CN116986895B - Anion modified high-voltage electrical property lead-free piezoelectric ceramic and preparation method thereof - Google Patents
Anion modified high-voltage electrical property lead-free piezoelectric ceramic and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 124
- 150000001450 anions Chemical class 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 230000010287 polarization Effects 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 15
- 239000004480 active ingredient Substances 0.000 claims abstract 2
- 239000000843 powder Substances 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 31
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000000498 ball milling Methods 0.000 claims description 20
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 claims description 14
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 13
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 13
- 239000004408 titanium dioxide Substances 0.000 claims description 13
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 239000010431 corundum Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 6
- 238000007747 plating Methods 0.000 claims description 6
- -1 sulfide ions Chemical class 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
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- 230000007547 defect Effects 0.000 abstract description 13
- 238000006467 substitution reaction Methods 0.000 abstract description 10
- 229910002113 barium titanate Inorganic materials 0.000 abstract description 9
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 abstract description 9
- 230000001965 increasing effect Effects 0.000 abstract description 8
- 230000002269 spontaneous effect Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 description 12
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- 229910010293 ceramic material Inorganic materials 0.000 description 7
- 238000005245 sintering Methods 0.000 description 5
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
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- 238000000227 grinding Methods 0.000 description 4
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- 238000002441 X-ray diffraction Methods 0.000 description 3
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- 239000007858 starting material Substances 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
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- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 1
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- 229910052788 barium Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
- C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
- C04B35/4682—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
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Abstract
The application relates to the technical field of piezoelectric ceramics, and in particular discloses anion modified high-voltage electrical property lead-free piezoelectric ceramics and a preparation method thereof, wherein the lead-free piezoelectric ceramics has the chemical general formula: ba (Ba) 0.94 Sr 0.06 Ti 0.92 Sn 0.08 O x3‑0.08 S x0.08 Wherein, the content of the active ingredients is less than or equal to 0.2xAnd is less than or equal to 1. The application replaces SnO by SnS part 2 As a raw material, realize S 4‑ Substituted for O 2‑ Thereby realizing anion doping substitution. Compared with O 2‑ ，S 4‑ The chemical valence of the lead-free piezoelectric ceramic is higher, the non-equivalent anion substitution induced defect structure is favorably established, and the spontaneous polarization intensity of the defect pair is increased, so that the polarization intensity is enhanced, and the piezoelectric and dielectric properties and the piezoelectric constant of the lead-free piezoelectric ceramic are further improvedd 33 Up to 1010-1700pC/N, relative dielectric constant at room temperatureε r 6120-8830; is far higher than the piezoelectric property of barium titanate ceramics.
Description
Technical Field
The application relates to the technical field of piezoelectric ceramics, in particular to anion modified lead-free piezoelectric ceramics with high piezoelectric performance and a preparation method thereof.
Background
The piezoelectric effect includes a positive piezoelectric effect and a negative piezoelectric effect, that is, phenomena corresponding to the generation of electric charge by a crystal material under the action of force and the generation of strain by an electric field, respectively. Piezoelectric ceramics are a typical material with piezoelectric effect, and are widely concerned because of their function of interconversion of mechanical energy and electrical energy, and have been put into various fields of national security and national economy, and the global market has a demand of nearly billions of dollars each year. However, most of the piezoelectric ceramics on the market at present are lead-based piezoelectric ceramics, lead oxide in the production raw materials is toxic, the content of the lead oxide is above 60%, and the lead is a heavy metal element and has extremely high toxicity, so that serious harm is brought to the environment and human health in the large-scale production, use and discarding processes. With the demands of human beings on the strategy of ecological environment protection and social sustainable development, many countries have issued related laws to limit the use of lead elements in electronic and electrical products. The development of environmentally friendly lead-free piezoelectric materials has therefore become an urgent and significant research task.
Currently, in the study of lead-free piezoelectric ceramics, barium titanate (BaTiO 3 : BT) is widely studied by virtue of its superior performance and expected to be manufactured by adopting a conventional preparation process capable of realizing mass production, and is considered to be one of the lead-free piezoelectric ceramic systems most expected to replace lead-based piezoelectric ceramics. The phase boundary construction is reported to be a more effective means for improving the piezoelectric performance of BT-series ceramics, namely, simultaneously decreasingLow orthorhombic-tetragonal transformation temperatureT O-T And increasing the temperature of the three-way-orthogonal phase transitionT R-O To the vicinity of room temperature, a multiphase coexisting phase boundary is constructed around room temperature. The piezoelectric coefficient of the BT series ceramic prepared by the thought is improved to a certain extent, and particularly, the piezoelectric coefficient of the BT series ceramic can be greatly improved when a three-party-orthogonal-square or three-party-orthogonal-square-cubic phase boundary is constructed near room temperature.
However, compared with the high-performance lead-based piezoelectric ceramics, the piezoelectric constants of the lead-based piezoelectric ceramics still have a certain gap, so that a new method is needed to be searched for to further improve the performance of the BT-based piezoelectric ceramics.
Disclosure of Invention
The application aims to provide anion modified lead-free piezoelectric ceramic with high piezoelectric performance and a preparation method thereof, and SnS is adopted to replace SnO 2 Obtaining the lead-free piezoelectric ceramic with the ultrahigh piezoelectric constant and the piezoelectric constantd 33 Up to 1010-1700 pC/N, relative dielectric constant at room temperatureε r Can reach 6120-8330.
The application is realized by the following technical scheme:
an anionically modified high voltage electrical property lead-free piezoelectric ceramic, the chemical formula of which is:
Ba 0.94 Sr 0.06 Ti 0.92 Sn 0.08 O x3-0.08 S x0.08 wherein, the method comprises the steps of, wherein,xto replace SnO with SnS 2 Molar ratio of 0.2-0x≤1。
The high-voltage electrical property lead-free piezoelectric ceramic disclosed by the application has the advantages that Sr and Sn are doped into the barium titanate ceramic, the orthorhombic-tetragonal phase transition temperature and the orthorhombic-tetragonal phase transition temperature of the barium titanate ceramic are moved to be close to the room temperature, and the orthorhombic-tetragonal multiphase coexisting structure is constructed at the room temperature. On the basis, snS is adopted to replace SnO 2 As a raw material, the molar ratio of substitution is regulated, the defect structure induced by non-equivalent anions is substituted, and the spontaneous polarization intensity of the defect pair is increased, so that the dielectric constant of the material is improved, and the piezoelectric constant of the material is further improved.
Anion modified lead-free piezoelectric with high piezoelectric performancePreparation method of ceramic by replacing oxide with sulfide, specifically SnS for SnO 2 Realize that sulfur ions replace oxygen ions in the lead-free piezoelectric ceramic to obtain the lead-free piezoelectric ceramic with high piezoelectric performance, so that the piezoelectric constant of the prepared lead-free piezoelectric ceramic with high piezoelectric performanced 33 Up to 1010-1700 pC/N, relative dielectric constant at room temperatureε r Can reach 6120-8330.
Specifically, the present application relates to a method for manufacturing a semiconductor device; the method comprises the following steps:
s101, rolling ball milling is carried out by taking barium carbonate, strontium carbonate, titanium dioxide, tin dioxide and tin sulfide as raw materials and absolute ethyl alcohol as a ball milling medium according to mole percentage to obtain powder;
s102, drying the powder obtained in the step S101 to obtain uniformly mixed powder;
s103, presintering the powder obtained in the step S102 at 900-1200 ℃ for 1-3 hours to obtain calcined dry powder;
s104, carrying out rolling ball milling on the dry powder obtained in the step S103 by taking absolute ethyl alcohol as a ball milling medium for 4-8 hours to obtain powder, and drying the powder to obtain uniformly mixed dry powder;
s105, adding a polyvinyl alcohol aqueous solution into the dry powder obtained in the step S104, and sequentially granulating, pressing and discharging glue to obtain a ceramic blank;
and S106, burying and burning the ceramic body obtained in the step S105 for 2-6 hours at 1250-1400 ℃ to obtain the piezoelectric ceramic body.
Further; the method also comprises the following steps:
and S107, plating silver electrodes on the piezoelectric ceramic body obtained in the step S106, and applying voltage to polarize the piezoelectric ceramic body.
Specifically, the present application relates to a method for manufacturing a semiconductor device; the polarization process is as follows:
and plating a silver electrode on the piezoelectric ceramic body, and polarizing the piezoelectric ceramic body at 3-4kV/mm for 25-30 minutes in silicone oil by using a withstand voltage tester.
Further; in step S101, analytical purities of barium carbonate, strontium carbonate, titanium dioxide, tin dioxide and tin sulfide are used.
Further; in the step S101, barium carbonate, strontium carbonate, titanium dioxide, tin dioxide and tin sulfide are all in powder structures; the particle size of the barium carbonate, the strontium carbonate, the titanium dioxide, the tin dioxide and the tin sulfide is 100-700 microns.
Further, in step S101, the ball milling tank used for ball milling is a nylon tank; the adopted grinding balls are zirconium balls.
Further; and step S103, placing the powder into a corundum crucible, and presintering the corundum crucible at 900-1200 ℃ for 1-3 hours to obtain dry powder.
Further; in step S105, the mass percentage of the polyvinyl alcohol aqueous solution is 6-10 wt%.
Further; in step S105, the specific pressing process is as follows: and pressing the powder into a sheet by using an isostatic press, wherein the pressure is 100-150MPa.
Compared with the prior art, the application has the following advantages and beneficial effects:
1. the application utilizes SnS to partially replace SnO 2 As a raw material, realize S 4- Substituted for O 2- Thereby realizing anion doping substitution. Compared with O 2- ，S 4- The chemical valence of the lead-free piezoelectric ceramic is higher, the lead-free piezoelectric ceramic is favorable for establishing a defect structure induced by non-equivalent anion substitution, and the spontaneous polarization intensity of a defect pair is increased, so that the polarization intensity is enhanced, the piezoelectric and dielectric properties of the lead-free piezoelectric ceramic are further improved, and the lead-free piezoelectric ceramic has ultrahigh piezoelectric and dielectric properties and a piezoelectric constantd 33 Up to 1010-1700pC/N, relative dielectric constant at room temperatureε r 6120-8830; is far higher than the piezoelectric property of barium titanate ceramics.
2. The lead-free piezoelectric ceramic with high piezoelectric performance does not contain lead element, belongs to an environment-friendly material, accords with the sustainable development strategy in the current international social development, and has a very wide application range.
3. The preparation method of the lead-free piezoelectric ceramic with high piezoelectric performance has the advantages of simple and stable process, easy operation and convenient industrial production.
Drawings
The accompanying drawings, which are included to provide a further understanding of embodiments of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the principles of the application. In the drawings:
FIG. 1 is a schematic flow chart of a method for preparing a lead-free piezoelectric ceramic according to the present application;
FIG. 2 is an X-ray diffraction pattern of the lead-free piezoelectric ceramics according to examples 1 to 4 of the present application, wherein (a) is a normal X-ray diffraction pattern and (b) is an X-ray diffraction pattern with characteristic peaks enlarged;
FIG. 3 is a graph showing the change of dielectric constant with temperature of the leadless piezoelectric ceramics provided in example 1 of the application;
FIG. 4 is a graph showing the change of dielectric loss with temperature of the leadless piezoelectric ceramics provided in example 1 of the application;
FIG. 5 is a graph showing the change of dielectric constant with temperature of the leadless piezoelectric ceramics provided in example 2 of the application;
FIG. 6 is a graph showing the change of dielectric loss with temperature of the leadless piezoelectric ceramics provided in example 2 of the application;
FIG. 7 is a graph showing the change of the dielectric constant with temperature of the leadless piezoelectric ceramics provided in example 3 of the application;
FIG. 8 is a graph showing the change of dielectric loss with temperature of the leadless piezoelectric ceramics provided in example 3 of the application;
FIG. 9 is a graph showing the change of dielectric constant with temperature of the leadless piezoelectric ceramics provided in example 4 of the application;
fig. 10 is a graph showing the change of dielectric loss with temperature of the lead-free piezoelectric ceramic provided in example 4 of the present application.
Description of the embodiments
For the purpose of making apparent the objects, technical solutions and advantages of the present application, the present application will be further described in detail with reference to the following examples and the accompanying drawings, wherein the exemplary embodiments of the present application and the descriptions thereof are for illustrating the present application only and are not to be construed as limiting the present application.
Examples:
an anionically modified high voltage electrical property lead-free piezoelectric ceramic, the chemical formula of which is:
Ba 0.94 Sr 0.06 Ti 0.92 Sn 0.08 O x3-0.08 S x0.08 wherein, the method comprises the steps of, wherein,xto replace tin oxide SnO with tin sulfide SnS 2 Molar ratio of 0.ltoreq.0xIs less than or equal to 1, wherein,x=0 as control group.
Sr and Sn are doped in the barium titanate ceramic, and the orthorhombic-tetragonal phase transition temperature of the barium titanate ceramic are moved to be near the room temperature, so that a 'orthorhombic-tetragonal' multiphase coexisting structure near the room temperature is constructed. On the basis, S element is introduced again, a defect structure induced by non-equivalent anion substitution is established, the spontaneous polarization intensity of a defect pair is increased, the polarization intensity is enhanced, and the dielectric constant of the material is further improved, so that the ultra-high piezoelectric performance is obtained.
In the above-mentioned lead-free piezoelectric ceramic, according to the principle of equilibrium of electricity valence, the atomic proportions of the elements Ba, sr, ti, sn are respectively: 0.94, 0.06, 0.92 and 0.08. Otherwise, when the proportion is changed, the microstructure will be changed, thereby affecting the electrical property. Even when the element ratio is severely deviated, impurities and a second phase are liable to be formed during sintering, and the piezoelectric performance thereof is seriously deteriorated.
The present embodiment replaces some of SnO with SnS 2 As a raw material, realize S 4- Substituted for O 2- Thereby realizing anion doping and obtaining the lead-free piezoelectric ceramic. Compared with O 2- ，S 4- The chemical valence of the ceramic is higher, which is favorable for establishing a defect structure induced by non-equivalent anion substitution, increasing the spontaneous polarization intensity of defect pairs, enhancing the polarization intensity of the defect pairs, and leading the piezoelectric ceramic to have ultrahigh piezoelectric and dielectric properties and piezoelectric constantsd 33 Up to 1010-1700pC/N, relative dielectric constant at room temperatureε r 6120-8830; is far higher than the piezoelectric property of barium titanate ceramics.
As shown in figure 1, the preparation method of the anion modified high-voltage electrical property lead-free piezoelectric ceramic utilizes sulfide to replace oxide, and specifically utilizes tin sulfide SnS to replace tin oxide SnO 2 Realize that sulfur ions replace oxygen ions in the piezoelectric ceramic to obtain lead-free piezoelectric ceramicPiezoelectric constant of the leadless piezoelectric ceramicsd 33 1010-1700pC/N, relative dielectric constant at room temperatureε r 6120-8830.
The method specifically comprises the following steps:
s101, according to mole percent, using barium carbonate BaCO 3 Strontium carbonate SrCO 3 Titanium dioxide TiO 2 Tin dioxide SnO 2 And tin sulfide SnS is used as a raw material, absolute ethyl alcohol is used as a ball milling medium for rolling ball milling to obtain powder; the barium carbonate, the strontium carbonate, the titanium dioxide, the tin dioxide and the tin sulfide are all analytically pure; barium carbonate, strontium carbonate, titanium dioxide, tin dioxide and tin sulfide are all in powder structures; the particle size of the barium carbonate, the strontium carbonate, the titanium dioxide, the tin dioxide and the tin sulfide is 100-700 microns.
Specifically, the raw materials and absolute ethyl alcohol are subjected to rolling ball milling in a ball milling tank, wherein the ball milling tank is a nylon tank, and grinding balls in the nylon tank are zirconium balls.
S102, drying the powder obtained in the step S101 to obtain uniformly mixed powder;
s103, presintering the powder obtained in the step S102 at 900-1200 ℃ for 1-3 hours to obtain calcined dry powder; specifically, the powder is placed into a corundum crucible, and the corundum crucible is presintered for 1-3 hours at 900-1200 ℃ to obtain calcined dry powder.
S104, carrying out rolling ball milling on the dry powder obtained in the step S103 by taking absolute ethyl alcohol as a ball milling medium for 4-8 hours to obtain powder, and drying the powder to obtain uniformly mixed calcined dry powder;
s105, adding a polyvinyl alcohol aqueous solution into the dry powder obtained in the step S104, and sequentially granulating, pressing and discharging glue to obtain a ceramic blank;
further specifically, 6-10wt% of polyvinyl alcohol aqueous solution is added into the dry powder to be granulated sequentially to obtain powder. The powder is pressed into a sheet shape by an isostatic press, and the shape of the powder can be a round sheet shape or other sheet shapes; the pressure of the dynamic tablet press is 100-150 MPa; the powder is placed in a grinding tool with a cavity during pressing.
In the application, the content of the polyvinyl alcohol aqueous solution is preferably 6wt% to 10wt%. If the added polyvinyl alcohol aqueous solution is less than 6wt%, the sample is easy to be non-formed, the piezoelectric ceramic material cannot be obtained, and if the added polyvinyl alcohol aqueous solution is more than wt%, the sample is easy to have more holes after glue discharge, so that the density of the ceramic is reduced, and the piezoelectric performance of the ceramic is reduced.
And S106, burying and burning the ceramic body obtained in the step S105 for 2-6 hours at 1250-1400 ℃ to obtain the piezoelectric ceramic body.
And S107, plating silver electrodes on the piezoelectric ceramic body obtained in the step S106, and applying voltage to polarize the piezoelectric ceramic body.
Specifically, the piezoelectric ceramic body is plated with a silver electrode, and then the ceramic sheet is polarized for 25-30 minutes at 3-4kV/mm by using a withstand voltage tester, and specifically can be polarized for 30 minutes at 2 kV/mm.
The preparation method of the leadless piezoelectric ceramics provided by the embodiment can obviously improve the piezoelectric constant and the dielectric constant of the leadless piezoelectric ceramics provided by the embodiment, so that the leadless piezoelectric ceramics of the application has wide application range. In addition, the lead-free piezoelectric ceramic of the embodiment of the application does not contain toxic heavy metal element lead, belongs to an environment-friendly material, accords with the sustainable development strategy in the current international society development, and is beneficial to environmental protection.
In order to better understand the technical scheme provided by the application, the following specific processes for preparing the leadless piezoelectric ceramics by applying the preparation method provided by the embodiment of the application and the performances thereof are respectively described in a plurality of specific examples.
Example 1:
selected from the general formulaxThe chemical formula of the piezoelectric ceramic material obtained in the embodiment is =0: ba (Ba) 0.94 Sr 0.06 Ti 0.92 Sn 0.08 O 3 The method for preparing the piezoelectric ceramic comprises the following steps:
to analytically pure barium carbonate BaCO 3 Strontium carbonate SrCO 3 Titanium dioxide TiO 2 Tin dioxide SnO 2 The method comprises the steps of taking the raw materials as raw materials, accurately weighing the raw materials according to mole percentage, adding absolute ethyl alcohol as a ball milling medium, rolling and ball milling for 24 hours, and taking out and bakingDrying to obtain uniformly mixed powder; the obtained powder is kept at 1200 ℃ for 2 hours to obtain calcined dry powder, then the obtained dry powder is ball-milled for 4-8 hours by taking absolute ethyl alcohol as a ball milling medium to obtain powder, and the powder is dried to obtain dry powder; then adding 8wt% concentration polyvinyl alcohol water solution into the obtained dry powder for granulation; after granulation, the mixture is preliminarily molded under 10MPa by using a grinding tool with the diameter of 10mm, and then is further molded under 150MPa by using an isostatic press, so that small discs with the diameter of 10mm and the thickness of 1mm are formed, and glue is arranged. Then preserving the temperature of the small wafer subjected to glue discharge at 1400 ℃ for 3 hours for sintering to obtain a piezoelectric ceramic body (ceramic wafer); finally, plating silver electrodes on the surface of the sintered ceramic sheet, and polarizing the ceramic sheet for 30 minutes under the voltage of 2kV in a silicone oil bath. The ceramic sheet after polarization was left in air and allowed to stand for 24 hours, and electrical properties were tested using the IEEE standard.
Example 2:
selected from the general formulaxThe chemical formula of the lead-free piezoelectric ceramic material obtained in the embodiment is shown as follows: ba (Ba) 0.94 Sr 0.06 Ti 0.9 2 Sn 0.08 O 2.984 S 0.016 . The method of preparing the ceramic of this example is similar to the preparation method of example 1, except that the raw material species are augmented with analytically pure SnS; the molar ratios of the starting materials were calculated, weighed and prepared according to the chemical formula in example 2.
The preparation method of this example also differs from that of example 1 in that:
the pre-firing conditions of example 2 were 1100℃for 3 hours and the sintering conditions were 1350℃for 2 hours.
Example 3:
selected from the general formulaxThe chemical formula of the piezoelectric ceramic material obtained in the embodiment is =0.6: ba (Ba) 0.94 Sr 0.06 Ti 0.92 Sn 0.08 O 2.964 S 0.036 . The method of preparing the ceramic of this example is similar to the preparation method of example 1, except that the raw material species are augmented with analytically pure SnS; the molar ratios of the starting materials were calculated, weighed and prepared according to the chemical formula in example 3.
The preparation method of this example also differs from that of example 1 in that:
the pre-firing conditions of example 3 were 1000℃for 2 hours and the sintering conditions 1300℃for 4 hours.
Example 4:
selected from the general formulaxThe chemical formula of the piezoelectric ceramic material obtained in the embodiment is =1.0: ba (Ba) 0.94 Sr 0.06 Ti 0.92 Sn 0.08 O 2.92 S 0.08 . The method of preparing the ceramic of this example is similar to that of example 1, except that the feedstock species are augmented with analytically pure SnS ； The molar ratios of the starting materials were calculated, weighed and prepared according to the chemical formula in example 4.
The preparation method of this example also differs from that of example 1 in that:
the pre-firing conditions of example 4 were 900℃for 1 hour and the sintering conditions were 1250℃for 6 hours.
Fig. 2 is a powder X-ray diffraction pattern of the lead-free piezoelectric ceramics provided in examples 1 to 4 of the present application.
As shown in fig. 2 (a), 7 strong characteristic peaks appear between 20 and 70 °, and as the diffraction angle increases, the following steps are sequentially performed: [100]、[110]、[111]、[002]、[210]、[211]This ceramic is shown to be a typical perovskite structure. As shown in FIG. 2 (b), a significant peak separation occurred in the range of 45 to 46℃as respectively [002 ]]And [200 ]]A peak. And the two peaks are fused, and the peak intensity ratio is more than 1:2 and less than 2:1. And in ceramicsxThe content is 0-1.0, and the XRD spectrum is not obviously changed, which indicates that the ceramics have multiphase coexisting structures.
FIGS. 3, 5, 7 and 9 are schematic diagrams showing the change of dielectric constant with temperature at 1kHz,10kHz and 100kHz of the leadless piezoelectric ceramics provided in examples 1 to 4 of the application, respectively.
FIGS. 3, 5, 7 and 9 show examples 1 to 4 in which SnS is substituted for SnO 2 The dielectric constants at 0, 0.2, 0.6 and 1.0 vary with temperature. From the curve, it can be found that the ceramic provided by each embodiment is between-60 and 60%The dielectric peaks are 3 at 120 ℃ and correspond to three-orthogonal, orthogonal-tetragonal and tetragonal-cubic phase changes respectively along with the temperature rise. And along withxThe phase transition temperature is gradually moved to the high temperature direction when the temperature is increased, but the phase structure of the material is not changed near the room temperature, which indicates that the phase structure is not changed due to anion doping. And the three-party-orthogonal and the orthogonal-tetragonal are both positioned near the room temperature, and the combination of XRD can prove that the ceramic materials are all in multi-phase coexistence of 'three-party-orthogonal-tetragonal' at the room temperature. When the temperature is higher than 45-50 ℃, the ceramic presents a cubic phase, does not have ferroelectricity any more, the piezoelectric performance disappears, and the dielectric performance is seriously deteriorated. By contrast, it was found that the anionic doping can sharpen the dielectric anomalous peak, reduce the dispersion, increase the dielectric constant, indicating an increase in the polarization of the material.
Fig. 4, 6, 8 and 10 are schematic diagrams showing the dielectric loss with temperature of the leadless piezoelectric ceramics provided in examples 1 to 4 of the application, respectively, under 1kHz,10kHz,100 kHz.
FIGS. 4, 6, 8 and 10 show the substitution of SnS for SnO in the piezoelectric ceramic material 2 The dielectric loss at 0, 0.2, 0.6 and 1.0 with temperature. From the curve, it can be found that the ceramic provided by each embodiment has 3 abnormal peaks of dielectric loss at-60-120 ℃, and the abnormal peaks also correspond to three-party-orthogonal, orthogonal-tetragonal and tetragonal-cubic phase changes along with the temperature rise. And along withxThe increase, the slow shift of the abnormal loss peak to the high temperature direction, but the phase structure of the material near room temperature is not changed, which indicates that the anion doping does not cause the phase structure change. By contrast, it can be found that the anionic doping can sharpen the loss anomaly peak and enhance the polarity of the material.
The present application also tested the electrical properties of the lead-free piezoelectric ceramics of examples 1 to 4 described above, and the results obtained are shown in table 1.
TABLE 1
As can be seen from the data in table 1:
this example replaces SnO with SnS 2 As a raw material, realize S 4- Substituted for O 2- Thereby realizing anion doping substitution. Compared with O 2- ，S 4- The chemical valence of the lead-free piezoelectric ceramic is higher, the lead-free piezoelectric ceramic is favorable for establishing a defect structure induced by non-equivalent anion substitution, and the spontaneous polarization intensity of a defect pair is increased, so that the polarization intensity is enhanced, the piezoelectric and dielectric properties of the lead-free piezoelectric ceramic are further improved, and the lead-free piezoelectric ceramic has ultrahigh piezoelectric and dielectric properties and a piezoelectric constantd 33 Up to 1010-1700pC/N, relative dielectric constant at room temperatureε r 6120-8830; is far higher than the piezoelectric property of barium titanate ceramics.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the application, and is not meant to limit the scope of the application, but to limit the application to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the application are intended to be included within the scope of the application.
Claims (10)
1. The anion modified high-voltage electrical property lead-free piezoelectric ceramic is characterized by having a chemical general formula:
Ba 0.94 Sr 0.06 Ti 0.92 Sn 0.08 O x3-0.08 S x0.08 wherein, the content of the active ingredients is less than or equal to 0.2x≤1。
2. The method for preparing the anion modified lead-free piezoelectric ceramic with high piezoelectric performance according to claim 1, wherein sulfide is used for replacing oxide, and sulfide ions in the lead-free piezoelectric ceramic are used for replacing oxygen ions, so that the lead-free piezoelectric ceramic with high piezoelectric performance is obtained.
3. The method for preparing the anion modified lead-free piezoelectric ceramic with high piezoelectric property according to claim 2, which is characterized by comprising the following steps:
s101, rolling ball milling is carried out by taking barium carbonate, strontium carbonate, titanium dioxide, tin dioxide and tin sulfide as raw materials and absolute ethyl alcohol as a ball milling medium according to mole percentage to obtain powder;
s102, drying the powder obtained in the step S101 to obtain uniformly mixed powder;
s103, presintering the powder obtained in the step S102 at 900-1200 ℃ for 1-3 hours to obtain calcined dry powder;
s104, carrying out rolling ball milling on the dry powder obtained in the step S103 by taking absolute ethyl alcohol as a ball milling medium for 4-8 hours to obtain powder, and drying the powder to obtain uniformly mixed dry powder;
s105, adding a polyvinyl alcohol aqueous solution into the dry powder obtained in the step S104, and sequentially granulating, pressing and discharging glue to obtain a ceramic blank;
and S106, burying and burning the ceramic body obtained in the step S105 for 2-6 hours at 1250-1400 ℃ to obtain the piezoelectric ceramic body.
4. The method for preparing the anionically modified lead-free piezoelectric ceramic with high piezoelectric properties according to claim 3, further comprising the steps of:
and S107, plating silver electrodes on the piezoelectric ceramic body obtained in the step S106, and applying voltage to polarize the piezoelectric ceramic body.
5. The method for preparing the anion modified lead-free piezoelectric ceramic with high piezoelectric property according to claim 4, wherein the polarization process is as follows:
and plating a silver electrode on the piezoelectric ceramic body, and polarizing the piezoelectric ceramic body at 3-4kV/mm for 25-30 minutes in silicone oil by using a withstand voltage tester.
6. The method for preparing an anionically modified, high voltage, lead-free piezoelectric ceramic according to claim 3, wherein in step S101, the barium carbonate, strontium carbonate, titanium dioxide, tin dioxide and tin sulfide are all analytically pure.
7. The method for preparing the anionically modified lead-free piezoelectric ceramic with high piezoelectric properties according to claim 3, wherein in step S101, barium carbonate, strontium carbonate, titanium dioxide, tin dioxide and tin sulfide are all in powder structures; the particle size of the barium carbonate, the strontium carbonate, the titanium dioxide, the tin dioxide and the tin sulfide is 100-700 microns.
8. The method for preparing the anion modified lead-free piezoelectric ceramic with high piezoelectric property according to claim 3, wherein in the step S103, the powder is put into a corundum crucible, and the corundum crucible is presintered for 1-3 hours at 900-1200 ℃ to obtain dry powder.
9. The method for preparing the anion modified lead-free piezoelectric ceramic with high piezoelectric performance according to claim 3, wherein in the step S105, the mass percentage of the polyvinyl alcohol aqueous solution is 6-10 wt%.
10. The method for preparing the anion modified lead-free piezoelectric ceramic with high piezoelectric property according to claim 3, wherein in the step S105, the specific pressing process is as follows: and pressing the powder into a sheet by using an isostatic press, wherein the pressure is 100-150MPa.
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