Piezoelectric ceramic material between p4 and p5 systems and method for manufacturing the same

Abstract

This invention discloses a piezoelectric ceramic material intermediate between P4 and P5 systems and its preparation method, belonging to the field of piezoelectric ceramics and their preparation methods; aiming to provide a piezoelectric ceramic material with low energy consumption and high energy conversion efficiency and its preparation method. The composition formula of the piezoelectric ceramic chip of this invention is: (1-x-y-z)Pb(Zr,Ti)O3-xPb(Mn) 1 / 3Sb 2 / 3 )O3-yPb(Ni 1 / 3 Nb 2 / 3 )O3-zPb(Zn 1 / 3 Nb 2 / 3 The composition is: Pb3O4 + 0.25wt% CeO2; Zr / Ti = 1.08–1.1, x = 0.01–0.015; y = 0.04–0.06, z = 0.08–0.1. The method of this invention is as follows: Pb3O4, ZrO2, TiO2, MnO2, Sb2O3, CeO2, Nb2O5, NiO, and ZnO are mixed, wet-milled, dried, and sieved; the abrasive is pre-fired once; the pre-fired material is pulverized and then wet-milled again, dried, and sieved to obtain ceramic powder; the ceramic powder is spray-granulated and pressed into ceramic blanks; the ceramic blanks are sintered to obtain ceramic sheets; the ceramic sheets are silvered; the silvered ceramic sheets are polarized. The piezoelectric ceramic material of this invention exhibits excellent piezoelectric and dielectric properties and low dielectric loss, and can be widely used in ultrasonic atomizing devices, transducer devices, and other fields.

Description

Technical Field

[0001] This invention relates to a piezoelectric ceramic material and its preparation method, and more particularly to a piezoelectric ceramic material and its preparation method that are intermediate between P4 and P5 systems. Background Technology

[0002] P4 piezoelectric ceramics are mainly used in medium-power transducers such as ultrasonic atomizers and sonar systems. The main parameter is ε. 33 T / ε0≤2200、d 33 ≥300pC / N, tanδ≤0.4%, Kp≥0.5; The P5 system is mainly used in electroacoustic and ultrasonic sensor devices. The main parameter ε 33 T / ε0≥1500、d 33 ≥300pC / N, tanδ≥1.0%, Kp≥0.65. It is easy to see that the P4 system piezoelectric ceramics have small dielectric loss tanδ and a high piezoelectric constant d. 33 The small planar electromechanical coupling coefficient Kp value has the advantage of low energy consumption at high frequencies, but the disadvantage of low energy conversion efficiency; the P5 system piezoelectric ceramics have a large dielectric loss tanδ and a piezoelectric constant d 33 The large planar electromechanical coupling coefficient Kp value has the advantage of high energy conversion efficiency, but the disadvantage of high energy consumption at high frequencies.

[0003] With market development, ultrasonic transducers and ultrasonic atomizers are being forced to develop towards low energy consumption and high energy conversion efficiency. The technical parameters of simple P4 and P5 piezoelectric ceramics are gradually failing to meet market demands. Summary of the Invention

[0004] In view of the above-mentioned defects in the prior art, the present invention aims to provide a piezoelectric ceramic material with low energy consumption and high energy conversion efficiency, which is between the P4 and P5 systems. Another objective of the present invention is to provide a method for preparing the piezoelectric ceramic material.

[0005] To achieve the above objectives, the piezoelectric ceramic material provided by this invention has the following composition formula:

[0006] (1-xyz)Pb(Zr,Ti)O3-xPb(Mn) 1 / 3 Sb 2 / 3 )O3-yPb(Ni 1 / 3 Nb 2 / 3 )O3-zPb(Zn 1 / 3 Nb 2 / 3)O3+0.25wt%CeO2; where Zr / Ti=1.08~1.1, x=0.01~0.015, y=0.04~0.06, z=0.08-0.1.

[0007] In the above technical solution, the preferred Zr / Ti ratio is 1.08, x = 0.012, y = 0.005, and z = 0.095.

[0008] The preparation method provided by this invention adopts the following technical solution:

[0009] 1) According to the proportions in the composition formula, Pb3O4, ZrO2, TiO2, MnO2, Sb2O3, CeO2, Nb2O5, NiO, ZnO and deionized water are mixed, ball-milled for 3-6 hours, dried, and passed through a 20-40 mesh sieve to obtain primary abrasive.

[0010] 2) Place the primary abrasive material in a sintering furnace, heat it to 900-1000℃ at a rate of 2.5-3℃ / min, and hold it at that temperature for 2 hours to obtain the pre-burned material;

[0011] 3) After crushing the pre-fired material, add deionized water, ball mill for 3-5 hours, dry, and pass through a 40-mesh sieve to obtain ceramic powder;

[0012] 4) The ceramic powder is spray-granulated and pressed to a density of 4.9–5.1 g / cm³. 3 Flake-shaped porcelain blanks;

[0013] 5) Place the ceramic blank in a sintering furnace and heat it to 600°C at a rate of 0.5-1°C / min, then heat it to 1250-1300°C at a rate of 2-3°C / min and hold it for 2 hours to obtain ceramic slabs.

[0014] 6) Grind the front and back sides of the ceramic tile, then clean and dry it;

[0015] 7) Print silver paste on the front and back of the ground ceramic sheet, then place it in a sintering furnace, heat it to 750℃ and hold it for 1.5 hours to obtain silver-coated ceramic sheets.

[0016] 8) The silver-coated ceramic sheet is placed in an environment with a temperature of 350-380℃ and an electric field strength of 600-800V / mm for a polarization time of 5-10 minutes.

[0017] Compared with existing technologies, the piezoelectric ceramic chip d provided by this invention... 33 ≥500pC / N, ε 33 T With ε0≥2400, tanδ≤0.4%, and Kp≥0.72, it exhibits excellent piezoelectric and dielectric properties and low dielectric loss, making it widely applicable in fields such as ultrasonic atomizing devices and transducers. Detailed Implementation

[0018] The present invention will be further described below with reference to specific embodiments:

[0019] Example 1: The prepared component has the following formula: 0.87Pb(Zr,Ti)O3-0.01Pb(Mn) 1 / 3 Sb 2 / 3 O3

[0020] -0.04Pb(Ni 1 / 3 Nb 2 / 3 O3-0.08Pb(Zn) 1 / 3 Nb 2 / 3 A piezoelectric ceramic material with O3 + 0.25wt% CeO2 and Zr / Ti = 1.1. The steps are as follows:

[0021] 1) According to the proportions in the above component formula, Pb3O4, ZrO2, TiO2, MnO2, Sb2O3, CeO2, Nb2O5, NiO, ZnO and deionized water are mixed, ball-milled for 4 hours, dried, and passed through a 20-mesh sieve to obtain primary abrasive; wherein, the weight ratio of zirconia balls, raw materials and deionized water is 2:1:0.8, and the ball mill speed is 360 r / min;

[0022] 2) Place the primary abrasive material in a sintering furnace, heat it to 900°C at a rate of 2.5°C / min, hold it at that temperature for 2 hours, and then cool it with the furnace to obtain the pre-burned material;

[0023] 3) After crushing the pre-fired material, add deionized water, ball mill for 5 hours, dry, and pass through a 40-mesh sieve to obtain ceramic powder; wherein, the weight ratio of zirconia balls, raw materials, and deionized water is 2:1:0.8, and the speed of the ball mill is 360 r / min.

[0024] 4) The ceramic powder is spray-granulated and pressed to a density of 5 g / cm³. 3 Flake-shaped porcelain blanks;

[0025] 5) Place the ceramic blank in a sintering furnace, heat it to 600°C at a rate of 0.5°C / min, then heat it to 1270°C at a rate of 3°C / min and hold it for 2 hours. Cool it with the furnace to obtain ceramic slabs.

[0026] 6) Grind the front and back sides of the ceramic tile, then clean and dry it;

[0027] 7) Print silver paste on the front and back of the ground ceramic sheet, then place it in a sintering furnace, heat it to 750℃ and hold it for 1.5 hours to obtain silver-coated ceramic sheets.

[0028] 8) The silver-coated ceramic sheet was placed in an environment with a temperature of 350℃ and an electric field strength of 600V / mm for 10 minutes for polarization. After polarization, it was left to stand for 24 hours, and then the performance of the ceramic sheet was tested. The results are shown in Table 1.

[0029] Example 2, the prepared component has the following formula: 0.87Pb(Zr,Ti)O3-0.01Pb(Mn) 1 / 3 Sb 2 / 3 O3

[0030] -0.04Pb(Ni 1 / 3 Nb 2 / 3 O3-0.08Pb(Zn) 1 / 3 Nb 2 / 3 A piezoelectric ceramic material consisting of O3 + 0.25wt% CeO2; Zr / Ti = 1.08. The steps are as follows:

[0031] 1) According to the proportions in the above-mentioned component formula, Pb3O4, ZrO2, TiO2, MnO2, Sb2O3, CeO2, Nb2O5, NiO, ZnO and deionized water are mixed, ball-milled for 3 hours, dried, and passed through a 20-mesh sieve to obtain primary abrasive; wherein, the weight ratio of zirconia balls, raw materials and deionized water is 2.5:1:1, and the ball mill speed is 360 r / min;

[0032] 2) Place the primary abrasive material in a sintering furnace, heat it to 950°C at a rate of 2.5°C / min, hold it at that temperature for 2 hours, and then cool it with the furnace to obtain the pre-burned material;

[0033] 3) After crushing the pre-fired material, add deionized water, ball mill for 6 hours, dry, and pass through a 40-mesh sieve to obtain ceramic powder; wherein, the weight ratio of zirconia balls, raw materials, and deionized water is 2.5:1:1, and the speed of the ball mill is 360 r / min.

[0034] 4) The ceramic powder is spray-granulated and pressed to a density of 5.1 g / cm³. 3 Flake-shaped porcelain blanks;

[0035] 5) Place the ceramic blank in a sintering furnace, heat it to 600°C at a rate of 1°C / min, then heat it to 1250°C at a rate of 2.5°C / min, hold it at that temperature for 2 hours, and then cool it with the furnace to obtain ceramic slabs.

[0036] 6) Grind the front and back sides of the ceramic tile, then clean and dry it;

[0037] 7) Print silver paste on the front and back of the ground ceramic sheet, then place it in a sintering furnace, heat it to 750℃ and hold it for 1.5 hours to obtain silver-coated ceramic sheets.

[0038] 8) The silver-coated ceramic sheet was placed in an environment with a temperature of 380℃ and an electric field strength of 700V / mm for 8 minutes for polarization. After polarization, it was left to stand for 24 hours, and then the performance of the ceramic sheet was tested. The results are shown in Table 1.

[0039] Example 3, the prepared component has the following formula: 0.87Pb(Zr,Ti)O3-0.01Pb(Mn) 1 / 3 Sb 2 / 3 O3

[0040] -0.04Pb(Ni 1 / 3 Nb 2 / 3 O3-0.08Pb(Zn) 1 / 3 Nb 2 / 3 A piezoelectric ceramic material consisting of O3 + 0.25wt% CeO2; Zr / Ti = 1.06. The steps are as follows:

[0041] 1) According to the proportions in the above-mentioned component formula, Pb3O4, ZrO2, TiO2, MnO2, Sb2O3, CeO2, Nb2O5, NiO, ZnO and deionized water are mixed, ball-milled for 6 hours, dried, and passed through a 40-mesh sieve to obtain primary abrasive; wherein, the weight ratio of zirconia balls, raw materials and deionized water is 2.5:1:0.6, and the ball mill speed is 360 r / min;

[0042] 2) Place the primary abrasive material in a sintering furnace, heat it to 1000℃ at a rate of 2.5℃ / min, hold it at that temperature for 2 hours, and then cool it with the furnace to obtain the pre-burned material;

[0043] 3) After crushing the pre-fired material, add deionized water, ball mill for 6 hours, dry, and pass through a 40-mesh sieve to obtain ceramic powder; wherein, the weight ratio of zirconia balls, raw materials, and deionized water is 2.5:1:0.6, and the speed of the ball mill is 360 r / min;

[0044] 4) The ceramic powder is spray-granulated and pressed to a density of 4.9 g / cm³. 3 Flake-shaped porcelain blanks;

[0045] 5) Place the ceramic blank in a sintering furnace, heat it to 600°C at a rate of 0.8°C / min, then heat it to 1300°C at a rate of 2°C / min and hold it for 2 hours. Cool it with the furnace to obtain ceramic slabs.

[0046] 6) Grind the front and back sides of the ceramic tile, then clean and dry it;

[0047] 7) Print silver paste on the front and back of the ground ceramic sheet, then place it in a sintering furnace, heat it to 750℃ and hold it for 1.5 hours to obtain silver-coated ceramic sheets.

[0048] 8) The silver-coated ceramic sheet was placed in an environment with a temperature of 360℃ and an electric field strength of 800V / mm for 5 minutes for polarization. After polarization, it was left to stand for 24 hours, and then the performance of the ceramic sheet was tested. The results are shown in Table 1.

[0049] Example 4, the prepared component has the following formula: 0.843Pb(Zr,Ti)O3-0.012Pb(Mn) 1 / 3 Sb 2 / 3 O3-0.05Pb(Ni) 1 / 3Nb 2 / 3 O3-0.095Pb(Zn) 1 / 3 Nb 2 / 3 Piezoelectric ceramic material with O3 + 0.25wt% CeO2 and Zr / Ti = 1.08.

[0050] Each step is the same as in Example 1. After polarization, the ceramic sheet is left to stand for 24 hours, and then its performance is tested. The results are shown in Table 1.

[0051] Example 5, the prepared component has the following formula: 0.835Pb(Zr,Ti)O3-0.015Pb(Mn)O3 1 / 3 Sb 2 / 3 O3-0.05Pb(Ni) 1 / 3Nb 2 / 3 O3-0.1Pb(Zn) 1 / 3 Nb 2 / 3 Piezoelectric ceramic material with O3 + 0.25wt% CeO2 and Zr / Ti = 1.08.

[0052] Each step is the same as in Example 2. After polarization, the ceramic sheet is left to stand for 24 hours, and then the performance of the ceramic sheet is tested. The results are shown in Table 1.

[0053] Example 6, the prepared component has the following formula: 0.835Pb(Zr,Ti)O3-0.015Pb(Mn) 1 / 3 Sb 2 / 3 O3-0.06Pb(Ni 1 / 3Nb 2 / 3 O3-0.09Pb(Zn) 1 / 3 Nb 2 / 3 Piezoelectric ceramic material with O3 + 0.25wt% CeO2 and Zr / Ti = 1.08.

[0054] Each step is the same as in Example 3. After polarization, the ceramic sheet is left to stand for 24 hours, and then its performance is tested. The results are shown in Table 1.

[0055] Example 7, the prepared component has the following formula: 0.86Pb(Zr,Ti)O3-0.01Pb(Mn) 1 / 3 Sb 2 / 3 O3-0.05Pb(Ni) 1 / 3Nb 2 / 3 O3-0.08Pb(Zn) 1 / 3 Nb 2 / 3 Piezoelectric ceramic material with O3 + 0.25wt% CeO2 and Zr / Ti = 1.1.

[0056] Each step is the same as in Example 1. After polarization, the ceramic sheet is left to stand for 24 hours, and then its performance is tested. The results are shown in Table 1.

[0057] Example 8, the prepared component has the following formula: 0.858Pb(Zr,Ti)O3-0.012Pb(Mn) 1 / 3 Sb 2 / 3 O3-0.05Pb(Ni) 1 / 3Nb 2 / 3 O3-0.08Pb(Zn) 1 / 3 Nb 2 / 3 Piezoelectric ceramic material with O3 + 0.25wt% CeO2 and Zr / Ti = 1.06.

[0058] Each step is the same as in Example 2. After polarization, the ceramic sheet is left to stand for 24 hours, and then the performance of the ceramic sheet is tested. The results are shown in Table 1.

[0059] Example 9, the prepared component has the following formula: 0.828Pb(Zr,Ti)O3-0.012Pb(Mn) 1 / 3 Sb 2 / 3 O3-0.06Pb(Ni 1 / 3Nb 2 / 3 O3-0.1Pb(Zn) 1 / 3 Nb 2 / 3 Piezoelectric ceramic material with O3 + 0.25wt% CeO2 and Zr / Ti = 1.08.

[0060] Each step is the same as in Example 3. After polarization, the ceramic sheet is left to stand for 24 hours, and then its performance is tested. The results are shown in Table 1.

[0061] Table 1 Performance indicators of the piezoelectric ceramic material of the present invention

[0062]

[0063] As can be seen from Table 1, the piezoelectric ceramic material d prepared according to the formulation of this invention... 33 ≥500pC / N, ε 33 T With ε0≥2400, tanδ≤0.4%, and Kp≥0.72, it exhibits excellent piezoelectric and dielectric properties and low dielectric loss, making it widely applicable in fields such as ultrasonic atomizing devices and transducers.

Claims

1. A piezoelectric ceramic material intermediate between P4 and P5 systems, characterized in that... The composition formula of this piezoelectric ceramic material is: (1-xyz)Pb(Zr,Ti)O3-xPb(Mn 1 / 3 Sb 2 / 3 )O3–yPb(Ni 1 / 3 Nb 2 / 3 )O3-zPb(Zn 1 / 3 Nb 2 / 3 )O3 +0.25wt%CeO2, where Zr / Ti = 1.08~1.1, x = 0.01~0.015; y = 0.04~0.06, z = 0.08~0.

1.

2. The piezoelectric ceramic material intermediate between the P4 and P5 systems according to claim 1, characterized in that: x=0.012。 3. The piezoelectric ceramic material intermediate between the P4 and P5 systems according to claim 1, characterized in that: z=0.095。 4. A method for preparing a piezoelectric ceramic material intermediate between the P4 and P5 systems as described in any one of claims 1 to 3, characterized in that... The specific steps are as follows: 1) According to the proportions in the composition formula, Pb3O4, ZrO2, TiO2, MnO2, Sb2O3, CeO2, Nb2O5, NiO, ZnO and deionized water are mixed, ball-milled for 3-6 hours, dried and passed through a 20-40 mesh sieve to obtain primary abrasive; 2) Place the primary abrasive material in a sintering furnace, heat it to 900-1000℃ at a rate of 2.5-3℃ / min, and hold it for 2 hours to obtain pre-burned material; 3) After crushing the pre-fired material, add deionized water, ball mill for 3-5 hours, dry, and pass through a 40-mesh sieve to obtain ceramic powder; 4) The ceramic powder is spray-granulated and pressed to a density of 4.9–5.1 g / cm³. 3 Flake-shaped porcelain blanks; 5) Place the ceramic blank in a sintering furnace, heat it to 600°C at a rate of 0.5-1°C / min, then heat it to 1250-1300°C at a rate of 2-3°C / min and hold it for 2 hours to obtain ceramic slabs; 6) Grind, clean, and dry the front and back sides of the ceramic tile; 7) Print silver paste on the front and back of the ground ceramic sheet, then place it in a sintering furnace, heat it to 750℃ and hold it for 1.5 hours to obtain silver-coated ceramic sheets. 8) The silver-coated ceramic sheet is placed in an environment with a temperature of 350-380℃ and an electric field strength of 600-800V / mm for a polarization time of 5-10 minutes.

Images