CN117263674A - Lanthanide and Cr, W co-doped CaBi 4 Ti 4 O 15 High-temperature piezoelectric ceramic material and preparation method thereof - Google Patents

Lanthanide and Cr, W co-doped CaBi 4 Ti 4 O 15 High-temperature piezoelectric ceramic material and preparation method thereof Download PDF

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CN117263674A
CN117263674A CN202311185545.XA CN202311185545A CN117263674A CN 117263674 A CN117263674 A CN 117263674A CN 202311185545 A CN202311185545 A CN 202311185545A CN 117263674 A CN117263674 A CN 117263674A
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cabi
ceramic material
piezoelectric ceramic
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沈宗洋
文启来
王竹梅
李月明
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Jingdezhen Ceramic Institute
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Abstract

The invention discloses a lanthanide and Cr, W co-doped CaBi 4 Ti 4 O 15 High-temperature piezoelectric ceramic material and preparation method thereof, aiming at CaBi 4 Ti 4 O 15 Ca at A-position of ceramic material 2+ Ions, doped substitution is carried out by adopting +3 lanthanide metal ions with 12 coordination, and Ti is aimed at B site 4+ Ion, composite high valence ion [ Cr ] 1/3 W 2/3 ] 5+ The doping substitution is carried out, the Curie temperature is not reduced, and the piezoelectric performance and the high-temperature resistivity are improved, so that the novel environment-friendly piezoelectric ceramic material with excellent comprehensive electrical performance and good high-temperature stability is provided,has wide application prospect in the high-temperature field. The preparation method of the invention adopts an advanced ceramic preparation process, has low firing temperature, low preparation cost, simple process, easy operation and easily controlled influencing factors, is suitable for mass industrialized production, and is beneficial to popularization and application.

Description

Lanthanide and Cr, W co-doped CaBi 4 Ti 4 O 15 High temperature piezoelectricCeramic material and preparation method thereof
Technical Field
The invention relates to the technical field of piezoelectric ceramic materials, in particular to a bismuth calcium titanate high-temperature piezoelectric ceramic material with a bismuth layered structure and a preparation method thereof.
Background
At present, the most widely applied piezoelectric ceramic materials are mainly PZT-based piezoelectric ceramics with perovskite structures, but the Curie temperature of the piezoelectric ceramics is generally below 400 ℃, and the piezoelectric materials cannot work normally above the Curie temperature due to the existence of depolarization phenomena of the piezoelectric materials. With the rapid development of aerospace, geological exploration and other works and the demand of sustainable development of human society, it is necessary to find an environment-friendly piezoelectric material with high curie temperature and excellent piezoelectric performance.
The bismuth layered structure ceramic has the advantages of high Curie temperature, good fatigue resistance and the like, and is a candidate material suitable for high-temperature environment. The bismuth layer-structured ceramic material is composed of (Bi) 2 O 2 ) 2+ The layers and perovskite structure lattice layers are alternately stacked with each other, and the chemical general formula is (Bi 2 O 2 ) 2+ (A m-1 B m O 3m+1 ) 2- Wherein CaBi 4 Ti 4 O 15 (CBT) is a typical bismuth layered structure ferroelectric material, A is 12 coordinated Ca 2+ And Bi (Bi) 3+ B is 6-coordinated Ti 4+ M=4, the material having a high curie temperature (T C Low piezoelectric activity and high resonant frequency temperature coefficient, and these factors limit the application in high temperature field. Therefore, how to obtain a CBT piezoelectric ceramic material with excellent comprehensive electrical properties without reducing the Curie temperature and improving the piezoelectric activity becomes an important subject in the research of the field of high-temperature piezoelectric ceramic materials.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the lanthanide and Cr, W co-doped CaBi 4 Ti 4 O 15 High temperature piezoelectricCeramic material for CaBi 4 Ti 4 O 15 Ca at A-position of ceramic material 2+ Ions, doped substitution is carried out by adopting +3 lanthanide metal ions with 12 coordination, and Ti is aimed at B site 4+ Ion, composite high valence ion [ Cr ] 1/3 W 2/3 ] 5+ The doping substitution is carried out so as to improve the piezoelectric performance and the high-temperature resistivity of the piezoelectric ceramic material without reducing the Curie temperature by the composite doping modification, thereby providing a novel environment-friendly piezoelectric ceramic material with excellent comprehensive electrical performance. Another object of the present invention is to provide the lanthanide and Cr, W co-doped CaBi 4 Ti 4 O 15 A preparation method of a high-temperature piezoelectric ceramic material.
The aim of the invention is realized by the following technical scheme:
the invention provides a lanthanide and Cr, W co-doped CaBi 4 Ti 4 O 15 High temperature piezoelectric ceramic material with +3 valence lanthanide metal ion M with 12 coordination to replace CaBi 4 Ti 4 O 15 Ca in position A of the middle 2+ Ion by compounding high valence ion [ Cr 1/3 W 2/3 ] 5+ Doping substituted CaBi 4 Ti 4 O 15 Ti of B-position in the middle 4+ Ions of the general chemical formula Ca 1-x M x Bi 4 Ti 4-y [Cr 1/ 3 W 2/3 ] y O 15 Wherein x is more than or equal to 0.04 and less than or equal to 0.1,0.04, y is more than or equal to 0.08, and M is La 3+ 、Nd 3+ Or Sm 3+ Ions.
In the scheme, d of the piezoelectric ceramic material 33 ≥24pC/N，T C Not less than 780 ℃; the resistivity (rho) is more than or equal to 2.0X10 at 500 DEG C 7 Omega cm, dielectric loss (tan delta) less than or equal to 0.5%; d after 600 ℃ annealing 33 ≥20pC/N。
The other object of the invention is achieved by the following technical scheme:
the invention provides the lanthanide series element and Cr, W co-doped CaBi 4 Ti 4 O 15 The preparation method of the high-temperature piezoelectric ceramic material comprises the following steps ofThe steps are as follows:
(1) Preparation of presynthesized precursor powders
By CaCO 3 、Bi 2 O 3 、TiO 2 、Cr 2 O 3 、WO 3 As a raw material corresponding to Ca, bi, ti, cr, W in the chemical formula, la is used 2 O 3 、Nd 2 O 3 Or Sm 2 O 3 As a raw material corresponding to M in the chemical formula; proportioning the raw materials according to the chemical quantity in the chemical formula, performing ball milling treatment for one time by taking absolute ethyl alcohol as a ball milling medium, drying, sieving, pressing and molding the obtained materials, and then placing the materials in a sealed crucible for calcination treatment; grinding and sieving the calcined material, performing secondary ball milling treatment, and drying, grinding and sieving the obtained material to obtain pre-synthesized precursor powder;
(2) Preparation of high-temperature piezoelectric ceramic material
Loading the pre-synthesized precursor powder into a graphite mold, and placing the graphite mold in a discharge plasma sintering furnace for primary calcination treatment to obtain a carbon-containing sintered product; then placing the carbon-containing sintered product in a common high-temperature furnace for secondary calcination treatment to decarburize, so as to obtain a decarburized sintered product; and finally, carrying out polarization treatment on the decarburized sintered product to obtain the high-temperature piezoelectric ceramic material.
Further, the purity of each raw material in the step (1) in the preparation method is not lower than 99.9%. The pressure of the compression molding is 4-6 Mpa; the calcination treatment is to raise the temperature to 800-850 ℃ at 5 ℃/min.
Further, in the step (2) of the preparation method, the primary calcination treatment is that the pressure of a discharge plasma sintering furnace is 25-30 MPa, the direct current pulse current is 500-550A, the temperature is increased to 800-850 ℃ at 100 ℃/min, the direct current pulse current is stopped after the heat preservation is carried out for 5-8 min, then the pressure is released, and the furnace is cooled to the room temperature. The secondary calcination treatment is that 5 ℃/min is raised to 600-650 ℃, the temperature is kept for 3-4 hours, and the mixture is cooled to room temperature along with a furnace.
Further, in the step (2) of the preparation method, the polarization treatment is that the surface of the decarburized and sintered product is polished; then electrode coating treatment is carried out, namely, the upper surface and the lower surface of the decarburized and sintered product are coated with silver electrodes after polishing; then heating to 650-680 ℃ at 5 ℃/min for calcination, preserving heat for 40-60 min, and cooling to room temperature along with a furnace; finally, the polarization is carried out in high-temperature silicone oil at 180-200 ℃ by adding direct current voltage of 5-10 kV/mm, and the polarization time is 20-30 min.
Co-doping the lanthanide with Cr and W to obtain CaBi 4 Ti 4 O 15 The product is prepared by the preparation method of the high-temperature piezoelectric ceramic material.
The invention has the following beneficial effects:
(1) In the preparation of CaBi 4 Ti 4 O 15 In the process of the piezoelectric ceramic material, bismuth vacancies are necessarily formed due to volatilization of bismuth at high temperature, thereby generating vacancy defects. In order to solve the problem, the invention adopts the valence state ratio A-position Ca 2+ High ionic La 3+ 、Nd 3+ Or Sm 3+ The ion is doped and substituted, and simultaneously the valence state ratio B-bit Ti is adopted 4+ Ion-high composite ion [ Cr 1/3 W 2/3 ] 5+ The perovskite-like layer (A) is doped and substituted to cause A, B to be located at the defect m-1 B m O 3m+1 ) 2- Electrons are generated, thereby enhancing the bismuth oxide layer (Bi 2 O 2 ) 2+ And perovskite-like layer (A) m-1 B m O 3m+1 ) 2- The interaction between the two components changes the growth behavior of the crystal grains, and finally obtains CaBi with excellent performance 4 Ti 4 O 15 High temperature piezoelectric ceramic material.
(2) The invention adopts the advanced spark plasma sintering technology, the sintering technology has low sintering temperature and short time, thus the energy consumption is low, the density of the sintered material is high, and the CaBi with excellent performance can be obtained 4 Ti 4 O 15 High temperature piezoelectric ceramic material.
(3) The lanthanide element and Cr, W co-doped CaBi 4 Ti 4 O 15 Piezoelectric ceramic material with Curie temperature not less than 780 ℃ and piezoelectric constant d 33 24pC/N or more, d after 600℃ annealing 33 Not less than 20pC/N; the resistivity at 500 ℃ is more than or equal to 2.0X10 7 Omega cm, dielectric loss is less than or equal to 0.5%. The material has good high-temperature stability and wide application prospect in the high-temperature field.
(4) The preparation method of the invention adopts an advanced ceramic preparation process, has low firing temperature, low preparation cost, simple process, easy operation and easily controlled influencing factors, is suitable for mass industrialized production, and is beneficial to popularization and application.
Drawings
The invention will be described in further detail with reference to examples and figures:
FIG. 1 is a schematic illustration of a lanthanide-Cr-W co-doped CaBi prepared in accordance with an embodiment of the present invention 4 Ti 4 O 15 XRD patterns of high temperature piezoceramic, and comparative piezoceramic materials;
FIG. 2 is a schematic illustration of a CaBi co-doped with Cr and W in accordance with an embodiment of the present invention 4 Ti 4 O 15 The dielectric constant of the high temperature piezoelectric ceramic changes with temperature.
Detailed Description
Embodiment one:
this example is a CaBi co-doped with lanthanoid and Cr, W 4 Ti 4 O 15 The preparation method of the high-temperature piezoelectric ceramic material comprises the following steps:
(1) Preparation of presynthesized precursor powders
With CaCO of 99.9% purity 3 、La 2 O 3 、Bi 2 O 3 、TiO 2 、Cr 2 O 3 、WO 3 As and of the chemical formula Ca 0.95 La 0.05 Bi 4 Ti 3.94 [Cr 1/3 W 2/3 ] 0.06 O 15 Corresponding to Ca, la, bi, ti, cr, W, proportioning the raw materials according to the stoichiometric amount in the chemical formula, then taking absolute ethyl alcohol as a ball milling medium, performing ball milling treatment on a planetary ball mill for 24 hours according to the ratio of ball to material to absolute ethyl alcohol=4:1:3 at the rotating speed of 400r/min, drying the obtained material, sieving with a 80-mesh sieve, pressing and molding under 4Mpa, and then placing in a sealed crucibleCalcining at a temperature of 5 ℃/min to 800 ℃ in an oxidizing atmosphere, and keeping the temperature for 2 hours; grinding the calcined material, sieving with an 80-mesh sieve, performing secondary ball milling treatment by adopting the same process as the primary ball milling treatment, and drying, grinding and sieving with an 80-mesh sieve the obtained material to obtain pre-synthesized precursor powder;
(2) Preparation of high-temperature piezoelectric ceramic material
(2-1) loading 0.8g of the pre-synthesized precursor powder into a cylindrical graphite mold with the diameter of 20mm, placing the cylindrical graphite mold into a discharge plasma sintering furnace, setting the pressure to be 25MPa and the direct current pulse current to be 500A, heating to 800 ℃ at 100 ℃/min for primary calcination treatment, keeping the temperature for 5min, stopping the direct current pulse current, releasing the pressure, and cooling to room temperature along with the furnace to obtain a carbon-containing sintered product;
(2-2) placing the carbon-containing sintered product in a common high-temperature furnace, carrying out secondary calcination treatment at a speed of 5 ℃/min to 600 ℃ to carry out decarburization, preserving heat for 3 hours, and cooling to room temperature along with the furnace to obtain a decarburized sintered product;
(2-3) subjecting the decarburized fired product to a polarization treatment, wherein the surface of the decarburized fired product is polished; then electrode coating treatment is carried out, namely, the upper surface and the lower surface of the decarburized and sintered product are coated with silver electrodes after polishing; then, heating to 650 ℃ at 5 ℃ per minute for calcination, preserving heat for 40 minutes, and cooling to room temperature along with a furnace; finally, the high-temperature piezoelectric ceramic material is prepared by polarizing the high-temperature silicon oil at 180 ℃ with direct current voltage of 5-10 kV/mm for 20 min.
Embodiment two:
this example is a CaBi co-doped with lanthanoid and Cr, W 4 Ti 4 O 15 The preparation method of the high-temperature piezoelectric ceramic material is different from the embodiment in that:
1. the chemical formula of this example is Ca 0.94 Nd 0.06 Bi 4 Ti 3.94 [Cr 1/3 W 2/3 ] 0.06 O 15 The raw material corresponding to Nd is Nd 2 O 3 。
2. The calcination temperature in step (1) is 820 ℃; the calcination temperature in step (2-1) was 820 ℃.
Embodiment III:
this example is a CaBi co-doped with lanthanoid and Cr, W 4 Ti 4 O 15 The preparation method of the high-temperature piezoelectric ceramic material is different from the embodiment in that:
1. the chemical formula of this example is Ca 0.93 Sm 0.07 Bi 4 Ti 3.94 [Cr 1/3 W 2/3 ] 0.06 O 15 The raw material corresponding to Sm is Sm 2 O 3 。
2. The calcination temperature in step (1) is 820 ℃; the calcination temperature in step (2-1) was 820 ℃.
Comparative example:
undoped CaBi of the chemical formula 4 Ti 4 O 15 As a comparative example, the preparation process was the same as in example one.
As can be seen from FIG. 1, each diffraction peak of the piezoelectric ceramic materials prepared in each example and comparative example is completely matched with the standard spectrum PDF 00-052-1640, which shows that the obtained material is CaBi with single crystal phase 4 Ti 4 O 15 A material.
The lanthanide series element and Cr, W co-doped CaBi prepared by the embodiment of the invention 4 Ti 4 O 15 The dielectric constant of the high temperature piezoelectric ceramic is plotted as a function of temperature as shown in fig. 2. The results of the performance test of the piezoelectric ceramic materials of the examples and comparative examples of the present invention are shown in table 1.
TABLE 1 Properties of the ceramic materials of examples and comparative examples according to the invention

Claims (9)

1. Lanthanide and Cr, W co-doped CaBi 4 Ti 4 O 15 The high-temperature piezoelectric ceramic material is characterized in that: to have 12 coordinationSubstitution of CaBi by M doping of +3 valent lanthanide metal ions 4 Ti 4 O 15 Ca in position A of the middle 2+ Ion by compounding high valence ion [ Cr 1/ 3 W 2/3 ] 5+ Doping substituted CaBi 4 Ti 4 O 15 Ti of B-position in the middle 4+ Ions of the general chemical formula Ca 1-x M x Bi 4 Ti 4-y [Cr 1/3 W 2/3 ] y O 15 Wherein x is more than or equal to 0.04 and less than or equal to 0.1,0.04, y is more than or equal to 0.08, and M is La 3+ 、Nd 3+ Or Sm 3+ Ions.
2. The lanthanide-Cr, W co-doped CaBi of claim 1 4 Ti 4 O 15 The high-temperature piezoelectric ceramic material is characterized in that: d of the piezoelectric ceramic material 33 ≥24pC/N，T C Not less than 780 ℃; the resistivity (rho) is more than or equal to 2.0X10 at 500 DEG C 7 Omega cm, dielectric loss (tan delta) less than or equal to 0.5%; d after 600 ℃ annealing 33 ≥20pC/N。
3. The co-doped CaBi of a lanthanide with Cr, W according to claim 1 or 2 4 Ti 4 O 15 The preparation method of the high-temperature piezoelectric ceramic material is characterized by comprising the following steps of:
(1) Preparation of presynthesized precursor powders
By CaCO 3 、Bi 2 O 3 、TiO 2 、Cr 2 O 3 、WO 3 As a raw material corresponding to Ca, bi, ti, cr, W in the chemical formula, la is used 2 O 3 、Nd 2 O 3 Or Sm 2 O 3 As a raw material corresponding to M in the chemical formula; proportioning the raw materials according to the chemical quantity in the chemical formula, performing ball milling treatment for one time by taking absolute ethyl alcohol as a ball milling medium, drying, sieving, pressing and molding the obtained materials, and then placing the materials in a sealed crucible for calcination treatment; grinding and sieving the calcined material, performing secondary ball milling treatment, and drying, grinding and sieving the obtained material to obtain the pre-synthesized precursorA bulk powder;
(2) Preparation of high-temperature piezoelectric ceramic material
Loading the pre-synthesized precursor powder into a graphite mold, and placing the graphite mold in a discharge plasma sintering furnace for primary calcination treatment to obtain a carbon-containing sintered product; then placing the carbon-containing sintered product in a common high-temperature furnace for secondary calcination treatment to decarburize, so as to obtain a decarburized sintered product; and finally, carrying out polarization treatment on the decarburized sintered product to obtain the high-temperature piezoelectric ceramic material.
4. A lanthanide and Cr, W co-doped CaBi according to claim 3 4 Ti 4 O 15 The preparation method of the high-temperature piezoelectric ceramic material is characterized by comprising the following steps of: the purity of each raw material in the step (1) is not lower than 99.9 percent.
5. A lanthanide and Cr, W co-doped CaBi according to claim 3 4 Ti 4 O 15 The preparation method of the high-temperature piezoelectric ceramic material is characterized by comprising the following steps of: the pressure of the compression molding in the step (1) is 4-6 Mpa; the calcination treatment is to raise the temperature to 800-850 ℃ at 5 ℃/min.
6. A lanthanide and Cr, W co-doped CaBi according to claim 3 4 Ti 4 O 15 The preparation method of the high-temperature piezoelectric ceramic material is characterized by comprising the following steps of: the primary calcination treatment in the step (2) is that the pressure of a discharge plasma sintering furnace is 25-30 MPa, the direct current pulse current is 500-550A, the temperature is raised to 800-850 ℃ at 100 ℃/min, the direct current pulse current is stopped after the heat preservation is carried out for 5-8 min, then the pressure is released, and the furnace is cooled to the room temperature.
7. A lanthanide and Cr, W co-doped CaBi according to claim 3 4 Ti 4 O 15 The preparation method of the high-temperature piezoelectric ceramic material is characterized by comprising the following steps of: and (3) in the step (2), the secondary calcination treatment is that the temperature is raised to 600-650 ℃ at 5 ℃/min, the temperature is kept for 3-4 hours, and the mixture is cooled to the room temperature along with a furnace.
8. A lanthanide and Cr, W co-doped CaBi according to claim 3 4 Ti 4 O 15 The preparation method of the high-temperature piezoelectric ceramic material is characterized by comprising the following steps of: the polarization treatment in the step (2) is that the surface of the decarburized and burnt product is polished; then electrode coating treatment is carried out, namely, the upper surface and the lower surface of the decarburized and sintered product are coated with silver electrodes after polishing; then heating to 650-680 ℃ at 5 ℃/min for calcination, preserving heat for 40-60 min, and cooling to room temperature along with a furnace; finally, the polarization is carried out in high-temperature silicone oil at 180-200 ℃ by adding direct current voltage of 5-10 kV/mm, and the polarization time is 20-30 min.
9. Co-doping CaBi with Cr, W using a lanthanide according to any one of claims 3-8 4 Ti 4 O 15 The product is prepared by the preparation method of the high-temperature piezoelectric ceramic material.
CN202311185545.XA 2023-09-14 2023-09-14 Lanthanide and Cr, W co-doped CaBi 4 Ti 4 O 15 High-temperature piezoelectric ceramic material and preparation method thereof Pending CN117263674A (en)

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