CN110698195B - High-resistivity and high-piezoelectric-activity bismuth calcium titanate-based high-temperature piezoelectric ceramic and preparation method thereof - Google Patents

High-resistivity and high-piezoelectric-activity bismuth calcium titanate-based high-temperature piezoelectric ceramic and preparation method thereof Download PDF

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CN110698195B
CN110698195B CN201911096777.1A CN201911096777A CN110698195B CN 110698195 B CN110698195 B CN 110698195B CN 201911096777 A CN201911096777 A CN 201911096777A CN 110698195 B CN110698195 B CN 110698195B
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郑鹏
刘洋
白王峰
郑辉
郑梁
张阳
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Hangzhou Dianzi University
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Abstract

The invention discloses a high-resistivity and high-voltage electroactive calcium bismuth titanate-based high-temperature piezoelectric ceramic and a preparation method thereof, wherein CaBi is adopted4Ti4O15Based on the system piezoelectric material, Mn and Ta are doped into Ti position according to a certain molar ratio, and a solid-phase synthesis method is adopted to prepare the novel bismuth layer-structured piezoelectric ceramic material, wherein the general formula of the piezoelectric ceramic material is CaBi4Ti4‑x(Mn1/3Ta2/3)xO12Wherein 0 is<x is less than or equal to 0.1. Compared with the prior art, the piezoceramic material obtained by the invention has the main performance parameter d33＝24pC/N，TC793 ℃, at 400 ℃, ρ 9.63 × 107Omega cm, stable and reliable preparation process, low production cost, easy realization of industrial production and good application prospect in the high-temperature field. The ceramic element prepared by the material is assembled into various piezoelectric sensors, and can be applied to special high-temperature environments such as aerospace, petrochemical industry and the like.

Description

High-resistivity and high-voltage electroactive bismuth calcium titanate-based high-temperature piezoelectric ceramic and preparation method thereof
Technical Field
The invention relates to a preparation method of a bismuth calcium titanate high-temperature piezoelectric ceramic material with a bismuth layer-structured structure, in particular to Mn/Ta co-doped bismuth calcium titanate (CaBi) with a bismuth layer-structured structure4Ti4O15) The preparation of piezoelectric ceramic material belongs to the field of piezoelectric ceramic material technology.
Background
At present, the most widely applied piezoelectric materials are mainly PZT-based piezoelectric ceramics with perovskite structures, but the Curie temperature of the piezoelectric ceramics is generally below 390 ℃, and the piezoelectric materials cannot normally work below the Curie temperature due to the depolarization phenomenon of the piezoelectric materials. With the rapid development of industries such as aerospace and geological exploration and the requirement of sustainable development of human society, an environment-friendly piezoelectric material with high curie temperature and excellent piezoelectric performance is needed to be sought.
Because of high curie temperature and good fatigue resistance, bismuth layer structured ceramics are considered to be an ideal choice for high temperature piezoelectric materials. The bismuth layer structured ceramic material is composed of (Bi)2O2)2+The layers and the lattice layers of perovskite structure are alternately superposed, and the chemical general formula is (Bi)2O2)2+(Am-1BmO3m+1)2-In the above formula, A is an ion suitable for dodecahedral coordination, such as Na+，Ca2+，La3+Etc., B is an ion suitable for octahedral coordination, e.g. Ti4+，Nb5+，Ta5+And m is an integer and takes the value of 1 to 6. Bismuth titanate (CaBi)4Ti4O12) Is a bismuth layer structure material with m-4, Curie temperature as high as 790 ℃, piezoelectric constant d33About 7pC/N, and compared with the practical application, the piezoelectric property of the piezoelectric ceramic can not meet the application requirement (d) although the Curie temperature meets the use requirement at high temperature33>20 pC/N). Therefore, it is an important subject of research in the field of piezoelectric ceramic materials to improve the piezoelectric performance without lowering the curie temperature and to obtain a bismuth layered piezoelectric ceramic material that can be stably used in a high temperature range.
At present, the Mn/Ta co-doping for improving the bismuth layer-structured bismuth calcium titanate (CaBi) is not seen4Ti4O15) The related report of the performance of the piezoelectric ceramic material.
Disclosure of Invention
In view of the above-mentioned deficiencies of the prior art, the present invention aims to provide a bismuth calcium titanate-based high temperature piezoelectric ceramic with high resistivity and high piezoelectric activity and a preparation method thereof, wherein the bismuth calcium titanate (CaBi) with a bismuth layer structure is prepared by using Mn and Ta elements4Ti4O15) The piezoelectric ceramic material is codoped and modified, so that the piezoelectric property of the piezoelectric ceramic material is improved while the Curie temperature is not reduced, and the novel environment-friendly piezoelectric ceramic material is prepared.
In order to overcome the defects in the prior art, the invention provides the following technical scheme:
the high-resistivity and high-voltage electroactive bismuth calcium titanate-based high-temperature piezoelectric ceramic is characterized in that the chemical general formula of the piezoelectric ceramic is CaBi4Ti4-x(Mn1/3Ta2/3)xO12Wherein 0 is<x≤0.1。
The invention also provides a preparation method of the high-resistivity and high-piezoelectric-activity bismuth calcium titanate-based high-temperature piezoelectric ceramic, which comprises the following steps:
preparing materials: with CaCO3Powder of Bi2O3Powder, TiO2Powder, MnCO3Powder and Ta2O5The powder is used as raw material and is represented by the general formula CaBi4Ti4-x(Mn1/3Ta2/3)xO12Proportioning the Ca, Bi, Ti, Mn and Ta in the stoichiometric ratio of 0<x≤0.1；
Primary ball milling: adding absolute ethyl alcohol with the same amount as the mixture into the mixture, and continuously ball-milling for 12-24 hours to uniformly mix the powder to form slurry, so that the comprehensive performance of the bismuth calcium titanate high-temperature piezoelectric ceramic material can be further improved;
drying: placing the slurry in a constant-temperature oven for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder;
and (3) tabletting and pre-sintering: placing the powder into a grinding tool to be pre-pressed into material blocks, pre-burning the material blocks, wherein the pre-burning temperature is 750-825 ℃, and the heat preservation time is 2-4 hours;
secondary ball milling: putting the pre-sintered material blocks in a mortar, grinding and grinding to obtain primary powder, adding absolute ethyl alcohol with the same amount as the primary powder into the obtained primary powder, and continuously ball-milling for 12-24 hours to uniformly mix the powder to form slurry;
drying: placing the slurry in a constant-temperature oven for baking, removing absolute ethyl alcohol, and grinding the slurry into powder in a mortar;
and (3) granulation and forming: adding distilled water and polyvinyl alcohol solution (PVA) with the concentration of 8% into the powder as a binder, wherein the mass of the added distilled water is 2.5% of the mass of the powder, the mass of the added binder is 5% of the mass of the powder, and uniformly mixing in a mortar; placing the mixed powder in a grinding tool, and pressing into a green body; grinding the green body into powder in a mortar, sieving the powder through 60-mesh and 120-mesh sieves, and taking the powder in the middle layers of the 60-mesh and 120-mesh sieves to obtain the powder with proper particle size; putting the powder into a grinding tool, and pressing the powder into a green body under the pressure of 200 MPa;
rubber discharging: removing the glue from the green body, calcining for 3 hours at the temperature of 650 ℃, and removing PVA in the green body to obtain a porcelain body;
and (3) sintering: sintering the ceramic blank at the sintering temperature of 1000-1100 ℃ for 2-4 hours to obtain a ceramic wafer;
coating an electrode: cleaning and drying the ceramic wafer, screen-printing a silver-coated electrode, and burning silver at the silver burning temperature of 500-600 ℃ for 1-2 hours;
polarization: and (3) placing the ceramic plate plated with the silver electrode in silicone oil at 120-160 ℃, wherein the polarization voltage is 12 kV/mm-15 kV/mm, and the polarization time is 20 min-40 min.
Preferably, in the primary and secondary ball milling processes, the ball milling time is 12 hours.
Preferably, in the pre-sintering process, the pre-sintering temperature is 825 ℃ and the heat preservation time is 4 hours.
Preferably, in the sintering process, the sintering temperature is 1025 ℃, and the holding time is 1 hour.
Preferably, x is 0.02.
Preferably, x is 0.03.
Preferably, x is 0.04.
Preferably, x is 0.05.
Preferably, x is 0.06.
Preferably, x is 0.1.
Compared with the prior art, the technical scheme of the invention effectively improves the piezoelectric property of the bismuth calcium titanate high-temperature piezoelectric ceramic material by replacing Ti at the B site with Mn and Ta and controlling the addition amount of the doping elements. It should be noted that although there are many reports about element doping of a piezoelectric ceramic material in the prior art, different doping elements and different addition amounts of the doping elements all have a great influence on the overall performance of the piezoelectric ceramic material, and thus, the doping of bismuth titanate high-temperature piezoelectric ceramic material with various elements is continuously searched in a test process and obtained through repeated tests.
Experimental data show that the invention has excellent performance:
the invention relates to Mn and Ta element co-doped modified bismuth layer-shaped bismuth calcium titanate (CaBi)4Ti4O15) A piezoelectric ceramic material having a Curie temperature of 793 ℃ and a piezoelectric constant d33Up to 24pC/N, good high-temp stability and high resistivity (9.63X 10) at 400 deg.C7Omega cm, and has good application prospect in the high-temperature field.
In addition, the invention is prepared by the traditional piezoelectric ceramic industry, has low preparation cost and simple industry, is suitable for large-scale industrial production, improves the piezoelectric property of the doped and modified ceramic material by more than four times than the previous ceramic material, and promotes the development of high-temperature piezoelectric materials.
Drawings
FIG. 1 is a CaBi prepared in example 14Ti4-x(Mn1/3Ta2/3)xO15X is the XRD diffraction pattern of 0.02 ceramic, and the curve of dielectric constant with temperature;
FIG. 2 is CaBi prepared in example 24Ti4-x(Mn1/3Ta2/3)xO15The XRD diffraction pattern of the ceramic, and the curve of the dielectric constant changing along with the temperature;
FIG. 3 is a CaBi prepared in example 34Ti4-x(Mn1/3Ta2/3)xO15X is the XRD diffraction pattern of 0.04 ceramic, and the curve of dielectric constant with temperature;
FIG. 4 is a block diagramCaBi prepared in example 44Ti4-x(Mn1/3Ta2/3)xO15The XRD diffraction pattern of the ceramic, and the curve of the dielectric constant changing along with the temperature are 0.05;
FIG. 5 is a CaBi prepared in example 54Ti4-x(Mn1/3Ta2/3)xO15X is the XRD diffraction pattern of 0.06 ceramic, and the curve of dielectric constant with temperature;
FIG. 6 is CaBi prepared in example 54Ti4-x(Mn1/3Ta2/3)xO15X is the XRD diffraction pattern of 0.1 ceramic, and the curve of dielectric constant with temperature;
FIG. 7 shows different amounts of Mn/Ta doped CaBi4Ti4-x(Mn1/3Ta2/3)xO15Curie temperature profile of the ceramic;
FIG. 8 shows different amounts of Mn/Ta doped CaBi4Ti4-x(Mn1/3Ta2/3)xO15A room temperature piezoelectric coefficient change diagram of the ceramic;
FIG. 9 shows different amounts of Mn/Ta doped CaBi4Ti4-x(Mn1/3Ta2/3)xO15Graph of change in resistivity at 400 ℃ of the ceramic.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Preparation of CaBi conforming to chemical composition4Ti4-x(Mn1/3Ta2/3)xO15Mn/Ta codoped modified bismuth calcium titanate (CaBi) with x being 0.024Ti4O15) The lead-free piezoelectric ceramic comprises the following steps:
(1) preparing materials: with CaCO3Powder of Bi2O3Powder, TiO2Powder, MnCO3Powder and Ta2O5The powder is taken as a raw material, and the materials are proportioned according to the stoichiometric amount of Ca, Bi, Ti, Mn and Ta in the general formula;
(2) primary ball milling: adding absolute ethyl alcohol with the same quantity as the mixture into the mixture, and continuously ball-milling for 12 hours to uniformly mix the powder to form slurry, so that the comprehensive performance of the bismuth calcium titanate high-temperature piezoelectric ceramic material can be further improved;
(3) drying: placing the slurry in a constant-temperature oven for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder;
(4) and (3) tabletting and pre-sintering: putting the powder into a grinding tool to be pre-pressed into material blocks, pre-burning the material blocks, wherein the pre-burning temperature is 825 ℃, and the heat preservation time is 4 hours;
(5) secondary ball milling: putting the pre-sintered material blocks into a mortar, grinding and grinding to obtain primary powder, adding absolute ethyl alcohol with the same amount as the primary powder into the obtained primary powder, and continuously ball-milling for 12 hours to uniformly mix the powder to form slurry;
(6) drying: placing the slurry in a constant-temperature oven for baking, removing absolute ethyl alcohol, and grinding the slurry into powder in a mortar;
(7) and (3) granulation and forming: adding distilled water and polyvinyl alcohol solution (PVA) with the concentration of 8% into the powder as a binder, wherein the mass of the added distilled water is 2.5% of the mass of the powder, the mass of the added binder is 5% of the mass of the powder, and uniformly mixing in a mortar; placing the mixed powder in a grinding tool, and pressing into a green body; grinding the green body into powder in a mortar, sieving the powder through 60-mesh and 120-mesh sieves, and taking the powder in the middle layers of the 60-mesh and 120-mesh sieves to obtain the powder with proper particle size; putting the powder into a grinding tool, and pressing the powder into a green body under the pressure of 200 MPa;
(8) rubber discharging: removing the glue from the green body, calcining for 3 hours at the temperature of 650 ℃, and removing PVA in the green body to obtain a porcelain body;
(9) and (3) sintering: sintering the ceramic blank at 1025 ℃ for 1 hour to obtain a ceramic wafer;
(10) coating an electrode: cleaning and drying the ceramic wafer, screen-printing a silver-coated electrode, and burning silver at the silver burning temperature of 500-600 ℃ for 1-2 hours;
(11) polarization: and (3) placing the ceramic plate plated with the silver electrode in silicone oil at 120-160 ℃, wherein the polarization voltage is 12 kV/mm-15 kV/mm, and the polarization time is 20 min-40 min.
Shown in FIG. 1 is the CaBi prepared in example 14Ti4-x(Mn1/3Ta2/3)xO15X is the XRD diffraction pattern of 0.02 ceramic, and the curve of dielectric constant with temperature; FIG. 7 shows different amounts of Mn/Ta doped CaBi4Ti4-x(Mn1/3Ta2/3)xO15Curie temperature profile of the ceramic; FIG. 8 shows different amounts of Mn/Ta doped CaBi4Ti4-x(Mn1/3Ta2/3)xO15A room temperature piezoelectric coefficient change diagram of the ceramic; FIG. 9 shows different amounts of Mn/Ta doped CaBi4Ti4-x(Mn1/3Ta2/3)xO15Graph of change in resistivity at 400 ℃ of the ceramic.
As can be seen from FIG. 1, the XRD patterns of the Mn/Ta co-doped modified bismuth calcium titanate lead-free piezoelectric ceramic prepared in the example are basically consistent with those of pure-phase bismuth calcium titanate piezoelectric ceramic.
The test results were as follows: d is a radical of33＝18pC/N，TCAt 794 deg.C, resistivity at 400 deg.C rho is 1.12 × 108Ω·cm。
Example 2
Preparation of CaBi conforming to chemical composition4Ti4-x(Mn1/3Ta2/3)xO15Mn/Ta co-doped modified bismuth calcium titanate (CaBi) with x being 0.034Ti4O15) The lead-free piezoelectric ceramic comprises the following steps:
(1) preparing materials: with CaCO3Powder of Bi2O3Powder, TiO2Powder, MnCO3Powder and Ta2O5The powder is taken as a raw material, and the materials are proportioned according to the stoichiometric amount of Ca, Bi, Ti, Mn and Ta in the general formula;
(2) primary ball milling: adding absolute ethyl alcohol with the same quantity as the mixture into the mixture, and continuously ball-milling for 12 hours to uniformly mix the powder to form slurry, so that the comprehensive performance of the bismuth calcium titanate high-temperature piezoelectric ceramic material can be further improved;
(3) drying: placing the slurry in a constant-temperature oven for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder;
(4) and (3) tabletting and pre-sintering: putting the powder into a grinding tool to be pre-pressed into material blocks, pre-burning the material blocks, wherein the pre-burning temperature is 825 ℃, and the heat preservation time is 4 hours;
(5) secondary ball milling: putting the pre-sintered material blocks into a mortar, grinding and grinding to obtain primary powder, adding absolute ethyl alcohol with the same amount as the primary powder into the obtained primary powder, and continuously ball-milling for 12 hours to uniformly mix the powder to form slurry;
(6) drying: placing the slurry in a constant-temperature oven for baking, removing absolute ethyl alcohol, and grinding the slurry into powder in a mortar;
(7) and (3) granulation and forming: adding distilled water and polyvinyl alcohol solution (PVA) with the concentration of 8% into the powder as a binder, wherein the mass of the added distilled water is 2.5% of the mass of the powder, the mass of the added binder is 5% of the mass of the powder, and uniformly mixing in a mortar; placing the mixed powder in a grinding tool, and pressing into a green body; grinding the green body into powder in a mortar, sieving the powder through 60-mesh and 120-mesh sieves, and taking the powder in the middle layers of the 60-mesh and 120-mesh sieves to obtain the powder with proper particle size; putting the powder into a grinding tool, and pressing the powder into a green body under the pressure of 200 MPa;
(8) rubber discharging: removing the glue from the green body, calcining for 3 hours at the temperature of 650 ℃, and removing PVA in the green body to obtain a porcelain body;
(9) and (3) sintering: sintering the ceramic blank at 1025 ℃ for 4 hours to obtain a ceramic wafer;
(10) coating an electrode: cleaning and drying the ceramic wafer, screen-printing a silver-coated electrode, and burning silver at the silver burning temperature of 500-600 ℃ for 1-2 hours;
(11) polarization: and (3) placing the ceramic plate plated with the silver electrode in silicone oil at 120-160 ℃, wherein the polarization voltage is 12 kV/mm-15 kV/mm, and the polarization time is 20 min-40 min.
Shown in FIG. 2 is the CaBi prepared in example 24Ti4-x(Mn1/3Ta2/3)xO15The XRD diffraction pattern of the ceramic, and the curve of the dielectric constant changing along with the temperature; FIG. 7 shows different amounts of Mn/Ta doped CaBi4Ti4-x(Mn1/3Ta2/3)xO15Curie temperature profile of the ceramic; FIG. 8 shows different amounts of Mn/Ta doped CaBi4Ti4-x(Mn1/3Ta2/3)xO15A room temperature piezoelectric coefficient change diagram of the ceramic; FIG. 9 shows different amounts of Mn/Ta doped CaBi4Ti4-x(Mn1/3Ta2/3)xO15Graph of change in resistivity at 400 ℃ of the ceramic.
As can be seen from FIG. 2, the XRD patterns of the Mn/Ta co-doped modified bismuth calcium titanate lead-free piezoelectric ceramic prepared in the embodiment are basically consistent with those of pure-phase bismuth titanate piezoelectric ceramic.
The test results were as follows: d33＝21pC/N，T C793 deg.C, resistivity at 400 deg.C rho 4.11 × 108Ω·cm。
Example 3
Preparation of CaBi conforming to chemical composition4Ti4-x(Mn1/3Ta2/3)xO15Mn/Ta codoped modified bismuth calcium titanate (CaBi) with x being 0.044Ti4O15) The lead-free piezoelectric ceramic comprises the following steps:
(1) preparing materials: with CaCO3Powder of Bi2O3Powder, TiO2Powder, MnCO3Powder and Ta2O5The powder is taken as a raw material, and the materials are proportioned according to the stoichiometric amount of Ca, Bi, Ti, Mn and Ta in the general formula;
(2) primary ball milling: adding absolute ethyl alcohol with the same quantity as the mixture into the mixture, and continuously ball-milling for 12 hours to uniformly mix the powder to form slurry, so that the comprehensive performance of the bismuth calcium titanate high-temperature piezoelectric ceramic material can be further improved;
(3) drying: placing the slurry in a constant-temperature oven for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder;
(4) and (3) tabletting and pre-sintering: putting the powder into a grinding tool to be pre-pressed into material blocks, pre-burning the material blocks, wherein the pre-burning temperature is 825 ℃, and the heat preservation time is 4 hours;
(5) secondary ball milling: putting the pre-sintered material blocks into a mortar, grinding and grinding to obtain primary powder, adding absolute ethyl alcohol with the same amount as the primary powder into the obtained primary powder, and continuously ball-milling for 12 hours to uniformly mix the powder to form slurry;
(6) drying: placing the slurry in a constant-temperature oven for baking, removing absolute ethyl alcohol, and grinding the slurry into powder in a mortar;
(7) and (3) granulation and forming: adding distilled water and polyvinyl alcohol solution (PVA) with the concentration of 8% into the powder as a binder, wherein the mass of the added distilled water is 2.5% of the mass of the powder, the mass of the added binder is 5% of the mass of the powder, and uniformly mixing in a mortar; placing the mixed powder in a grinding tool, and pressing into a green body; grinding the green body into powder in a mortar, sieving the powder through 60-mesh and 120-mesh sieves, and taking the powder in the middle layers of the 60-mesh and 120-mesh sieves to obtain the powder with proper particle size; putting the powder into a grinding tool, and pressing the powder into a green body under the pressure of 200 MPa;
(8) rubber discharging: removing the glue from the green body, calcining for 3 hours at the temperature of 650 ℃, and removing PVA in the green body to obtain a porcelain body;
(9) and (3) sintering: sintering the ceramic blank at 1025 ℃ for 1 hour to obtain a ceramic wafer;
(10) coating an electrode: cleaning and drying the ceramic wafer, screen-printing a silver-coated electrode, and burning silver at the silver burning temperature of 500-600 ℃ for 1-2 hours;
(11) polarization: and (3) placing the ceramic plate plated with the silver electrode in silicone oil at 120-160 ℃, wherein the polarization voltage is 12 kV/mm-15 kV/mm, and the polarization time is 20 min-40 min.
Shown in FIG. 3 is the CaBi prepared in example 34Ti4-x(Mn1/3Ta2/3)xO15X is the XRD diffraction pattern of 0.04 ceramic, and the curve of dielectric constant with temperature; FIG. 7 shows different amounts of Mn/Ta doped CaBi4Ti4-x(Mn1/3Ta2/3)xO15Curie temperature change chart of ceramic(ii) a FIG. 8 shows different amounts of Mn/Ta doped CaBi4Ti4-x(Mn1/3Ta2/3)xO15A room temperature piezoelectric coefficient change diagram of the ceramic; FIG. 9 shows different amounts of Mn/Ta doped CaBi4Ti4-x(Mn1/3Ta2/3)xO15Graph of change in resistivity at 400 ℃ of the ceramic.
As can be seen from FIG. 3, the XRD patterns of the Mn/Ta co-doped modified bismuth calcium titanate lead-free piezoelectric ceramic prepared in the example are basically consistent with those of pure-phase bismuth calcium titanate piezoelectric ceramic.
The test results were as follows: d33＝24pC/N，TCAt 793 deg.C, resistivity at 400 deg.C rho 4.96X 108Ω·cm。
Example 4
Preparation of CaBi conforming to chemical composition4Ti4-x(Mn1/3Ta2/3)xO15Mn/Ta codoped modified bismuth titanate (Bi) with x being 0.054Ti3O12) The lead-free piezoelectric ceramic comprises the following steps:
(1) preparing materials: with CaCO3Powder of Bi2O3Powder, TiO2Powder, MnCO3Powder and Ta2O5The powder is taken as a raw material, and the materials are proportioned according to the stoichiometric amount of Ca, Bi, Ti, Mn and Ta in the general formula;
(2) primary ball milling: adding absolute ethyl alcohol with the same quantity as the mixture into the mixture, and continuously ball-milling for 12 hours to uniformly mix the powder to form slurry, so that the comprehensive performance of the bismuth calcium titanate high-temperature piezoelectric ceramic material can be further improved;
(3) drying: placing the slurry in a constant-temperature oven for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder;
(4) and (3) tabletting and pre-sintering: putting the powder into a grinding tool to be pre-pressed into material blocks, pre-burning the material blocks, wherein the pre-burning temperature is 825 ℃, and the heat preservation time is 4 hours;
(5) secondary ball milling: putting the pre-sintered material blocks into a mortar, grinding and grinding to obtain primary powder, adding absolute ethyl alcohol with the same amount as the primary powder into the obtained primary powder, and continuously ball-milling for 12 hours to uniformly mix the powder to form slurry;
(6) drying: placing the slurry in a constant-temperature oven for baking, removing absolute ethyl alcohol, and grinding the slurry into powder in a mortar;
(7) and (3) granulation and forming: adding distilled water and polyvinyl alcohol solution (PVA) with the concentration of 8% into the powder as a binder, wherein the mass of the added distilled water is 2.5% of the mass of the powder, the mass of the added binder is 5% of the mass of the powder, and uniformly mixing in a mortar; placing the mixed powder in a grinding tool, and pressing into a green body; grinding the green body into powder in a mortar, sieving the powder through 60-mesh and 120-mesh sieves, and taking the powder in the middle layers of the 60-mesh and 120-mesh sieves to obtain the powder with proper particle size; putting the powder into a grinding tool, and pressing the powder into a green body under the pressure of 200 MPa;
(8) rubber discharging: removing the glue from the green body, calcining for 3 hours at the temperature of 650 ℃, and removing PVA in the green body to obtain a porcelain body;
(9) and (3) sintering: sintering the ceramic blank at 1025 ℃ for 1 hour to obtain a ceramic wafer;
(10) coating an electrode: cleaning and drying the ceramic wafer, screen-printing a silver-coated electrode, and burning silver at the silver burning temperature of 500-600 ℃ for 1-2 hours;
(11) polarization: and (3) placing the ceramic plate plated with the silver electrode in silicone oil at 120-160 ℃, wherein the polarization voltage is 12 kV/mm-15 kV/mm, and the polarization time is 20 min-40 min.
Shown in FIG. 4 is the CaBi prepared in example 44Ti4-x(Mn1/3Ta2/3)xO15The XRD diffraction pattern of the ceramic, and the curve of the dielectric constant changing along with the temperature are 0.05; FIG. 7 shows different amounts of Mn/Ta doped CaBi4Ti4-x(Mn1/3Ta2/3)xO15Curie temperature profile of the ceramic; FIG. 8 shows different amounts of Mn/Ta doped CaBi4Ti4-x(Mn1/3Ta2/3)xO15A room temperature piezoelectric coefficient change diagram of the ceramic; FIG. 9 shows different amounts of Mn/Ta doped CaBi4Ti4-x(Mn1/3Ta2/3)xO15Graph of change in resistivity at 400 ℃ of the ceramic.
As can be seen from FIG. 4, the XRD patterns of the Mn/Ta co-doped modified bismuth calcium titanate lead-free piezoelectric ceramic prepared in the example are substantially consistent with those of pure-phase bismuth calcium titanate piezoelectric ceramic.
The test results were as follows: d33＝23pC/N，TCAt 793 deg.C, resistivity at 400 deg.C rho 2.33X 108Ω·cm。
Example 5
Preparation of CaBi conforming to chemical composition4Ti4-x(Mn1/3Ta2/3)xO15Mn/Ta codoped modified bismuth calcium titanate (CaBi) with x being 0.064Ti4O15) The lead-free piezoelectric ceramic comprises the following steps:
(1) preparing materials: with CaCO3Powder of Bi2O3Powder, TiO2Powder, MnCO3Powder and Ta2O5The powder is taken as a raw material, and the materials are proportioned according to the stoichiometric amount of Ca, Bi, Ti, Mn and Ta in the general formula;
(2) primary ball milling: adding absolute ethyl alcohol with the same quantity as the mixture into the mixture, and continuously ball-milling for 12 hours to uniformly mix the powder to form slurry, so that the comprehensive performance of the bismuth calcium titanate high-temperature piezoelectric ceramic material can be further improved;
(3) drying: placing the slurry in a constant-temperature oven for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder;
(4) and (3) tabletting and pre-sintering: putting the powder into a grinding tool to be pre-pressed into material blocks, pre-burning the material blocks, wherein the pre-burning temperature is 825 ℃, and the heat preservation time is 4 hours;
(5) secondary ball milling: putting the pre-sintered material blocks into a mortar, grinding and grinding to obtain primary powder, adding absolute ethyl alcohol with the same amount as the primary powder into the obtained primary powder, and continuously ball-milling for 12 hours to uniformly mix the powder to form slurry;
(6) drying: placing the slurry in a constant-temperature oven for baking, removing absolute ethyl alcohol, and grinding the slurry into powder in a mortar;
(7) and (3) granulation and forming: adding distilled water and polyvinyl alcohol solution (PVA) with the concentration of 8% into the powder as a binder, wherein the mass of the added distilled water is 2.5% of the mass of the powder, the mass of the added binder is 5% of the mass of the powder, and uniformly mixing in a mortar; placing the mixed powder in a grinding tool, and pressing into a green body; grinding the green body into powder in a mortar, sieving the powder through 60-mesh and 120-mesh sieves, and taking the powder in the middle layers of the 60-mesh and 120-mesh sieves to obtain the powder with proper particle size; putting the powder into a grinding tool, and pressing the powder into a green body under the pressure of 200 MPa;
(8) rubber discharging: removing the glue from the green body, calcining for 3 hours at the temperature of 650 ℃, and removing PVA in the green body to obtain a porcelain body;
(9) and (3) sintering: sintering the ceramic blank at 1025 ℃ for 1 hour to obtain a ceramic wafer;
(10) coating an electrode: cleaning and drying the ceramic wafer, screen-printing a silver-coated electrode, and burning silver at the silver burning temperature of 500-600 ℃ for 1-2 hours;
(11) polarization: and (3) placing the ceramic plate plated with the silver electrode in silicone oil at 120-160 ℃, wherein the polarization voltage is 12 kV/mm-15 kV/mm, and the polarization time is 20 min-40 min.
Shown in FIG. 5 is the CaBi prepared in example 54Ti4-x(Mn1/3Ta2/3)xO15X is the XRD diffractogram of 0.06 ceramic, and the curve of dielectric constant as a function of temperature; FIG. 7 shows different amounts of Mn/Ta doped CaBi4Ti4-x(Mn1/3Ta2/3)xO15A curie temperature profile of the ceramic; FIG. 8 shows different amounts of Mn/Ta doped CaBi4Ti4-x(Mn1/3Ta2/3)xO15A room temperature piezoelectric coefficient change diagram of the ceramic; FIG. 9 shows different amounts of Mn/Ta doped CaBi4Ti4-x(Mn1/3Ta2/3)xO15Graph of change in resistivity at 400 ℃ of the ceramic.
As can be seen from FIG. 5, the XRD patterns of the Mn/Ta co-doped modified bismuth calcium titanate lead-free piezoelectric ceramic prepared in the example are substantially consistent with those of pure-phase bismuth calcium titanate piezoelectric ceramic.
The test results were as follows: d33＝22pC/N，T C792 deg.C, and resistivity rho 6.19 × 10 at 400 deg.C7Ω·cm。
Example 6
Preparation of CaBi conforming to chemical composition4Ti4-x(Mn1/3Ta2/3)xO15Mn/Ta codoped modified bismuth calcium titanate (CaBi) with x being 0.14Ti4O15) The lead-free piezoelectric ceramic comprises the following steps:
(1) preparing materials: with CaCO3Powder of Bi2O3Powder, TiO2Powder, MnCO3Powder and Ta2O5The powder is taken as a raw material, and the materials are proportioned according to the stoichiometric amount of Ca, Bi, Ti, Mn and Ta in the general formula;
(2) primary ball milling: adding absolute ethyl alcohol with the same quantity as the mixture into the mixture, and continuously ball-milling for 12 hours to uniformly mix the powder to form slurry, so that the comprehensive performance of the bismuth calcium titanate high-temperature piezoelectric ceramic material can be further improved;
(3) drying: placing the slurry in a constant-temperature oven for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder;
(4) and (3) tabletting and pre-sintering: putting the powder into a grinding tool to be pre-pressed into material blocks, pre-burning the material blocks, wherein the pre-burning temperature is 825 ℃, and the heat preservation time is 4 hours;
(5) secondary ball milling: putting the pre-sintered material blocks into a mortar, grinding and grinding to obtain primary powder, adding absolute ethyl alcohol with the same amount as the primary powder into the obtained primary powder, and continuously ball-milling for 12 hours to uniformly mix the powder to form slurry;
(6) drying: placing the slurry in a constant-temperature oven for baking, removing absolute ethyl alcohol, and grinding the slurry into powder in a mortar;
(7) and (3) granulation and forming: adding distilled water and polyvinyl alcohol solution (PVA) with the concentration of 8% into the powder as a binder, wherein the mass of the added distilled water is 2.5% of the mass of the powder, the mass of the added binder is 5% of the mass of the powder, and uniformly mixing in a mortar; placing the mixed powder in a grinding tool, and pressing into a green body; grinding the green body into powder in a mortar, sieving the powder through 60-mesh and 120-mesh sieves, and taking the powder in the middle layers of the 60-mesh and 120-mesh sieves to obtain the powder with proper particle size; putting the powder into a grinding tool, and pressing the powder into a green body under the pressure of 200 MPa;
(8) rubber discharging: removing the glue from the green body, calcining for 3 hours at the temperature of 650 ℃, and removing PVA in the green body to obtain a porcelain body;
(9) and (3) sintering: sintering the ceramic blank at 1025 ℃ for 1 hour to obtain a ceramic wafer;
(10) coating an electrode: cleaning and drying the ceramic wafer, screen-printing a silver-coated electrode, and burning silver at the silver burning temperature of 500-600 ℃ for 1-2 hours;
(11) polarization: and (3) placing the ceramic plate plated with the silver electrode in silicone oil at 120-160 ℃, wherein the polarization voltage is 12 kV/mm-15 kV/mm, and the polarization time is 20 min-40 min.
Shown in FIG. 6 is the CaBi prepared in example 64Ti4-x(Mn1/3Ta2/3)xO15X is the XRD diffraction pattern of 0.1 ceramic, and the curve of dielectric constant with temperature; FIG. 7 shows different amounts of Mn/Ta doped CaBi4Ti4-x(Mn1/3Ta2/3)xO15Curie temperature profile of the ceramic; FIG. 8 shows different amounts of Mn/Ta doped CaBi4Ti4-x(Mn1/3Ta2/3)xO15A room temperature piezoelectric coefficient change diagram of the ceramic; FIG. 9 shows different amounts of Mn/Ta doped CaBi4Ti4-x(Mn1/3Ta2/3)xO15Graph of change in resistivity at 400 ℃ of the ceramic.
As can be seen from FIG. 6, the XRD patterns of the Mn/Ta co-doped modified bismuth calcium titanate lead-free piezoelectric ceramic prepared in the example are substantially consistent with those of pure-phase bismuth calcium titanate piezoelectric ceramic.
The test results were as follows: d33＝21pC/N，TCAt 791 deg.C, resistivity at 400 deg.C rho 3.39 × 107Ω·cm。
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (5)

1. The high-resistivity and high-voltage electroactive bismuth calcium titanate-based high-temperature piezoelectric ceramic is characterized in that the chemical general formula of the piezoelectric ceramic is CaBi4Ti4-x(Mn1/3Ta2/3)xO12Wherein 0 is<x is less than or equal to 0.1, and the preparation method comprises the following steps:
preparing materials: with CaCO3Powder of Bi2O3Powder of TiO2Powder, MnCO3Powder and Ta2O5The powder is used as raw material and is represented by the general formula CaBi4Ti4-x(Mn1/3Ta2/3)xO12Proportioning the Ca, Bi, Ti, Mn and Ta in the stoichiometric ratio of 0<x≤0.1；
Primary ball milling: adding absolute ethyl alcohol with the same quantity as the mixture into the mixture, and continuously ball-milling for 12-24 hours to uniformly mix the powder to form slurry;
drying: placing the slurry in a constant-temperature oven for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder;
and (3) tabletting and pre-sintering: placing the powder into a grinding tool to be pre-pressed into material blocks, pre-burning the material blocks, wherein the pre-burning temperature is 750-825 ℃, and the heat preservation time is 2-4 hours;
secondary ball milling: putting the pre-sintered material blocks in a mortar, grinding and grinding to obtain primary powder, adding absolute ethyl alcohol with the same amount as the primary powder into the obtained primary powder, and continuously ball-milling for 12-24 hours to uniformly mix the powder to form slurry;
drying: placing the slurry in a constant-temperature oven for baking, removing absolute ethyl alcohol, and grinding the slurry into powder in a mortar;
and (3) granulation and forming: adding distilled water and polyvinyl alcohol solution (PVA) with the concentration of 8% into the powder as a binder, wherein the mass of the added distilled water is 2.5% of the mass of the powder, the mass of the added binder is 5% of the mass of the powder, and uniformly mixing in a mortar; placing the mixed powder in a grinding tool, and pressing into a green body; grinding the green body into powder in a mortar, sieving the powder through 60-mesh and 120-mesh sieves, and taking the powder in the middle layers of the 60-mesh and 120-mesh sieves to obtain the powder with proper particle size; putting the powder into a grinding tool, and pressing the powder into a green body under the pressure of 200 MPa;
rubber discharging: removing the glue from the green body, calcining for 3 hours at the temperature of 650 ℃, and removing PVA in the green body to obtain a porcelain body;
and (3) sintering: sintering the ceramic blank at the sintering temperature of 1000-1100 ℃ for 2-4 hours to obtain a ceramic wafer;
coating an electrode: cleaning and drying the ceramic wafer, screen-printing a silver-coated electrode, and burning silver at the silver burning temperature of 500-600 ℃ for 1-2 hours;
polarization: and (3) placing the ceramic plate plated with the silver electrode in silicone oil at 120-160 ℃, wherein the polarization voltage is 12 kV/mm-15 kV/mm, and the polarization time is 20 min-40 min.
2. The high-resistivity, high-piezoelectric-activity bismuth calcium titanate-based high-temperature piezoelectric ceramic as claimed in claim 1, wherein the ball milling time is 12 hours in the primary and secondary ball milling processes.
3. The high-resistivity, high-piezoelectric-activity bismuth calcium titanate-based high-temperature piezoelectric ceramic of claim 1, wherein in the pre-sintering process, the pre-sintering temperature is 825 ℃, and the heat preservation time is 4 hours.
4. The method for preparing the bismuth calcium titanate-based high-temperature piezoelectric ceramic with high resistivity and high piezoelectric activity according to claim 1, wherein in the sintering process, the sintering temperature is 1025 ℃, and the heat preservation time is 1 hour.
5. The method of claim 1, wherein x is any one of 0.02, 0.03, 0.04, 0.05, 0.06, or 0.1.
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