Piezoceramic material with high mechanical quality factor and preparation method thereof

Abstract

The invention relates to the field of piezoelectric ceramic materials, in particular to a piezoelectric ceramic material with a high mechanical quality factor and a preparation method of the piezoelectric ceramic material, the chemical structural formula of the piezoelectric ceramic material is as follows: (1-alpha-beta-gamma) Pb1-xLnx (MnyNb1-y) q (ZrzTi1-z) 1-qO3-alpha (SrpBa1-p) SnO3-beta CaTiSiO5-gamma transition metal oxide, 0 < x < = 0.1, 0.2 < = y < = 0.4, 0.4 < = z < = 0.6, and 0.1 < = q < = 0.3; 0.4 < = p < = 0.6; 0 < alpha < = 0.5, 0 < beta < = 0.1, and 0 < gamma < = 0.1. The prepared piezoelectric ceramic material has the characteristics of excellent piezoelectric property and high mechanical quality factor.

Description

Technical Field

[0001] The present invention relates to the field of piezoelectric ceramic materials, and specifically to a piezoelectric ceramic material with a high mechanical quality factor and a preparation method thereof. Background Art

[0002] Continuous vibration of ordinary piezoelectric ceramics at high power will lead to an increase in internal friction and dielectric loss, thereby generating a large amount of heat, which is prone to cause stress damage and performance deterioration. Currently, the widely used piezoelectric ceramics are mainly perovskite-structured PZT piezoelectric ceramics. As a piezoelectric ceramic material that is widely used at present, PZT-based piezoelectric ceramics have been developed and widely applied in fields such as sensors, actuators, and transducers due to their excellent piezoelectric and dielectric properties near the morphotropic phase boundary.

[0003] Of course, in different application fields, different requirements are put forward for its performance. For example, for piezoelectric ceramic materials used to make transducers, it is necessary to ensure that such materials have a high electromechanical coupling coefficient. Piezoelectric ceramic materials applied in the field of transmission and reception need to ensure that they have a high mechanical quality factor and small dielectric loss in a strong electric field environment at high frequencies. However, research shows that these piezoelectric properties are often restricted. Therefore, it is still relatively difficult to prepare PZT piezoelectric ceramic materials with high-level piezoelectric properties, which limits their further application. Summary of the Invention

[0004] Objective of the Invention: Aiming at the above technical problems, the present invention provides a piezoelectric ceramic material with a high mechanical quality factor and a preparation method thereof.

[0005] The technical solution adopted is as follows:

[0006] A piezoelectric ceramic material with a high mechanical quality factor has the following chemical structural formula:

[0007] (1-α-β-γ)Pb 1-x Ln x (Mn y Nb 1-y ) q (Zr z Ti 1-z ) 1-q O3-α(Sr p Ba 1-p )SnO3-

[0008] βCaTiSiO5-γ transition metal oxide

[0009] Wherein, Ln is a lanthanide element;

[0010] 0<x≤0.1, 0.2≤y≤0.4, 0.4≤z≤0.6, 0.1≤q≤0.3;

[0011] 0.4 ≤ p ≤ 0.6;

[0012] 0 < α ≤ 0.5, 0 < β ≤ 0.1, 0 < γ ≤ 0.1.

[0013] Further, Ln is La.

[0014] Further, 0.01 ≤ x ≤ 0.03, 0.25 ≤ y ≤ 0.35, 0.45 ≤ z ≤ 0.55, 0.15 ≤ q ≤ 0.25.

[0015] Further, x = 0.02, y = 1 / 3, z = 0.5, q = 0.25.

[0016] Further, 0.45 ≤ p ≤ 0.55.

[0017] Further, p = 0.5.

[0018] Further, 0.1 ≤ α ≤ 0.2, 0.04 ≤ β ≤ 0.06, 0.01 ≤ γ ≤ 0.02.

[0019] Further, α = 0.15, β = 0.05, γ = 0.015.

[0020] Further, the transition metal oxide is CuO and / or Fe2O3.

[0021] The present invention also provides a method for preparing a high mechanical quality factor piezoelectric ceramic material:

[0022] Mix Pb 1-x Ln x (Mn y Nb 1-y ) q (Zr z Ti 1-z ) 1-q O3, (Sr p Ba 1-p )SnO3, CaTiSiO5, and the transition metal oxide by ball milling, then dry, followed by granulation, sieving, debinding after pressing the green body, and finally sintering at 1200 - 1300 °C for 1 - 5 h.

[0023] Advantages of the present invention:

[0024] The present invention provides a high mechanical quality factor piezoelectric ceramic material. The PMN - PZT composite perovskite solid solution has characteristics such as high dielectric and piezoelectric constants, good electromechanical coupling performance, fast response, high precision, and good stability, and has been widely studied and applied. In this application, part of the lanthanide element replaces Pb 2+, it can reduce the lattice diffusion rate during sintering, hinder the grain growth of piezoelectric ceramics, and refine the grains;

[0025] Barium strontium stannate also has a perovskite structure and can diffuse and dissolve into the PMN-PZT composite perovskite solid solution, improving its structural density and the piezoelectric properties of the piezoelectric ceramic material. Si in CaTiSiO5 4+ segregates at the grain boundaries and can form a large number of crystal nuclei during sintering, preventing the movement of grain boundaries. Due to the intensified growth competition among crystal nuclei, it can inhibit the abnormal growth of grains to a certain extent. Ca 2+ partially replaces Pb 2+ , and Pb 2+ vacancies will be formed, showing the characteristics of hard doping, increasing the mechanical quality factor. Transition metal oxides act as sintering aids, helping to reduce the sintering temperature, increase the ceramic density, and inhibit the abnormal growth of grains;

[0026] The piezoelectric ceramic material prepared by the present invention has excellent piezoelectric properties and a relatively high mechanical quality factor, and has broad application prospects in the fields of sensors, actuators, transducers, etc. Description of the Drawings

[0027] Figure 1 is a scanning electron microscope photograph of the piezoelectric ceramic material prepared in Example 1. It can be seen that the grains are well-developed, the combination between grains is relatively dense, and there are fewer pores at the grain boundaries. Detailed Embodiments

[0028] For those not specified in the embodiments, they are carried out according to conventional conditions or the conditions recommended by the manufacturer. For reagents or instruments not specified by the manufacturer, they are all conventional products that can be obtained through commercial purchase. Technologies not mentioned in the present invention refer to the prior art. Unless otherwise specified, the following examples and comparative examples are parallel experiments and adopt the same treatment steps and parameters.

[0029] Example 1:

[0030] This example provides a piezoelectric ceramic material with a high mechanical quality factor, and its chemical structural formula is as follows:

[0031] 0.785Pb 0.98 La 0.02 (Mn 1 / 3 Nb 2 / 3 ) 0.25 (Zr 0.5 Ti 0.5 ) 0.75 O3 - 0.15(Sr 0.5 Ba 0.5 )SnO3 - 0.05CaTiSiO5 - 0.015CuO

[0032] The preparation method of the above high mechanical quality factor piezoelectric ceramic material is as follows:

[0033] Add Pb3O4, La2O3, MnO2, Nb2O5, ZrO2, and TiO2 into the ball milling tank, use anhydrous ethanol as the ball milling medium, ball mill for 10 h on a planetary ball mill and then dry, and then pre-burn at 950 °C for 5 h to obtain Pb 0.98 La 0.02 (Mn 1 / 3 Nb 2 / 3 ) 0.25 (Zr 0.5 Ti 0.5 ) 0.75 O3;

[0034] Add SrCO3, BaCO3, and SnO2 into the ball milling tank, use anhydrous ethanol as the ball milling medium, ball mill for 10 h on a planetary ball mill and then dry, and then pre-burn at 1100 °C for 5 h to obtain (Sr 0.5 Ba 0.5 )SnO3;

[0035] Add CaCO3, TiO2, and SiO2 into the ball milling tank, use anhydrous ethanol as the ball milling medium, ball mill for 10 h on a planetary ball mill and then dry, and then pre-burn at 1100 °C for 5 h to obtain CaTiSiO5;

[0036] According to the stoichiometric ratio, add Pb 0.98 La 0.02 (Mn 1 / 3 Nb 2 / 3 ) 0.25 (Zr 0.5 Ti 0.5 ) 0.75 O3, (Sr 0.5 Ba 0.5 )SnO3, CaTiSiO5, and CuO into the ball milling tank, use anhydrous ethanol as the ball milling medium, ball mill for 5 h on a planetary ball mill and then dry, granulate with 5 wt% PVA solution as the binder, pass the obtained granulated material through a 120-mesh sieve and then press it into a green body under a pressure of 100 MPa, place the green body in a vacuum sintering furnace, first raise the temperature to 650 °C at a rate of 1 °C / min to remove the binder for 2 h, and then raise the temperature to 1250 °C at a rate of 10 °C / min and hold for sintering for 5 h.

[0037] Example 2:

[0038] This example provides a high mechanical quality factor piezoelectric ceramic material, and its chemical structural formula is as follows:

[0039] 0.785Pb 0.98 La 0.02 (Mn1 / 3 Nb 2 / 3 ) 0.25 (Zr 0.5 Ti 0.5 ) 0.75 O3-0.15(Sr 0.5 Ba 0.5 )SnO3-0.05CaTiSiO5-0.015CuO

[0040] The preparation method of the above high mechanical quality factor piezoelectric ceramic material is as follows:

[0041] Add Pb3O4, La2O3, MnO2, Nb2O5, ZrO2, and TiO2 into the ball milling tank, use anhydrous ethanol as the ball milling medium, ball mill for 10 h on a planetary ball mill and then dry, and then pre-burn at 950 °C for 5 h to obtain Pb 0.98 La 0.02 (Mn 1 / 3 Nb 2 / 3 ) 0.25 (Zr 0.5 Ti 0.5 ) 0.75 O3;

[0042] Add SrCO3, BaCO3, and SnO2 into the ball milling tank, use anhydrous ethanol as the ball milling medium, ball mill for 10 h on a planetary ball mill and then dry, and then pre-burn at 1100 °C for 5 h to obtain (Sr 0.5 Ba 0.5 )SnO3;

[0043] Add CaCO3, TiO2, and SiO2 into the ball milling tank, use anhydrous ethanol as the ball milling medium, ball mill for 10 h on a planetary ball mill and then dry, and then pre-burn at 1100 °C for 5 h to obtain CaTiSiO5;

[0044] According to the stoichiometric ratio, mix Pb 0.98 La 0.02 (Mn 1 / 3 Nb 2 / 3 ) 0.25 (Zr 0.5 Ti 0.5 ) 0.75 O3, (Sr 0.5 Ba 0.5)SnO3, CaTiSiO5, and CuO were added to a ball milling jar. Using absolute ethanol as the ball milling medium, they were ball milled for 5 h on a planetary ball mill and then dried. Granulation was carried out using a 5 wt% PVA solution as a binder. The obtained granulated material was passed through a 120-mesh sieve and then pressed into a green body under a pressure of 100 MPa. The green body was placed in a vacuum sintering furnace. First, it was heated to 650 °C at a rate of 1 °C / min for 2 h to remove the binder, and then heated to 1200 °C at a rate of 10 °C / min and held for sintering for 5 h.

[0045] Example 3:

[0046] This example provides a high mechanical quality factor piezoelectric ceramic material, and its chemical structural formula is as follows:

[0047] 0.785Pb 0.98 La 0.02 (Mn 1 / 3 Nb 2 / 3 ) 0.25 (Zr 0.5 Ti 0.5 ) 0.75 O3 - 0.15(Sr 0.5 Ba 0.5 )SnO3 - 0.05CaTiSiO5 - 0.015CuO

[0048] The preparation method of the above high mechanical quality factor piezoelectric ceramic material is as follows:

[0049] Pb3O4, La2O3, MnO2, Nb2O5, ZrO2, and TiO2 were added to a ball milling jar. Using absolute ethanol as the ball milling medium, they were ball milled for 10 h on a planetary ball mill and then dried. Then, they were pre-sintered at 950 °C for 5 h to obtain Pb 0.98 La 0.02 (Mn 1 / 3 Nb 2 / 3 ) 0.25 (Zr 0.5 Ti 0.5 ) 0.75 O3;

[0050] SrCO3, BaCO3, and SnO2 were added to a ball milling jar. Using absolute ethanol as the ball milling medium, they were ball milled for 10 h on a planetary ball mill and then dried. Then, they were pre-sintered at 1100 °C for 5 h to obtain (Sr 0.5 Ba 0.5 )SnO3;

[0051] CaCO3, TiO2, and SiO2 were added to a ball milling jar. Using absolute ethanol as the ball milling medium, they were ball milled for 10 h on a planetary ball mill and then dried. Then, they were pre-sintered at 1100 °C for 5 h to obtain CaTiSiO5;

[0052] According to the stoichiometric ratio, Pb 0.98 La 0.02 (Mn 1 / 3 Nb 2 / 3 ) 0.25 (Zr 0.5 Ti 0.5 ) 0.75 O3, (Sr 0.5 Ba 0.5 )SnO3, CaTiSiO5, CuO are added to the ball milling tank. Using anhydrous ethanol as the ball milling medium, ball mill for 5 h on a planetary ball mill and then dry. Use a 5 wt% PVA solution as the binder for granulation. After the obtained granular material passes through a 120-mesh sieve, press it into a green body under a pressure of 100 MPa. Place the green body in a vacuum sintering furnace. First, raise the temperature to 650 °C at a rate of 1 °C / min for degumming for 2 h, and then raise the temperature to 1300 °C at a rate of 10 °C / min and hold for sintering for 5 h to obtain the product.

[0053] Example 4:

[0054] This example provides a high mechanical quality factor piezoelectric ceramic material, and its chemical structural formula is as follows:

[0055] 0.785Pb 0.98 La 0.02 (Mn 1 / 3 Nb 2 / 3 ) 0.25 (Zr 0.5 Ti 0.5 ) 0.75 O3 - 0.15(Sr 0.5 Ba 0.5 )SnO3 - 0.05CaTiSiO5 - 0.015Fe2O3

[0056] The preparation method of the above high mechanical quality factor piezoelectric ceramic material is as follows:

[0057] Add Pb3O4, La2O3, MnO2, Nb2O5, ZrO2, TiO2 to the ball milling tank. Using anhydrous ethanol as the ball milling medium, ball mill for 10 h on a planetary ball mill and then dry. Then pre-burn at 950 °C for 5 h to obtain Pb 0.98 La 0.02 (Mn 1 / 3 Nb 2 / 3 ) 0.25 (Zr 0.5 Ti 0.5 ) 0.75 O3;

[0058] SrCO3, BaCO3, and SnO2 were added to a ball milling tank. Using absolute ethanol as the ball milling medium, it was ball milled for 10 h on a planetary ball mill and then dried. It was pre-sintered at 1100 °C for 5 h to obtain (Sr 0.5 Ba 0.5 )SnO3;

[0059] CaCO3, TiO2, and SiO2 were added to a ball milling tank. Using absolute ethanol as the ball milling medium, it was ball milled for 10 h on a planetary ball mill and then dried. It was pre-sintered at 1100 °C for 5 h to obtain CaTiSiO5;

[0060] According to the stoichiometric ratio, Pb 0.98 La 0.02 (Mn 1 / 3 Nb 2 / 3 ) 0.25 (Zr 0.5 Ti 0.5 ) 0.75 O3, (Sr 0.5 Ba 0.5 )SnO3, CaTiSiO5, and Fe2O3 were added to a ball milling tank. Using absolute ethanol as the ball milling medium, it was ball milled for 5 h on a planetary ball mill and then dried. Granulation was carried out using a 5 wt% PVA solution as a binder. The obtained granulated material was passed through a 120 mesh sieve and then pressed into a green body under a pressure of 100 MPa. The green body was placed in a vacuum sintering furnace. First, it was heated to 650 °C at a rate of 1 °C / min for 2 h to remove the binder, and then it was heated to 1250 °C at a rate of 10 °C / min and held for 5 h for sintering.

[0061] Comparative Example 1:

[0062] It was basically the same as Example 1, except that Pb 0.98 La 0.02 (Zr 0.5 Ti 0.5 )O3 was used to replace Pb 0.98 La 0.02 (Mn 1 / 3Nb 2 / 3 ) 0.25 (Zr 0.5 Ti 0.5 ) 0.75 O3.

[0063] This example provides a piezoelectric ceramic material with a high mechanical quality factor, and its chemical structural formula is as follows:

[0064] 0.785Pb 0.98 La 0.02 (Zr 0.5 Ti 0.5 )O3 - 0.15(Sr 0.5 Ba0.5 ) SnO3 - 0.05CaTiSiO5 - 0.015CuO

[0065] The preparation method of the above high mechanical quality factor piezoelectric ceramic material is as follows:

[0066] Add Pb3O4, La2O3, ZrO2, and TiO2 into the ball milling tank, use anhydrous ethanol as the ball milling medium, ball mill for 10 h on a planetary ball mill and then dry, and then pre - sinter at 950 °C for 5 h to obtain Pb 0.98 La 0.02 (Zr 0.5 Ti 0.5 )O3;

[0067] Add SrCO3, BaCO3, and SnO2 into the ball milling tank, use anhydrous ethanol as the ball milling medium, ball mill for 10 h on a planetary ball mill and then dry, and then pre - sinter at 1100 °C for 5 h to obtain (Sr 0.5 Ba 0.5 )SnO3;

[0068] Add CaCO3, TiO2, and SiO2 into the ball milling tank, use anhydrous ethanol as the ball milling medium, ball mill for 10 h on a planetary ball mill and then dry, and then pre - sinter at 1100 °C for 5 h to obtain CaTiSiO5;

[0069] According to the stoichiometric ratio, add Pb 0.98 La 0.02 (Zr 0.5 Ti 0.5 )O3, (Sr 0.5 Ba 0.5 )SnO3, CaTiSiO5, and CuO into the ball milling tank, use anhydrous ethanol as the ball milling medium, ball mill for 5 h on a planetary ball mill and then dry, granulate with 5 wt% PVA solution as the binder, pass the obtained granulated material through a 120 - mesh sieve, and then press it into a green body under a pressure of 100 MPa. Place the green body in a vacuum sintering furnace, first raise the temperature to 650 °C at a rate of 1 °C / min for degumming for 2 h, and then raise the temperature to 1250 °C at a rate of 10 °C / min for heat - preservation sintering for 5 h.

[0070] Comparative Example 2:

[0071] It is basically the same as Example 1, the difference is that (Sr 0.5 Ba 0.5 )SnO3 is not added.

[0072] Comparative Example 3:

[0073] It is basically the same as Example 1, the difference is that CaTiSiO5 is not added.

[0074] Comparative Example 4:

[0075] It is basically the same as Example 1, except that Fe2O3 is not added.

[0076] Performance test:

[0077] The surfaces of the piezoelectric ceramic materials prepared in Examples 1-4 and Comparative Examples 1-4 were polished respectively, silver paste was coated on both sides, and they were kept at 750 °C for 10 min. Finally, they were polarized in silicone oil at 120 °C under a DC voltage of 4 kV / mm for 20 min and then left for 24 h to be used as specimens to test their electrical properties.

[0078] The room-temperature piezoelectric constant of the specimen was measured using a ZJ-3AN type quasi-static piezoelectric constant tester;

[0079] The electromechanical coupling coefficient kp, mechanical quality factor Qm and dielectric loss tanδ (25 °C, 1 v, 1 kHz) of the specimen were measured and analyzed using a precision impedance analyzer (Agilent HP4294A);

[0080] The test results are shown in Table 1 below:

[0081] Table 1:

[0082]

[0083] As can be seen from Table 1 above, the piezoelectric ceramic material prepared by the present invention has the characteristics of excellent piezoelectric performance and relatively high mechanical quality factor.

[0084] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A high mechanical quality factor piezoelectric ceramic material, characterized in that, Its chemical structural formula is as follows: (1-α-β-γ)Pb 1-x Ln x (Mn y Nb 1-y ) q (Zr z Ti 1-z ) 1-q O3-α(Sr p Ba 1-p )SnO3- βCaTiSiO5-γ transition metal oxide wherein, Ln is a lanthanide element; 0 < x ≤ 0.1, 0.2 ≤ y ≤ 0.4, 0.4 ≤ z ≤ 0.6, 0.1 ≤ q ≤ 0.3; 0.4≤p≤0.6； 0 < α ≤ 0.5, 0 < β ≤ 0.1, 0 < γ ≤ 0.

1.

2. The high mechanical quality factor piezoelectric ceramic material according to claim 1, characterized in that, Ln is La.

3. The high mechanical quality factor piezoelectric ceramic material according to claim 1, wherein 0.01 ≤ x ≤ 0.03, 0.25 ≤ y ≤ 0.35, 0.45 ≤ z ≤ 0.55, 0.15 ≤ q ≤ 0.

25.

4. The high mechanical quality factor piezoelectric ceramic material according to claim 1, characterized in that x = 0.02, y = 1 / 3, z = 0.5, q = 0.

25.

5. The high mechanical quality factor piezoelectric ceramic material as described in claim 1, wherein, 0.45≤p≤0.55。 6. The high mechanical quality factor piezoelectric ceramic material according to claim 1, wherein, p＝0.5。 7. The high mechanical quality factor piezoelectric ceramic material according to claim 1, characterized in that, 0.1 ≤ α ≤ 0.2, 0.04 ≤ β ≤ 0.06, 0.01 ≤ γ ≤ 0.

02.

8. The high mechanical quality factor piezoelectric ceramic material according to claim 1, wherein α = 0.15, β = 0.05, γ = 0.

015.

9. The high mechanical quality factor piezoelectric ceramic material according to claim 1, characterized in that, The transition metal oxide is CuO and / or Fe2O3.

10. A method for preparing a high mechanical quality factor piezoelectric ceramic material as described in any one of claims 1-9, characterized in that, Mix Pb 1-x Ln x (Mn y Nb 1-y ) q (Zr z Ti 1-z ) 1-q O3, (Sr p Ba 1-p )SnO3, CaTiSiO5, and transition metal oxides by ball milling, then dry, followed by granulation, sieving, debinding after pressing the green body, and finally sinter at 1200 - 1300 °C for 1 - 5 h.

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