A multi-element piezoelectric ceramic sensor material and preparation method thereof

Abstract

The present invention relates to the field of piezoelectric ceramic materials, and in particular to a multi-element piezoelectric ceramic sensor material and a preparation method thereof, wherein the chemical structure is as follows: Pb 1‑x A x (Mn α Sb 1‑α ) y (Mg β Nb 1‑β ) z (Zr γ Ti 1‑γ ) 1‑y‑z O3‑uat.%BWO4‑vat.%BiInO3A is an alkaline earth metal element and / or a rare earth element, B is Ca and / or Li, 0.01≤x≤0.2, 0.01≤y≤0.05, 0.01≤z≤0.1, 0.1≤α≤0.5, 0.1≤β≤0.5, 0.25≤γ≤0.75, 1≤u≤10, 1≤v≤10. The multi-element piezoelectric ceramic sensor material prepared by the present invention has excellent piezoelectric properties and can be widely used in various sensors.

Description

Technical Field

[0001] The present invention relates to the field of piezoelectric ceramic materials, in particular to a multi-element piezoelectric ceramic sensor material and a preparation method thereof. Background Art

[0002] Lead zirconate titanate (PZT) and its ternary and quaternary piezoelectric ceramics have excellent piezoelectric, dielectric and photoelectric electrical properties. They are widely used in high-tech fields such as electronics, measurement and control, aerospace, etc., and are used to prepare electronic components such as sensors, transducers, and memories. They are a very promising functional material.

[0003] At present, there are many studies on PZT-based multi-component piezoelectric ceramics in China. For example, PMN-PZT ceramics doped with lithium and manganese were used to study the effects of different LiCO3 and MnO2 additions on the mechanical quality factor Qm, electromechanical coupling coefficient Kp, and piezoelectric constant d 33 Or, solid oxides are used as raw materials to prepare PSN-PZT piezoelectric ceramics using a one-time synthesis process, and the effects of PSN content, B-site ion Nb vacancy, ZrO2 reduction, trace element addition, and sintering process parameters on the piezoelectric properties of ceramics are studied. However, these research results show that although new components are added, the piezoelectric properties are only slightly increased compared to pure PZT ceramics. Therefore, it is urgent to optimize the component formula and study piezoelectric ceramic materials with better piezoelectric properties. Summary of the invention

[0004] Purpose of the invention: In view of the above technical problems, the present invention proposes a multi-element piezoelectric ceramic sensor material and a preparation method thereof.

[0005] The technical solutions adopted are as follows:

[0006] A multi-element piezoelectric ceramic sensor material, the chemical structure of which is as follows:

[0007] Pb 1-x A x (Mn α Sb 1-α ) y (Mg β Nb 1-β ) z (Zr γ Ti 1-γ ) 1-y-z O3-uat.%BWO4-vat.%BiInO3

[0008] A is an alkaline earth metal element and / or a rare earth element;

[0009] B is Ca and / or Li;

[0010] 0.01≤x≤0.2, 0.01≤y≤0.05, 0.01≤z≤0.1;

[0011] 0.1≤α≤0.5, 0.1≤β≤0.5, 0.25≤γ≤0.75;

[0012] 1≤u≤10, 1≤v≤10.

[0013] Further, A is La.

[0014] Furthermore, B is Ca and Li, and the molar ratio of Ca to Li is 5-15:1.

[0015] Furthermore, the molar ratio of Ca to Li is 9:1.

[0016] Further, 0.025≤x≤0.055, 0.02≤y≤0.04, 0.04≤z≤0.08.

[0017] Further, x=0.05, y=0.03, z=0.07.

[0018] Furthermore, 0.2≤α≤0.4, 0.2≤β≤0.4, 0.4≤γ≤0.6.

[0019] Furthermore, α=1 / 3, β=1 / 3, γ=0.5.

[0020] Furthermore, u=5, v=1.

[0021] The present invention provides a method for preparing a multi-element piezoelectric ceramic sensor material:

[0022] Pb3O4, oxide A, MnO2, Sb2O3, MgO, Nb2O5, ZrO2, TiO2, BWO4 and BiInO3 are mixed and ball-milled and dried. After pre-sintering at 900-1000℃ for 2-4h, they are ball-milled again and dried. After granulation, sieving and pressing, a green body is obtained. The green body is heated to 650-850℃ for debinding for 1-3h in the first stage, and then heated to 1150-1250℃ for sintering for 2-4h in the second stage.

[0023] Beneficial effects of the present invention:

[0024] The present invention provides a multi-element piezoelectric ceramic sensor material. By introducing PMS and PMN, a multi-element system piezoelectric ceramic material with a composite perovskite structure is constructed together with PZT. Compared with a pure PZT system, the multi-element system has higher piezoelectric activity, higher density and more uniform grain structure. Moreover, by doping A-site ions, the grains can be further refined, the density can be increased, and the electrical properties of the material can be improved. BWO4 belongs to a perovskite-like scheelite structure and is a type of electronic ceramic material with similar structure and phase change characteristics. After being added, it has a significant effect on improving the electrical properties of the material. The microscopic mechanism of macroscopic performance improvement is still unclear. It may be that the incorporation forms a special defect structure, which weakens the "pinning" effect of defect dipoles in the material, thereby improving the piezoelectric properties of the ceramic. BiInO3 has a typical perovskite structure and is used as an additional component in both lead-containing and lead-free piezoelectric ceramic systems to regulate the electrical properties of piezoelectric ceramics. After being added, it can form a solid solution with PZT-PMS-PMN to improve the electrical properties of the material. The multi-component piezoelectric ceramic sensor material prepared by the present invention has excellent piezoelectric properties and can be widely used in various sensors. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is the SEM image of the multi-element piezoelectric ceramic sensor material prepared in Example 1. It can be seen that there are basically no pores inside the material, and the structure is dense and has no impurities. DETAILED DESCRIPTION

[0026] If the specific conditions are not specified in the examples, the experiments were carried out under conventional conditions or the conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments is not specified, they are all conventional products that can be purchased commercially. The techniques not mentioned in the present invention are all referenced to the prior art. Unless otherwise specified, the following examples and comparative examples are parallel experiments, using the same processing steps and parameters.

[0027] Embodiment 1:

[0028] A multi-element piezoelectric ceramic sensor material, the chemical structure of which is as follows:

[0029] Pb 0.95 La 0.05 (Mn 1 / 3 Sb 2 / 3 ) 0.03 (Mg 1 / 3 Nb 2 / 3 ) 0.07 (Zr 0.5 Ti 0.5 ) 0.9 O3-4.5at.%CaWO4-0.5at.

[0030] %Li2WO4-1at.%BiInO3

[0031] Preparation method of the above multi-element piezoelectric ceramic sensor material:

[0032] Pb3O4, La2O3, MnO2, Sb2O3, MgO, Nb2O5, ZrO2, TiO2, CaWO4, Li2WO4 and BiInO3 were weighed according to the chemical structural formula and added into the ball milling jar of a planetary ball mill with deionized water as the ball milling medium. After mixing and ball milling for 10 hours, the mixed powder was put into an oven for drying. The obtained mixed powder was pre-calcined at 950°C for 3 hours, ball milled again for 5 hours and dried. After granulation with 8wt% polyvinyl alcohol aqueous solution, the mixture was sieved through an 80-mesh sieve and pressed into a green body at a pressure of 100MPa. The green body was placed in a crucible and heated to 800°C at a rate of 0.5°C / min in a sintering furnace for 2 hours for heat preservation and debinding, and then heated to 1220°C at a rate of 5°C / min in a second stage for heat preservation and sintering for 3 hours. Finally, the green body was cooled to room temperature with the furnace.

[0033] Embodiment 2:

[0034] A multi-element piezoelectric ceramic sensor material, the chemical structure of which is as follows:

[0035] Pb 0.95 La 0.05 (Mn 1 / 3 Sb 2 / 3 ) 0.03 (Mg 1 / 3 Nb 2 / 3 ) 0.07 (Zr 0.5 Ti 0.5 ) 0.9 O3-4.5at.%CaWO4-0.5at.

[0036] %Li2WO4-1at.%BiInO3

[0037] Preparation method of the above multi-element piezoelectric ceramic sensor material:

[0038] Pb3O4, La2O3, MnO2, Sb2O3, MgO, Nb2O5, ZrO2, TiO2, CaWO4, Li2WO4 and BiInO3 were weighed according to the chemical structural formula and added into the ball milling jar of a planetary ball mill with deionized water as the ball milling medium. After mixing and ball milling for 10 hours, the mixed powder was put into an oven for drying. The obtained mixed powder was pre-calcined at 1000°C for 4 hours, ball milled again for 5 hours and dried. After granulation with 8wt% polyvinyl alcohol aqueous solution, the mixture was sieved through an 80-mesh sieve and pressed into a green body at a pressure of 100MPa. The green body was placed in a crucible and heated to 850°C at a rate of 0.5°C / min in a sintering furnace for 3 hours for heat removal, and then heated to 1250°C at a rate of 5°C / min in a second stage for heat preservation and sintering for 4 hours. Finally, the green body was cooled to room temperature with the furnace.

[0039] Embodiment 3:

[0040] A multi-element piezoelectric ceramic sensor material, the chemical structure of which is as follows:

[0041] Pb 0.95 La 0.05 (Mn 1 / 3 Sb 2 / 3 ) 0.03 (Mg 1 / 3 Nb 2 / 3 ) 0.07 (Zr 0.5 Ti 0.5 ) 0.9 O3-4.5at.%CaWO4-0.5at.

[0042] %Li2WO4-1at.%BiInO3

[0043] Preparation method of the above multi-element piezoelectric ceramic sensor material:

[0044] Pb3O4, La2O3, MnO2, Sb2O3, MgO, Nb2O5, ZrO2, TiO2, CaWO4, Li2WO4 and BiInO3 were weighed according to the chemical structural formula and added into the ball milling jar of a planetary ball mill with deionized water as the ball milling medium. After mixing and ball milling for 10 hours, the mixed powder was put into an oven for drying. The obtained mixed powder was pre-calcined at 900°C for 2 hours, ball milled again for 5 hours and dried. After granulation with 8wt% polyvinyl alcohol aqueous solution, the mixture was sieved through an 80-mesh sieve and pressed into a green body at a pressure of 100MPa. The green body was placed in a crucible and heated to 650°C at a rate of 0.5°C / min in a sintering furnace for 1 hour for heat removal, and then heated to 1150°C at a rate of 5°C / min in a second stage for heat preservation and sintering for 2 hours. Finally, the green body was cooled to room temperature with the furnace.

[0045] Embodiment 4:

[0046] It is basically the same as Example 1, except that CaWO4 is not added.

[0047] Embodiment 5:

[0048] It is basically the same as Example 1, except that Li2WO4 is not added.

[0049] Comparative Example 1:

[0050] It is basically the same as Example 1, except that BiInO3 is not added.

[0051] Comparative Example 2:

[0052] It is basically the same as Example 1, except that CaWO4 and Li2WO4 are not added.

[0053] Comparative Example 3:

[0054] It is basically the same as Example 1, except that BiInO3, CaWO4 and Li2WO4 are not added.

[0055] Comparative Example 4:

[0056] The same as Example 1, except that La doping is not performed. A multi-element piezoelectric ceramic sensor material has the following chemical structure:

[0057] Pb(Mn 1 / 3 Sb 2 / 3 ) 0.03 (Mg 1 / 3 Nb 2 / 3 ) 0.07 (Zr 0.5 Ti 0.5 ) 0.9 O3-4.5at.%CaWO4-0.5at.%Li2W

[0058] O4-1at.%BiInO3

[0059] Preparation method of the above multi-element piezoelectric ceramic sensor material:

[0060] Pb3O4, MnO2, Sb2O3, MgO, Nb2O5, ZrO2, TiO2, CaWO4, Li2WO4 and BiInO3 were weighed according to their chemical structural formulas and added into the ball milling jar of a planetary ball mill. Deionized water was used as the ball milling medium and the mixture was ball milled for 10 hours and then dried in an oven. The obtained mixed powder was pre-calcined at 950°C for 3 hours and then ball milled again for 5 hours and dried. An 8wt% polyvinyl alcohol aqueous solution was added for granulation and then passed through an 80-mesh sieve and pressed into a green body at a pressure of 100 MPa. The green body was placed in a crucible and heated to 800°C at a rate of 0.5°C / min in a sintering furnace for 2 hours of heat preservation and debinding, then heated to 1220°C at a rate of 5°C / min in a second stage and sintered for 3 hours, and finally cooled to room temperature with the furnace.

[0061] Performance Test:

[0062] The surfaces of the multi-element piezoelectric ceramic sensor materials prepared in Examples 1-5 and Comparative Examples 1-4 were polished, coated with silver paste on both sides, kept at 750°C for 10 min, and finally polarized at a DC voltage of 4 kV / mm for 20 min in silicone oil at 120°C and placed for 24 h as samples to test their electrical properties.

[0063] The room temperature piezoelectric constant of the sample was measured using a ZJ-3AN quasi-static piezoelectric constant tester (ZJ-3A);

[0064] The electromechanical coupling coefficient kp, mechanical quality factor Qm and dielectric loss tanδ (25°C, 1V, 1kHz) of the samples were analyzed using a precision impedance analyzer (Agilent HP4294A);

[0065] The test results are shown in Table 1 below:

[0066] Table 1:

[0067]

[0068] It can be seen from Table 1 above that the multi-element piezoelectric ceramic sensor material prepared in the present invention has excellent piezoelectric properties and can be widely used in various sensors.

[0069] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A multi-element piezoelectric ceramic sensor material, characterized in that: Its chemical structure is as follows: Pb 1-x A x (Mn α Sb 1-α ) y (Mg β Nb 1-β ) z (Zr γ Ti 1-γ ) 1-y-z O3-uat.%BWO4-vat.%BiInO3 A is La; B is Ca and Li, and the molar ratio of Ca to Li is 9:1; x=0.05, y=0.03, z=0.07; α=1 / 3, β=1 / 3, γ=0.5; u=5,v=1.

2. A method for preparing the multi-element piezoelectric ceramic sensor material as claimed in claim 1, characterized in that: Pb3O4, oxide A, MnO2, Sb2O3, MgO, Nb2O5, ZrO2, TiO2, BWO4 and BiInO3 are mixed and ball-milled and dried. After pre-sintering at 900-1000℃ for 2-4h, they are ball-milled again and dried. After granulation, sieving and pressing, a green body is obtained. The green body is heated to 650-850℃ for debinding for 1-3h in the first stage, and then heated to 1150-1250℃ for sintering for 2-4h in the second stage.

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