expensive high-melting point W/Mo inner electrode and low-temperature sintering technology below 950 C with Ag inner electrode have been developed. Owing to high sintering temperature, the former method accompanies with volatility of lead content, increased energy consumption and high fabrication costs. By using the additive of non-piezoelectric low-melting point glass or eutectic oxides, which occur usually at grain boundaries after sintering process to deteriorate transducer performances, the latter method remains to maximize piezoelectric performances [13]. In this paper, one sintering technology with low-sintering temperature ferroelectric of 0.6PbTiO3 0.3Bi(Zn0.5 Ti0.5 )O3 0.1BiFeO3 (labeled as PT-BZT-BF) as sintering additive for PZT piezoceramics was developed [4]. The (Pb,Bi,Sr)(Zr,Ti,Zn,Fe)O3 (labeled as PZTLTF) piezoceramics were prepared using modied conventional solid state reaction method, their phase structure, microstructure and piezoelectric properties were presented.

II. Experimental Procedure

The perovskite-type PZT-LTF piezoceramic samples were synthesized with conventional electronic ceramic processing. Firstly, the oxides of PbO, ZrO2 , TiO2 , SrCO3 and MnO2
Received August 23, 2009; in nal form September 23, 2009. Corresponding author. Tel: +86-21-65980544-103; Fax: +86-21-65985179. E-mail: jyu@ tongji.edu.cn

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were weighted in accordance with the chemical formula of (Pb0.95 Sr0.05 )(Zr0.53 Ti0.47 )O3 + 0.5wt% MnO2 (labeled as PSZT), ground with ethanol and calcined at 800 C for 5 h. Then, the oxides of PbO, TiO2 , Bi2 O3 , ZnO and Fe2 O3 were weighted and mixed in accordance with the formula of PT-BZT-BF. At last, the PZT-LTF ceramics were prepared by mixing the calcined PSZT powder and 9wt% PT-BZT-BF. The green pellets of 10 mm diameter were compacted under 250 MPa, and sintered at temperature between 990 and 1050 C for 5 h. For electrical characterization, the ceramic pellets were polished, coated with silver paste and red at 600 C for 10 min. The processing was described in detail elsewhere [4]. The phase structure and microstructure of those sintered ceramics were analyzed using an X-ray diffractometer (D8, Bruker, Germany) and a scanning electron microscopy (JSM EMP-800, Japan), respectively. Their dielectric properties were investigated with HP 4194A impedance analyzer under oscillation voltage of 1.0 V. The polarization-electric eld hysteresis loops were measured with ferroelectric materials analyzer (Radiant, Precision Premier II, USA). For piezoelectric measurements, the samples were poled in a silicone oil bath at 150 C by applying a DC electric eld of 3kV/mm for 15 min. The piezoelectric constant d33 was measured using a quasi-static piezoelectric d33 meter (Model ZJ-3d, Institute of Acoustics, Chinese Academy of Science).

III. Results and Discussion

For the perovskite-type PT-BZT-BF ferroelectrics is in the tetragonal structure with tetragonality of c/a = 1.105 [5] but PSZT is rhombohedral near the morphotropic phase boundary at room temperature, it is reasonable to expect the solid solution of PSZT and PT-BZT-BF in the tetragonal phase. For the PZT-LTF pellets sintered at temperature between 990 and 1050 C, the characterization of X-ray diffraction indicated that they are well crystallized in the tetragonal phase. As an illustration, Fig. 1 showed the pattern for the sample sintered at 1050 C for 5 h, of which the tetragonal phase is demonstrated by the splitting of the (001)/(100) and (002)/(200) peaks. Contemporarily, the microstructure of the fracture surface observed by scanning electron microscopy was presented in the Fig. 2 for the same

Figure 1. XRD pattern of PZT-LTF pellet sintered at 1050 C for 5 h.

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Figure 2. SEM microstructure picture of the fracture surface for the same sample as Fig. 1.

sample as in the Fig. 1. It was seen that the very densied pellet was obtained here at lower sintering temperature more 150 C than the conventional PZT ceramic processing. In the Fig. 3, the dielectric constant and loss as a function of frequency were presented for the poled PZT-LTF pellets sintered at temperature between 990 and 1050 C. The room temperature dielectric constant at 1kHz increases with increasing sintering temperature, = 760 and tan = 0.7% was obtained for the sample sintered at 1050 C. Moreover, the measurement of temperature-dependent dielectric constant indicated the ferroelectric- paraelectric Curie temperature Tc = 298 C. In comparison with (Pb0.95 Sr0.05 )(Zr0.53 Ti0.47 )O3 piezoceramics of = 1002 [6], the reduced dielectric constant of the PZT-LTF ceramics may result from both the effects of the Mn addition, which usually makes PZT become hard, and the PT-BZT-BF component with low dielectric constant of 170. On the other hand, the

Figure 3. Frequency-dependent dielectric constant and loss of PZT-LTF ceramics sintered at temperature between 990 and 1050 C for 5 h.

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Figure 4. Polarization-electric eld hysteresis loops recorded at room temperature for the same samples as Fig. 3.

Curie temperature of the PZT-LTF ceramics is lower than Tc = 360 C of the PSZT and Tc = 700 C of PT-BZT-BF components, which is similar to the case of PZT-BiFeO3 solid solution [7]. For the samples sintered between 990 and 1050 C, ferroelectric properties were measured and the obtained Polarization-Electric eld hysteresis loops were presented in the Fig. 4. With increasing sintering temperature, the crystallization of PZT-LTF piezoceramics was enhanced and a high permanent polarization Pr of 10.8 C/cm2 and coercive eld Ec of 2.11kV/mm was obtained for the sample sintered at 1050 C. Similar to ferroelectric properties, a high piezoelectric coefcient d33 was also observed as 241pC/N for the sample sintered at 1050 C. So far, it can be seen that the piezoelectric performance of PZT-LTF ceramics is equivalent to that of commercial PZT-8 with = 1000, d33 = 225pC/N, and Tc = 300 C [8].

IV. Conclusions
One novel low-temperature sintering technology for PZT piezoceramics below 1050 C was developed and demonstrated with the perovskite-type PSZT-PT-BZT-BF solid solution system. For the PZT-LTF piezoceramics sintered at 1050 C, a better piezoelectric performance with = 760, tan = 0.7%, d33 = 241pC/N, and Tc = 298 C was obtained, which is equivalent to PZT-8, and can be applied for manufacturing multilayer transducers with Ag/Pd inner electrode.

Acknowledgments
This work was partially supported by NSFC Grant 50875181, FANEDD-200744, Shanghai Pujiang Program-07pj14087 and NCET-07-0624.

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