CN109704757B - Lead-free piezoelectric ceramic with low-field and high-field piezoelectric properties and preparation method thereof - Google Patents
Lead-free piezoelectric ceramic with low-field and high-field piezoelectric properties and preparation method thereof Download PDFInfo
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- CN109704757B CN109704757B CN201910025697.0A CN201910025697A CN109704757B CN 109704757 B CN109704757 B CN 109704757B CN 201910025697 A CN201910025697 A CN 201910025697A CN 109704757 B CN109704757 B CN 109704757B
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- 239000000919 ceramic Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229910010252 TiO3 Inorganic materials 0.000 claims abstract description 10
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000005245 sintering Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000009694 cold isostatic pressing Methods 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 230000005684 electric field Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
Abstract
The invention discloses a lead-free piezoelectric ceramic with low-field and high-field piezoelectric properties and a preparation method thereof, wherein the lead-free piezoelectric ceramic is prepared by adopting a lead-free piezoelectric ceramicThe ceramics is (Bi)0.5Na0.5)TiO3、BaTiO3、Bi2CoMnO6、WO3And MgO as raw material according to the chemical composition general formula (1-y)(Bi0.5Na0.5)0.94Ba0.06Ti x1‑(W0.5Mg0.5) x O3‑yBi2CoMnO6Is prepared byx、yExpressed as a mole fraction, 0.01. ltoreqx≤0.05，0.01≤yLess than or equal to 0.05; the preparation method is optimized on the basis of the existing process. The lead-free piezoelectric ceramic disclosed by the invention can well give consideration to the piezoelectric performance under both low and high fields, and has low production cost and good practicability.
Description
Technical Field
The invention belongs to the field of inorganic non-metallic materials, and particularly relates to a lead-free piezoelectric ceramic with low-field and high-field piezoelectric properties and a preparation method thereof.
Background
Piezoelectric ceramics are important functional materials for realizing the interconversion of mechanical energy and electric energy, and when voltage acts on the piezoelectric ceramics, mechanical deformation is generated along with the change of the voltage and the frequency. On the other hand, when the piezoelectric ceramic is vibrated, electric charges are generated. Using this principle, when an electric signal is applied to a vibrator formed of a piezoelectric ceramic and a metal plate, ultrasonic waves are emitted due to bending vibration. On the contrary, when ultrasonic vibration is applied, an electric signal is generated, and the piezoelectric ceramic can be used as an ultrasonic sensor. At present, piezoelectric devices have been successfully applied in a variety of technical fields such as precision positioning, precision machining, intelligent structures, bioengineering, aerospace, electronic communications, automotive industry, robotic joints, medical devices, and the like.
For piezoelectric ceramics, there are two cases of small signal and large signal in piezoelectric performance. The small signal piezoelectric property is obtained by adopting a quasi-static piezoelectric constant tester (namely, the small signal piezoelectric property is obtained by testingd 33Value), is a low field ac small signal test patternAnd the large signal piezoelectric property is to test the strain under high electric field and calculate the equivalent piezoelectric coefficientd 33 *. In general, piezoelectric ceramics are required to have piezoelectric properties of small signals and large signals separately, and it is desired that not only the piezoelectric properties of small signals be high but also the piezoelectric properties of large signals be realized by applying a high electric field as low as possible. At the same time, it is also desirable to achieve both small and large signal piezoelectric performance in one material. But the lead-free piezoelectric ceramic is difficult to realize both low-field piezoelectric performance and high-field piezoelectric performance. So far, few reports have been made on lead-free ceramic materials having both low-field and high-field piezoelectric properties and methods for preparing the same.
Disclosure of Invention
The lead-free piezoelectric ceramic provided by the invention has low-field and high-field piezoelectric properties, and the piezoelectric properties of the piezoelectric ceramic in low field and high field can be well taken into consideration, and the lead-free piezoelectric ceramic is low in production cost and good in practicability. The low-field piezoelectric constant of the piezoelectric ceramicd 33The maximum can reach more than 200pC/N, the maximum high field strain S can reach more than 0.40 percent, and the equivalent piezoelectric coefficientd 33 *The maximum can reach over 800 pm/V.
The lead-free piezoelectric ceramic provided by the invention has a chemical composition general formula as follows: (1-y)(Bi0.5Na0.5)0.94Ba0.06Ti x1-(W0.5Mg0.5) x O3-yBi2CoMnO6Whereinx、yExpressed as a mole fraction, 0.01. ltoreqx≤0.05，0.01≤y≤0.05。
The invention also provides a preparation method of the lead-free piezoelectric ceramic, which is (Bi)0.5Na0.5)TiO3、BaTiO3、Bi2CoMnO6、WO3And MgO as raw material, assisted by the current mature process. In addition, the invention also provides a preferable process flow and parameters, so that the best product performance can be obtained. The provided preferred preparation method comprises the following steps:
(1) with (Bi)0.5Na0.5)TiO3、BaTiO3、Bi2CoMnO6、WO3And MgO as raw materials, mixing according to the chemical composition general formula, ball milling with absolute ethyl alcohol as a medium, drying, and calcining at 800-;
(2) adding the obtained pre-sintering powder into pure water for granulation, and preferably controlling the water content to be 6%;
(3) directly forming the granulated powder by cold isostatic pressing, and preferably selecting the green density to be more than 57%;
(4) sintering at 1100-1200 deg.c for 2-6 hr; the preferred sintering temperature is 1150 ℃.
Detailed Description
The following specific examples are given to illustrate the technical solutions of the present invention.
Example 1:
(1) according to the chemical formula (1-y)(Bi0.5Na0.5)0.94Ba0.06Ti x1-(W0.5Mg0.5) x O3-yBi2CoMnO6Is subjected to batching, whereinx=0.01，y=0.01, the raw material is (Bi)0.5Na0.5)TiO3、BaTiO3、Bi2CoMnO6、WO3And MgO, which is ball milled for 24 hours by taking absolute ethyl alcohol as a medium, dried and presintered for 2 hours at 800 ℃ to synthesize powder.
(2) The obtained powder was granulated by adding pure water to control the water content to 6%.
(3) The granulated powder was formed by cold isostatic pressing at 150MPa, with a green density of 57%.
(4) Heating to raise the temperature at room temperature, sintering at 1000 ℃ and keeping the temperature for 2 hours.
(5) The ceramic is processed into a sheet with two smooth surfaces and the thickness of about 0.5mm, the two surfaces are fired to obtain a silver electrode, and then the low-field and high-field piezoelectric properties are tested, the high-field test voltage is 60kV/cm, and the performance test results are shown in table 1.
Example 2:
(1) according to the chemical formula (1-y)(Bi0.5Na0.5)0.94Ba0.06Ti x1-(W0.5Mg0.5) x O3-yBi2CoMnO6Is subjected to batching, whereinx=0.05，y= 0.05; the raw material is (Bi)0.5Na0.5)TiO3、BaTiO3、Bi2CoMnO6、WO3And MgO, ball milling for 24 hours by taking absolute ethyl alcohol as a medium, drying, and presintering for 2 hours at 900 ℃ to synthesize powder.
(2) The obtained powder was granulated by adding pure water to control the water content to 6%.
(3) The granulated powder was formed by cold isostatic pressing at 200MPa, with a green density of 61%.
(4) Heating to raise the temperature at room temperature, sintering at 1200 ℃ and keeping the temperature for 2 hours.
(5) The ceramic is processed into a sheet with two smooth surfaces and the thickness of about 0.5mm, the two surfaces are fired to obtain a silver electrode, and then the low-field and high-field piezoelectric properties are tested, the high-field test voltage is 60kV/cm, and the performance test results are shown in table 1.
Example 3:
(1) according to the chemical formula (1-y)(Bi0.5Na0.5)0.94Ba0.06Ti x1-(W0.5Mg0.5) x O3-yBi2CoMnO6Is subjected to batching, whereinx=0.05，y= 0.05; the raw material is (Bi)0.5Na0.5)TiO3、BaTiO3、Bi2CoMnO6、WO3And MgO, ball milling for 24 hours by taking absolute ethyl alcohol as a medium, drying, and presintering for 2 hours at 900 ℃ to synthesize powder.
(2) The obtained powder was granulated by adding pure water to control the water content to 6%.
(3) The granulated powder was formed by cold isostatic pressing at 200MPa, with a green density of 61%.
(4) Heating to raise the temperature at room temperature, sintering at 1200 ℃ and keeping the temperature for 6 hours.
(5) The ceramic is processed into a sheet with two smooth surfaces and the thickness of about 0.5mm, the two surfaces are fired to obtain a silver electrode, and then the low-field and high-field piezoelectric properties are tested, the high-field test voltage is 60kV/cm, and the performance test results are shown in table 1.
Example 4:
(1) according to the chemical formula (1-y)(Bi0.5Na0.5)0.94Ba0.06Ti x1-(W0.5Mg0.5) x O3-yBi2CoMnO6Is subjected to batching, whereinx=0.03，y=0.03, the raw material is (Bi)0.5Na0.5)TiO3、BaTiO3、Bi2CoMnO6、WO3And MgO, ball milling for 24 hours by taking absolute ethyl alcohol as a medium, drying, and presintering for 2 hours at 880 ℃ to synthesize powder.
(2) The obtained powder was granulated by adding pure water to control the water content to 6%.
(3) The granulated powder was formed by cold isostatic pressing at 200MPa, with a green density of 61%.
(4) Heating to raise the temperature at room temperature, sintering at 1150 ℃ and keeping the temperature for 4 hours.
(5) The ceramic is processed into a sheet with two smooth surfaces and the thickness of about 0.5mm, the two surfaces are fired to obtain a silver electrode, and then the low-field and high-field piezoelectric properties are tested, the high-field test voltage is 60kV/cm, and the performance test results are shown in table 1.
Example 5:
(1) according to the chemical formula (1-y)(Bi0.5Na0.5)0.94Ba0.06Ti x1-(W0.5Mg0.5) x O3-yBi2CoMnO6Is subjected to batching, whereinx=0.04，y=0.01, the raw material is (Bi)0.5Na0.5)TiO3、BaTiO3、Bi2CoMnO6、WO3And MgO, ball milling for 24 hours by taking absolute ethyl alcohol as a medium, drying, and presintering for 2 hours at 880 ℃ to synthesize powder.
(2) The obtained powder was granulated by adding pure water to control the water content to 6%.
(3) The granulated powder was formed by cold isostatic pressing at 200MPa, with a green density of 61%.
(4) Heating to raise the temperature at room temperature, sintering at 1150 ℃ and keeping the temperature for 4 hours.
(5) The ceramic is processed into a sheet with two smooth surfaces and the thickness of about 0.5mm, the two surfaces are fired to obtain a silver electrode, and then the low-field and high-field piezoelectric properties are tested, the high-field test voltage is 60kV/cm, and the performance test results are shown in table 1.
Example 6:
(1) according to the chemical formula (1-y)(Bi0.5Na0.5)0.94Ba0.06Ti x1-(W0.5Mg0.5) x O3-yBi2CoMnO6Is subjected to batching, whereinx=0.02，y=0.04, the raw material is (Bi)0.5Na0.5)TiO3、BaTiO3、Bi2CoMnO6、WO3And MgO, ball milling for 24 hours by taking absolute ethyl alcohol as a medium, drying, and presintering for 2 hours at 880 ℃ to synthesize powder.
(2) The obtained powder was granulated by adding pure water to control the water content to 6%.
(3) The granulated powder was formed by cold isostatic pressing at 200MPa, with a green density of 61%.
(4) Heating to raise the temperature at room temperature, sintering at 1150 ℃ and keeping the temperature for 4 hours.
(5) The ceramic is processed into a sheet with two smooth surfaces and the thickness of about 0.5mm, the two surfaces are fired to obtain a silver electrode, and then the low-field and high-field piezoelectric properties are tested, the high-field test voltage is 60kV/cm, and the performance test results are shown in table 1.
Table 1: low and high field piezoelectric performance of the samples of the examples
| Sample (I) | d 33 (pC/N) | S (%) | d 33 * (pm/V) |
| Example 1 | 156 | 0.24 | 351 |
| Example 2 | 187 | 0.34 | 657 |
| Example 3 | 184 | 0.36 | 662 |
| Example 4 | 67 | 0.42 | 792 |
| Example 5 | 77 | 0.40 | 833 |
| Example 6 | 235 | 0.35 | 657 |
The data of the above embodiments clearly show that the technical scheme provided by the invention can prepare the lead-free piezoelectric ceramic which can give consideration to both low-field and high-field piezoelectric properties, and well solve the problems in the prior art.
Claims (3)
1. A leadless piezoelectric ceramic with low-field and high-field piezoelectric properties is characterized in that: the general formula of the composition of the leadless piezoelectric ceramic is as follows: (1-y)(Bi0.5Na0.5)0.94Ba0.06Ti x1-(W0.5Mg0.5) x O3-yBi2CoMnO6Whereinx、yExpressed as a mole fraction, 0.01. ltoreqx≤0.05，0.01≤y≤0.05。
2. A preparation method of lead-free piezoelectric ceramics with low-field and high-field piezoelectric properties comprises the following steps:
(1) with (Bi)0.5Na0.5)TiO3、BaTiO3、Bi2CoMnO6、WO3And MgO as raw material, mixing according to the composition formula of claim 1, ball milling with absolute ethyl alcohol as medium, drying, calcining at 800-;
(2) adding pure water into the obtained pre-sintering powder for granulation, and controlling the water content to be 6%;
(3) the granulated powder is directly formed by cold isostatic pressing, and the green density is more than 57%;
(4) sintering at 1100-1200 deg.c for 2-6 hr.
3. The method of claim 2, wherein the sintering temperature of step (4) is 1150 ℃.
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