KR100356640B1 - Oxide Compositions for Piezoelectric Materials - Google Patents

Abstract

In the present invention, an additive Nb ₂ O ₅ is added to the Pb (Al _1/2 Nb _1/2 ) O ₃ -Pb (Zr, Ti) O ₃ (PAN-PZT) piezoelectric ceramic composition, or Nb ₂ O ₅ And MnO ₂ are added to the oxide composition for piezoelectric materials having high dielectric constant (K ₃₃ ^T ), electromechanical coupling coefficient (k _p ) and piezoelectric constant (d ₃₃ ) as well as high mechanical quality coefficient (Q _m ). .

Description

Oxide Compositions for Piezoelectric Materials

In the present invention, an additive Nb ₂ O ₅ is added to the Pb (Al _1/2 Nb _1/2 ) O ₃ -Pb (Zr, Ti) O ₃ (PAN-PZT) piezoelectric ceramic composition, or Nb ₂ O ₅ And an oxide composition for piezoelectric materials to which MnO ₂ is added. The oxide composition for piezoelectric materials according to the present invention was found to have a high dielectric constant (K ₃₃ ^T ), an electromechanical coupling coefficient (k _p ), and a piezoelectric constant (d ₃₃ ) as well as a large mechanical quality factor (Q _m ).

Piezoelectric ceramic materials have been intensively applied to piezoelectric actuators that require high power, such as piezoelectric transformers, ultrasonic motors, sonar, etc. Is in development. As a material for actuators, Pb (Zr, Ti) O ₃ (PZT) -based piezoelectric ceramics have already been applied to various fields and commercialized. In recent years, the development of actuator materials has been progressed through various composition changes based on PZT. Representative examples thereof include Pb (Mg, Nb) O ₃ -Pb (Zr, Ti) O ₃ (PMN-PZT) disclosed in Japanese Patent No. 54025499, and Pb (Al _{1 / 2} Nb _1/2 ) O ₃ -Pb (Zr, Ti) O ₃ (PAN-PZT), but the oxide composition for piezoelectric materials of the prior art is generally electromechanical coupling coefficient, piezoelectric constant, mechanical quality coefficient In this regard, improvements are needed.

Korean Patent Publication No. 91-6710 (Patent No. 46753) discloses an oxide piezoelectric material further comprising an oxide of any one of Cr ₂ O ₃ , NiO and MnO ₂ based on a PAN-PZT-based composition. However, such a PAN-PZT-based composition also does not provide a piezoelectric material having a high electromechanical coupling coefficient, piezoelectric constant and mechanical quality coefficient.

Accordingly, the present inventors have found that piezoelectric materials such as dielectric constant and electromechanical coupling coefficient of conventional PAN-PZT piezoelectric ceramics are maintained at a high level, or piezoelectric material oxides exhibiting improved mechanical quality coefficients while maintaining piezoelectric properties at a high level. As a result of intensive studies for developing the composition, the present invention has been reached.

An object of the present invention is to change the composition of the conventional PAN-PZT-based piezoelectric ceramic composition, not only high piezoelectric properties such as dielectric constant, electromechanical coupling coefficient, piezoelectric constant, etc., but also high mechanical quality coefficient, which is excellent in piezoelectric properties, while maintaining energy loss. It is to provide an oxide composition for piezoelectric materials that can achieve a reduction.

1 is a graph showing the change in electromechanical coefficient (k _p ) of Nb ₂ O ₅ and MnO ₂ in the 0.05PAN-0.494PZ-0.456PT composition.

2 is a graph showing changes in piezoelectric constant (d ₃₃ ) values according to the amount of Nb ₂ O ₅ and MnO ₂ added to the 0.05PAN-0.494PZ-0.456PT composition.

3 is a graph showing the change in the mechanical quality factor (Q _m ) value according to the amount of Nb ₂ O ₅ and MnO ₂ addition of 0.05PAN-0.494PZ-0.456PT composition.

In the present invention, an additive Nb ₂ O ₅ is added to the Pb (Al _1/2 Nb _1/2 ) O ₃ -Pb (Zr, Ti) O ₃ (PAN-PZT) piezoelectric ceramic composition, or Nb ₂ O ₅ And MnO ₂ are added to the piezoelectric oxide composition having not only a high electromechanical coupling coefficient (k _p ) and a piezoelectric constant (d ₃₃ ) but also a high mechanical quality coefficient (Q _m ).

The composition ratio of the oxide composition for piezoelectric materials of the present invention is as follows.

0.05 Pb (Al _1/2 Nb _1/2 ) O ₃ -0.494PbZrO ₃ -0.456PbTiO ₃ + mNb ₂ O ₅

Wherein m is 0.1 to 1.0 wt% based on the total weight of the composition.

0.05 Pb (Al _1/2 Nb _1/2 ) O ₃ -0.494PbZrO ₃ -0.456PbTiO ₃ + mNb ₂ O ₅ + nMnO ₂

Wherein m is 0.6 to 0.9 wt% based on the total weight of the composition and n is 0.3 to 0.8 wt% based on the total weight of the composition.

The oxide composition for piezoelectric materials of the present invention is added with Nb ₂ O ₅ , or Nb ₂ O ₅ and MnO ₂ together to a PZT ternary composition of Pb (Al _1/2 Nb _1/2 ) O ₃ -PbZrO ₃ -PbTiO ₃ The oxide piezoelectric material of the present invention can be easily manufactured by the following general oxide mixing method.

First, oxides such as PbO, TiO ₂ , ZrO ₂ , Al ₂ O ₃ , Nb ₂ O ₅ , MnO _2, and the like are weighed at an appropriate ratio and mixed and calcined using a zirconia ball mill. At this time, the raw material used may be a compound which can be easily converted into an oxide by heating, that is, a hydroxide and a carbonate can be used as the raw material compound. The calcined compound is regrind in a ball mill to add a binder such as PVA and molded at a pressure of 100 MPa. The molded specimen is sintered at a temperature of 1100 to 1200 ° C. PbO, one of the constituents of the oxide during sintering, has a low volatilization temperature of about 880 ° C., which may result in a decrease in the piezoelectric properties of the resulting piezoelectric material due to inaccurate composition. PbZrO ₃ atmosphere powder of the composition was used in a sealed container to suppress volatilization of PbO.

The prepared sintered body was formed on both sides of the electrode and heat-treated at 600 ° C., and then polarized using a DC electric field of 3.5 kV / mm in 120 ° C. silicon oil. Through such a manufacturing process, a piezoelectric material having excellent piezoelectric properties having a composition different from that of the existing PAN-PZT ceramic can be easily manufactured.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to these examples.

<Example>

First, oxides such as PbO, TiO ₂ , ZrO ₂ , Al ₂ O ₃ , Nb ₂ O ₅ , MnO _2, etc. are precisely weighed at an appropriate ratio to be in the composition range of Chemical Formula 1 or Chemical Formula 2, and then mixed and ground using a zirconia ball mill. Then calcined at 800 to 900 ° C. The calcined compound was regrind in a ball mill to add a binder such as PVA and molded at a pressure of 100 MPa. The molded specimen was sintered at a temperature of 1100 to 1200 ° C. In order to suppress volatilization of PbO during sintering, PbZrO ₃ atmosphere powder was used in a sealed container.

The manufactured sintered body was processed into a disk shape having a diameter of 15 mm and a thickness of 1 mm, and then electrodes were formed on both sides, and heat-treated at 600 ° C., and then polarized using a DC electric field of 3.5 kV / mm in a silicon oil at 120 ° C.

The characteristics of the electromechanical coefficient (k _p ) for the polarized specimens were measured according to the literature (IRE, STD (Proc. Of the IRE 1961, pp. 1161-1169)). Table 2 shows changes in piezoelectric properties according to the amount of Nb ₂ O ₅ and MnO ₂ added to the compositions according to the present invention.

Characteristic results of the materials of the examples according to the invention Example Number Additive addition amount (wt%) characteristic Nb ₂ O ₅ MnO ₂ K _p (%) Q _m d ₃₃ (x10 ^-12 C / N) One 0.6 0.4 59.0 1388 332 2 0.6 0.5 58.2 1699 332 3 0.6 0.6 54.7 1420 330 4 0.6 0.7 50.2 360 234 5 0.6 0.8 46.5 358 206 6 0.7 0.3 46.2 1150 235 7 0.7 0.4 58.0 1498 309 8 0.7 0.5 61.6 1725 340 9 0.7 0.6 55.8 1869 302 10 0.7 0.7 49.6 568 221 11 0.7 0.8 44.3 356 181 12 0.8 0.4 58.1 1464 312 13 0.8 0.5 61.2 1695 314 14 0.8 0.6 57.9 1917 287 15 0.8 0.7 59.5 1676 309 16 0.8 0.8 35.3 303 140 17 0.9 0.4 61.4 1781 313 18 0.9 0.5 58.5 1739 310 19 0.9 0.6 60.9 1745 305 20 0.9 0.7 60.6 1579 302 21 0.9 0.8 59.1 1720 280 22 0.1 56.2 85 408 23 0.3 57.8 83 414 24 0.5 58.0 80 418 25 0.7 59.3 79 430 26 1.0 58.8 81 425

Comparison of the properties of the materials of the examples according to the invention with those of the comparative examples of the prior art literature division Composition (x10 ^-2 ) characteristic PAN PZ PT Nb ₂ O ₅ (wt%) MnO ₂ (wt%) K ₃₃ ^T k _p (%) Q _m d ₃₃ (10 ^-12 C / N) Reference Example ^{* 1)} 52 48 730 52.9 860 223 Example 19 ^{* 2)} 5 49.4 45.6 1544 57.4 80 396 Example 49 ^{* 2)} 5 50.4 44.6 0.1 830 48.3 152 Example 50 ^{* 2)} 5 50.4 44.6 0.3 579 34.5 305 Example 51 ^{* 2)} 5 50.4 44.6 0.5 315 30.7 523 Example 52 ^{* 2)} 5 50.4 44.6 1.0 274 18.1 208 Example 22 ^{* 3)} 5 49.4 45.6 0.1 1593 56.2 85 408 Example 23 ^{* 3)} 5 49.4 45.6 0.3 1653 57.8 83 414 Example 24 ^{* 3)} 5 49.4 45.6 0.5 1661 58.0 80 418 Example 25 ^{* 3)} 5 49.4 45.6 0.7 1689 59.3 79 430 Example 26 ^{* 3)} 5 49.4 45.6 1.0 1647 58.8 81 425 Example 6 ^{* 3)} 5 49.4 45.6 0.7 0.3 1041 46.2 1150 235 Example 8 ^{* 3)} 5 49.4 45.6 0.7 0.5 965 61.6 1725 340 Example 10 ^{* 3)} 5 49.4 45.6 0.7 0.7 544 49.6 568 221 * 1) Comparative Example 1: DA Berlincourt et al., Proc. IRE, 48 (1960) 220 * 2) Comparative Example 2: Patent Publication No. 91-6710 * 3) Invention PAN: Pb (Al _1/2 Nb _1/2 ) O ₃ PZ: PbZrO ₃ PT: PbTiO ₃ K ₃₃ ^T : Permittivity of specimen measured at 25 ℃ with frequency of 1 KHz

Referring to the drawings, FIG. 1 is a graph showing the change of the electromechanical coefficient (k _p ) according to the addition amount when the amounts of Nb ₂ O ₅ and MnO ₂ are added to the 0.05PAN-0.494PZ-0.456PT composition. . In Figure 1, when the addition amount of Nb ₂ O ₅ is 0.7 and 0.8 wt%, it can be seen that the high k _p value of more than 60% at 0.5 wt% of the addition amount of MnO ₂ . However, as the amount of MnO ₂ added increases, the K _p value tends to decrease. FIG. 2 is a graph showing the change in piezoelectric constant (d ₃₃ ) value according to the amount of Nb ₂ O ₅ and MnO ₂ added to the 0.05PAN-0.494PZ-0.456PT composition. In FIG. 2, the piezoelectric constant was the highest when 0.7 wt% of Nb ₂ O ₅ and 0.5 wt% of MnO ₂ were added. 3 is a graph showing a change in the mechanical quality factor (Q _m ) value indicating the degree of loss according to the amount of addition when the amount of Nb ₂ O ₅ and MnO ₂ is added to the 0.05PAN-0.494PZ-0.456PT composition. Mechanical quality factor indicates a high value in the MnO ₂ 0.5 wt% and 0.6 wt%, it could be understood that decreases with MnO ₂ added amount is increased more. 1 and 2, the mechanical quality factor of the piezoelectric material to which 0.7 wt% of Nb ₂ O ₅ and 0.5 wt% of MnO ₂ is added is about 1725. Thus, the piezoelectric material having excellent piezoelectric properties and low loss is shown. It can be seen that can be implemented.

Piezoelectric properties of the piezoelectric material of the present invention are piezoelectric properties of PAN-PZT-based materials of Korean Patent Publication No. 91-6710 and PZT materials known as representative piezoelectric ceramics (DA Berlincourt et al., Proc. IRE, 48 (1960) 220). It is shown in Table 2 above in comparison with the characteristics.

From Table 2, the piezoelectric material prepared according to the present invention has a high dielectric constant, electromechanical coupling coefficient, and piezoelectric constant when Nb ₂ O ₅ is added, compared to the piezoelectric material of the prior art document. It can be seen that, if Nb ₂ O ₅ and MnO ₂ is added, the mechanical quality coefficient is greatly improved while maintaining the dielectric constant, electromechanical coupling coefficient, and piezoelectric constant at high levels.

According to the present invention, it is possible to manufacture a piezoelectric material having excellent electromechanical coupling coefficients and mechanical quality coefficients when applied as an actuator, and when applied to the actuator, the piezoelectric characteristics are excellent while the heat generation is low and the loss is small. This can be improved.

Claims (2)

Oxide composition for piezoelectric materials represented by the following formula (1). <Formula 1> 0.05 Pb (Al _1/2 Nb _1/2 ) O ₃ -0.494PbZrO ₃ -0.456PbTiO ₃ + mNb ₂ O ₅ Wherein m is 0.1 to 1.0 wt% based on the total weight of the composition. The oxide composition of claim 1, wherein the oxide composition is represented by the following Chemical Formula 2 by substituting a portion of Nb ₂ O ₅ with MnO ₂ . <Formula 2> 0.05 Pb (Al _1/2 Nb _1/2 ) O ₃ -0.494PbZrO ₃ -0.456PbTiO ₃ + mNb ₂ O ₅ + nMnO ₂ Wherein m is 0.6 to 0.9 wt% based on the total weight of the composition and n is 0.3 to 0.8 wt% based on the total weight of the composition.