CN116573936A - Anion modified piezoelectric ceramic and preparation method thereof - Google Patents
Anion modified piezoelectric ceramic and preparation method thereof Download PDFInfo
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- CN116573936A CN116573936A CN202310850114.4A CN202310850114A CN116573936A CN 116573936 A CN116573936 A CN 116573936A CN 202310850114 A CN202310850114 A CN 202310850114A CN 116573936 A CN116573936 A CN 116573936A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 90
- 150000001450 anions Chemical class 0.000 title abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 16
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims description 33
- 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 15
- 238000005245 sintering Methods 0.000 claims description 14
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 13
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-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
- 229910001928 zirconium oxide Inorganic materials 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
- 239000010936 titanium Substances 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 8
- 239000010431 corundum Substances 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229920001778 nylon Polymers 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000007747 plating Methods 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical class O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 6
- 229910002113 barium titanate Inorganic materials 0.000 abstract description 6
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 5
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 229910010293 ceramic material Inorganic materials 0.000 description 42
- 230000008859 change Effects 0.000 description 15
- 238000010586 diagram Methods 0.000 description 14
- 238000011161 development Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000007704 transition Effects 0.000 description 6
- 241000894007 species Species 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- -1 fluoride ions Chemical class 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/49—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 zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates
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Abstract
The application relates to the technical field of piezoelectric ceramics, and particularly discloses anion modified piezoelectric ceramics and a preparation method thereof, wherein the chemical general formula of the piezoelectric ceramics is as follows: ba (Ba) 0.86 Sr 0.14 Ti 0.92 Zr 0.08 O x3‑0.16 F x0.32 Wherein, the method comprises the steps of, wherein,xfor use with zirconium fluoride ZrF 4 Substituted zirconia ZrO 2 Molar ratio of 0.2-0xAnd is less than or equal to 1. The application utilizes ZrF 4 Substituted part ZrO 2 As a raw material, realize F ‑ Substituted for O 2‑ Thereby realizing anion doping. Compared with O 2‑ ，F ‑ Has lower chemical valence and stronger electronegativity, is favorable for forming lattice defects, and increases the strength of chemical bonds, thereby enhancing the ferroelectric polarity, further improving the piezoelectric and dielectric properties of the piezoelectric ceramics and leading the piezoelectric ceramics to be pressedThe electroceramics have ultrahigh piezoelectric and dielectric properties and piezoelectric constantsd 33 Up to 950-1245pC/N, relative dielectric constant at room temperatureε r Up to 3201-3786; 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 piezoelectric ceramics and a preparation method thereof.
Background
The piezoelectric effect is a physical effect of the interconversion between charge forces and was found in quartz crystals in 1880 by curie brothers. The piezoelectric effect includes a positive piezoelectric effect and a negative piezoelectric effect, that is, under the action of an external force, the piezoelectric body generates dielectric polarization proportional to stress, positive and negative charges appear at both ends, and after the external force is removed, the piezoelectric body returns to an uncharged state, which is called a positive piezoelectric effect; when an electric field is applied to the crystal, deformation or stress proportional to the applied electric field is generated, and when the electric field is removed, the deformation disappears, which is called an inverse piezoelectric effect. Materials having a piezoelectric effect are called piezoelectric materials, mainly organic and inorganic piezoelectric materials. Among the inorganic piezoelectric materials, perovskite-type piezoelectric ceramics have been widely studied and used.
Since Jaffe et al reported for the first time in lead zirconate titanate (PZT) in 1954, lead-based piezoceramics have dominated commercial applications for their excellent piezoelectric properties and good temperature stability. However, lead-based piezoelectric ceramics contain a large amount of lead (Pb) element, and cause serious loss to the environment and human body. Therefore, the development of lead-free piezoelectric ceramics is an urgent task in the current research, and the development of lead-free piezoelectric ceramic materials with high performance has great significance for sustainable development of human society.
The development of piezoelectric ceramics not only needs to consider leadless, but also needs to consider obtaining high-performance leadless piezoelectric ceramics, i.e. the prepared leadless piezoelectric ceramics needs to have higher piezoelectric constantd 33 And relative dielectric constantε r 。
Disclosure of Invention
The application aims to provide anion modified piezoelectric ceramic and a preparation method thereof, and ZrF is adopted 4 Substituted for ZrO 2 Obtaining lead-free piezoelectric ceramic with ultrahigh piezoelectric constant and piezoelectric constantd 33 Up to 950-1245pC/N, relative dielectric constant at room temperatureε r Up to 3201-3786.
The application is realized by the following technical scheme:
an anionically modified piezoelectric ceramic having the chemical formula:
Ba 0.86 Sr 0.14 Ti 0.92 Zr 0.08 O x3-0.16 F x0.32 wherein, the method comprises the steps of, wherein,xfor use with zirconium fluoride ZrF 4 Substituted zirconia ZrO 2 Molar ratio of 0.2-0xAnd is less than or equal to 1. According to the piezoelectric ceramic, sr and Zr are doped in the barium titanate ceramic, the orthorhombic-tetragonal phase transition temperature and the orthorhombic-tetragonal phase transition temperature of the barium titanate ceramic are adjusted to be close to the room temperature, and the orthorhombic-tetragonal multiphase coexisting junction at the room temperature is constructed. On the basis of ZrF 4 Substituted for ZrO 2 As raw material, and adjusting the molar ratio of substitution, an anion defect structure is established, and chemical bonds are enhanced, so that the ferroelectric polarity of the material is improved.
A preparation method of anion modified piezoelectric ceramic, fluoride is utilized to replace oxide, so that fluoride ions in the piezoelectric ceramic are utilized to replace oxygen, and lead-free piezoelectric ceramic is obtained, and the piezoelectric constant of the lead-free piezoelectric ceramic is obtainedd 33 950-1245pC/N, relative dielectric constant at room temperatureε r 3201 to 3786.
Further, the method comprises the following steps:
s101, rolling and ball milling by taking barium carbonate, strontium carbonate, titanium dioxide, zirconium oxide and zirconium fluoride as raw materials and absolute ethyl alcohol as a ball milling medium according to mole percent 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 700-1200 ℃ for 2-3 hours to obtain dry powder;
s104, adding a polyvinyl alcohol aqueous solution into the dry powder obtained in the step S103, and sequentially granulating, pressing and discharging glue to obtain a ceramic blank;
and S105, sintering the ceramic body obtained in the step S104 at 1400-1450 ℃ for 3-5 hours to obtain the piezoelectric ceramic body.
Further, the method also comprises the following steps:
and S106, plating silver electrodes on the piezoelectric ceramic body obtained in the step S105, and applying voltage to polarize the piezoelectric ceramic body.
Further, in step S101, all of barium carbonate, strontium carbonate, titanium dioxide, zirconium oxide, and zirconium fluoride are analytically pure.
Further, in step S101, barium carbonate, strontium carbonate, titanium dioxide, zirconium oxide and zirconium fluoride are all in a powdery structure.
Further, the particle size of the barium carbonate, the strontium carbonate, the titanium dioxide, the zirconium oxide and the zirconium fluoride is 100-800 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, in step S103, the powder is placed into a corundum crucible, and the corundum crucible is presintered for 2-3 hours at 700-1200 ℃ to obtain dry powder.
Further, in step S104, the mass percentage of the polyvinyl alcohol aqueous solution is 6wt% to 8wt%.
Further, in step S104, the specific pressing process is as follows: pressing the powder into a sheet shape by using an isostatic press; the pressure of the isostatic press was 250MPa.
Compared with the prior art, the application has the following advantages and beneficial effects:
1. the application utilizes ZrF 4 Substituted part ZrO 2 As a raw material, realize F - Substituted for O 2- Thereby realizing anion doping. Compared with O 2- ，F - The chemical valence is lower, the electronegativity is stronger, the formation of lattice defects is facilitated, and the strength of chemical bonds is increased, so that the ferroelectric polarity is enhanced, the piezoelectric and dielectric properties of the piezoelectric ceramic are further improved, and the piezoelectric ceramic has ultrahigh piezoelectric and dielectric properties and piezoelectric constantsd 33 Up to 950-1245pC/N, relative dielectric constant at room temperatureε r Up to 3201-3786; is far higher than the piezoelectric property of barium titanate ceramics.
2. The piezoelectric ceramic material does not contain lead element, belongs to an environment-friendly material, accords with the sustainable development strategy in the previous international social development, and has a very wide application range.
3. The preparation method of the piezoelectric ceramic material has simple and stable process, is easy to operate and is convenient for 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 piezoelectric ceramic according to the present application;
FIG. 2 is an X-ray diffraction pattern of the piezoelectric ceramic material according to examples 1 to 6 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 schematic diagram showing the change of dielectric constant with temperature within the range of-120-200 ℃ for the piezoelectric ceramic material provided in embodiment 1 of the present application;
FIG. 4 is a schematic diagram showing the change of dielectric constant with temperature at 15-35 ℃ for the piezoelectric ceramic material according to embodiment 1 of the present application;
FIG. 5 is a schematic diagram showing the change of dielectric constant with temperature at 35-50deg.C of the piezoelectric ceramic material according to embodiment 1 of the present application;
FIG. 6 is a schematic diagram showing the change of dielectric constant with temperature in the range of-120-200 ℃ for the piezoelectric ceramic material provided in embodiment 2 of the present application;
FIG. 7 is a schematic diagram showing the change of dielectric constant with temperature at 15-35 ℃ for the piezoelectric ceramic material according to embodiment 2 of the present application;
FIG. 8 is a schematic diagram showing the change of dielectric constant with temperature at 35-50deg.C of the piezoelectric ceramic material according to embodiment 2 of the present application;
FIG. 9 is a schematic diagram showing the change of dielectric constant with temperature in the range of-120-200 ℃ for the piezoelectric ceramic material provided in embodiment 3 of the present application;
FIG. 10 is a schematic diagram showing the change of dielectric constant with temperature at 15-35 ℃ for the piezoelectric ceramic material according to embodiment 3 of the present application;
FIG. 11 is a schematic diagram showing the change of dielectric constant with temperature at 35-50deg.C of the piezoelectric ceramic material according to embodiment 3 of the present application;
FIG. 12 is a schematic diagram showing the change of dielectric constant with temperature in the range of-120-200deg.C for the piezoelectric ceramic material provided in example 4 of the present application;
FIG. 13 is a schematic diagram showing the change of dielectric constant with temperature at 15-35 ℃ for the piezoelectric ceramic material according to example 4 of the present application;
FIG. 14 is a schematic diagram showing the change of dielectric constant with temperature at 35-50deg.C for the piezoelectric ceramic material according to example 4 of the present application;
FIG. 15 is a graph showing the dielectric constant of the piezoelectric ceramic material according to embodiment 5 of the present application at-120-200deg.C with temperature;
FIG. 16 is a graph showing the dielectric constant of the piezoelectric ceramic material according to embodiment 5 of the present application at 15-35 ℃ with temperature;
FIG. 17 is a schematic diagram showing the change of dielectric constant with temperature at 35-50deg.C for the piezoelectric ceramic material according to example 5 of the present application;
FIG. 18 is a graph showing the dielectric constant of the piezoelectric ceramic material according to embodiment 6 of the present application at-120 to 200 ℃ with temperature;
FIG. 19 is a graph showing the dielectric constant of the piezoelectric ceramic material according to embodiment 6 of the present application over a temperature range of 15-35 ℃ with temperature;
FIG. 20 is a graph showing the change of dielectric constant with temperature at 35-50deg.C for the piezoelectric ceramic material according to example 6 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 piezoelectric ceramic having the chemical formula:
Ba 0.86 Sr 0.14 Ti 0.92 Zr 0.08 O x3-0.16 F x0.32 wherein, the method comprises the steps of, wherein,xfor use with zirconium fluoride ZrF 4 Substituted zirconia ZrO 2 Molar ratio of 0.ltoreq.0xIs less than or equal to 1, wherein,x=0 as control group.
The BaTiO is preferred to be prepared by using Sr and Zr elements 3 Ceramic modification to make fired Ba 0.86 Sr 0.14 Ti 0.92 Zr 0.08 O 3 The ceramic presents a three-party-orthogonal-tetragonal multiphase coexisting structure near room temperature, and on the basis, F element is introduced again to construct an anion defect structure and strengthen the polarity, so that the ultra-high piezoelectric performance is obtained. The piezoelectric property and dielectric property of the piezoelectric ceramic are far higher than those of barium titanate ceramics.
In the piezoelectric ceramic, according to the principle of equilibrium of electricity valence, the atomic ratios of the elements Ba, sr, ti, zr are respectively: 0.86, 0.14, 0.92, and 0.08. Otherwise, when the proportion is changed, the phase structure is changed, so that the electrical property is affected. Even when the proportion is severely deviated, excessive elements tend to form impurities during sintering, resulting in a decrease in piezoelectric properties.
The present embodiment utilizes ZrF 4 Substituted part ZrO 2 As a raw material, realize F - Substitution ofO 2- Thereby realizing anion doping and obtaining the lead-free piezoelectric ceramic. Compared with O 2- ，F - The chemical valence is lower, the electronegativity is stronger, the formation of lattice defects is facilitated, and the strength of chemical bonds is increased, so that the ferroelectric polarity is enhanced, the piezoelectric and dielectric properties of the piezoelectric ceramic are further improved, and the piezoelectric ceramic has ultrahigh piezoelectric and dielectric properties and piezoelectric constantsd 33 Up to 950-1245pC/N, relative dielectric constant at room temperatureε r Up to 3201-3786; is far higher than the piezoelectric property of barium titanate ceramics.
As shown in figure 1, a preparation method of anion modified piezoelectric ceramic utilizes fluoride to replace oxide to realize that fluoride ions replace oxygen in piezoelectric ceramic to obtain lead-free piezoelectric ceramic, and the piezoelectric constant of the lead-free piezoelectric ceramic is equal to that of the lead-free piezoelectric ceramicd 33 950-1245pC/N, relative dielectric constant at room temperatureε r 3201 to 3786.
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 Zirconium oxide ZrO 2 And zirconium fluoride is used as a raw material, absolute ethyl alcohol is used as a ball milling medium for rolling ball milling to obtain powder; barium carbonate, strontium carbonate, titanium dioxide, zirconium oxide and zirconium fluoride ZrF 4 All adopt analytical purity; barium carbonate, strontium carbonate, titanium dioxide, zirconium oxide and zirconium fluoride are all in powder structures; the particle size of the barium carbonate, the strontium carbonate, the titanium dioxide, the zirconium oxide and the zirconium fluoride is 100-800 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 700-1200 ℃ for 2-3 hours to obtain dry powder; specifically, the powder is placed into a corundum crucible, and the corundum crucible is presintered for 2-3 hours at 700-1200 ℃ to obtain dry powder.
S104, adding a polyvinyl alcohol aqueous solution into the dry powder obtained in the step S103, and sequentially granulating, pressing and discharging glue to obtain a ceramic blank.
Further specifically, 6-8wt% 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 250MPa; 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 8wt%. If the added aqueous solution of polyvinyl alcohol is less than 6wt%, the sample is liable to be non-formed, and the piezoelectric ceramic material cannot be obtained, and if it is more than 8wt%, the piezoelectric property is liable to be lowered or the sample has voids, resulting in the failure to obtain a dense piezoelectric ceramic material.
And S105, sintering the ceramic body obtained in the step S104 at 1400-1450 ℃ for 3-5 hours to obtain the piezoelectric ceramic body.
And S106, plating silver electrodes on the piezoelectric ceramic body obtained in the step S105, and applying voltage to polarize the piezoelectric ceramic body.
Specifically, the piezoelectric ceramic body is coated with silver electrodes, and then the ceramic sheet is polarized for 10-20 minutes under the condition of 2-3 kV/cm by using a withstand voltage tester.
The preparation method of the piezoelectric ceramic provided by the embodiment can obviously improve the piezoelectric constant and the dielectric constant of the piezoelectric ceramic material provided by the embodiment, so that the piezoelectric ceramic material provided by the application has a wide application range. In addition, the piezoelectric ceramic material of the embodiment of the application does not contain lead element, belongs to an environment-friendly material, accords with the sustainable development strategy in the current international social development, and is beneficial to environmental protection.
The preparation method of the piezoelectric ceramic material provided by the embodiment of the application has the advantages of simple and stable process, easiness in operation and convenience in industrial production.
In order to better understand the technical scheme provided by the application, the following specific processes for preparing the piezoelectric ceramic material and the performances thereof by applying the preparation method provided by the embodiment of the application 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) 0.86 Sr 0.14 Ti 0.92 Zr 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 Zirconium oxide ZrO 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, taking out and drying to obtain mixed dry powder; the obtained dry powder is kept at 1200 ℃ for 2 hours, and then polyvinyl alcohol water solution with the concentration of 8 weight percent is added into the presintered 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 250MPa 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. Sintering the small discs subjected to glue discharging at different temperatures and different heat preservation times to obtain ceramic sheets; finally, the surface of the sintered ceramic sheet is coated with a silver electrode and polarized for 20 minutes under the voltage of 3kV in a silicone oil bath. The ceramic sheet after polarization was left to stand in air for 24 hours, and electrical properties were tested using the IEEE standard.
Example 2:
selected from the general formulaxThe chemical formula of the piezoelectric ceramic material obtained in the embodiment is =0.2: ba (Ba) 0.86 Sr 0.14 Ti 0.92 Zr 0.08 O 2.968 F 0.064 . The method of preparing the ceramic of example 2 of the present application is similar to that of example 1, except that the raw material species is increased in analytically pure ZrF 4 The method comprises the steps of carrying out a first treatment on the surface of the The molar ratios of the starting materials were calculated, weighed and prepared according to the chemical formula in example 2.
Example 3:
selected from the general formulaxThe chemical formula of the piezoelectric ceramic material obtained in the embodiment is =0.4: ba (Ba) 0.86 Sr 0.14 Ti 0.92 Zr 0.08 O 2.936 F 0.128 . The method for preparing the ceramic of example 3 of the present application is similar to that of example 1, except thatIn that the raw material species is increased with analytically pure ZrF 4 The method comprises the steps of carrying out a first treatment on the surface of the The molar ratios of the starting materials were calculated, weighed and prepared according to the chemical formula in example 3.
Example 4:
selected from the general formulaxThe chemical formula of the piezoelectric ceramic material obtained in the embodiment is =0.6: ba (Ba) 0.86 Sr 0.14 Ti 0.92 Zr 0.08 O 2.904 F 0.192 . The method of preparing the ceramic of example 4 of the present application is similar to that of example 1, except that the raw material species is increased in analytically pure ZrF 4； The molar ratios of the starting materials were calculated, weighed and prepared according to the chemical formula in example 4.
Example 5:
selected from the general formulaxThe chemical formula of the piezoelectric ceramic material obtained in the embodiment is =0.8: ba (Ba) 0.86 Sr 0.14 Ti 0.92 Zr 0.08 O 2.872 F 0.256 . The method of preparing the ceramic of example 5 of the present application is similar to that of example 1, except that the raw material species is increased in analytically pure ZrF 4 The method comprises the steps of carrying out a first treatment on the surface of the The molar ratios of the starting materials were calculated, weighed and prepared according to the chemical formula in example 5.
Example 6:
selected from the general formulaxThe chemical formula of the piezoelectric ceramic material obtained in the embodiment is given by =1: ba (Ba) 0.86 Sr 0.14 Ti 0.92 Zr 0.0 8 O 2.84 F 0.32 . The method of preparing the ceramic of example 6 of the present application is similar to that of example 1, except that the raw material species is increased in analytically pure ZrF 4 : the molar ratios of the starting materials were calculated, weighed and prepared according to the chemical formula in example 6.
It should also be noted that examples 2-6 differ in burn-in and sintering conditions: the presintering condition of example 1 was 1200 ℃ for 2 hours, and the sintering condition was 1420 ℃ for 3 hours; the presintering condition of example 2 is 1100 ℃ for 2 hours, and the sintering condition is 1430 ℃ for 3 hours; the presintering condition of example 3 was 950℃for 2 hours and the sintering condition was 1430℃for 3 hours; the pre-sintering condition of example 4 was 800℃for 3 hours and the sintering condition was 1435℃for 3 hours; the presintering condition of example 5 was 700℃for 2 hours, and the sintering condition was 1425℃for 5 hours; the pre-sintering condition of example 6 was 700℃for 2 hours and the sintering condition was 1400℃for 5 hours.
FIG. 2 is a powder X-ray diffraction pattern of the piezoelectric ceramic materials provided in examples 1 to 6 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]、[220]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.
Fig. 3, 6, 9, 12, 15 and 18 are schematic diagrams showing the changes of the relative dielectric constants of the piezoelectric ceramic materials according to examples 1 to 6 of the present application with temperature at 0.1kHz, 1kHz,10kHz and 100kHz, respectively.
FIGS. 3, 6, 9, 12, 15 and 18 are ZrF in the piezoelectric ceramic materials of examples 1 to 6, respectively 4 Substituted for ZrO 2 The relative dielectric constants at 0, 0.2, 0.4, 0.6, 0.8, and 1.0 vary with temperature. From the curve, it can be found that the ceramic provided by each embodiment has 3 dielectric peaks at-120-200 ℃, and the three-party-orthogonal, orthogonal-tetragonal and tetragonal-cubic phase changes respectively correspond to the temperature rise. And along withxThe phase transition temperature did not significantly shift, indicating that the anion doping did not result in a change in phase structure. 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 60 ℃, the ceramic presents a cubic phase, does not have ferroelectricity any more, the piezoelectric performance disappears, and the dielectric performance is seriously deteriorated.
Fig. 4, 7, 10, 13, 16 and 19 are respectively enlarged graphs of the piezoelectric ceramic materials of examples 1 to 6, in which the relative dielectric constant is 15 to 35 ℃, corresponding to the orthogonal-tetragonal phase transition temperature region; fig. 5, 8, 11, 14, 17 and 20 are enlarged graphs of the piezoelectric ceramic materials of examples 1 to 6, respectively, with relative dielectric constants in the range of 35 to 40 ℃ corresponding to the orthogonal-tetragonal phase transition temperature region. By contrast, it can be found that the anion doping can make the orthorhombic-tetragonal phase transition peak more sharp, the dispersion is reduced, the dielectric constant is increased, indicating that the polarity of the material is enhanced.
The present application also carried out tests on the electrical properties of the piezoelectric ceramic materials of examples 1 to 6 described above, and the results obtained are shown in Table 1.
TABLE 1
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. An anionically modified piezoelectric ceramic, characterized in that the piezoelectric ceramic has the chemical formula:
Ba 0.86 Sr 0.14 Ti 0.92 Zr 0.08 O x3-0.16 F x0.32 ，0.2≤x≤1。
2. the method for producing an anionically modified piezoelectric ceramic according to claim 1, wherein fluoride is used in place of oxide to realize oxygen substitution of fluoride ion in the piezoelectric ceramic, and lead-free piezoelectric ceramic having a piezoelectric constant ofd 33 950-1245pC/N, relative to room temperatureDielectric constantε r 3201 to 3786.
3. The method for preparing an anionically modified piezoelectric ceramic according to claim 2, comprising the steps of:
s101, rolling and ball milling by taking barium carbonate, strontium carbonate, titanium dioxide, zirconium oxide and zirconium fluoride as raw materials and absolute ethyl alcohol as a ball milling medium according to mole percent 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 700-1200 ℃ for 2-3 hours to obtain dry powder;
s104, adding a polyvinyl alcohol aqueous solution into the dry powder obtained in the step S103, and sequentially granulating, pressing and discharging glue to obtain a ceramic blank;
and S105, sintering the ceramic body obtained in the step S104 at 1400-1450 ℃ for 3-5 hours to obtain the piezoelectric ceramic body.
4. A method of preparing an anionically modified piezoelectric ceramic according to claim 3, comprising the further steps of:
and S106, plating silver electrodes on the piezoelectric ceramic body obtained in the step S105, and applying voltage to polarize the piezoelectric ceramic body.
5. A method of preparing an anionically modified piezoelectric ceramic according to claim 3, characterized in that in step S101, barium carbonate, strontium carbonate, titanium dioxide, zirconium oxide and zirconium fluoride are all analytically pure.
6. The method for producing an anionically modified piezoelectric ceramic according to claim 3, wherein in step S101, barium carbonate, strontium carbonate, titanium dioxide, zirconium oxide and zirconium fluoride are all in a powder structure; the particle size of the barium carbonate, the strontium carbonate, the titanium dioxide, the zirconium oxide and the zirconium fluoride is 100-800 microns.
7. The method for preparing an anionically modified piezoelectric ceramic according to claim 3, wherein in step S101, the ball milling pot used for ball milling is a nylon pot; the adopted grinding balls are zirconium balls.
8. The method for preparing an anionically modified piezoelectric ceramic according to claim 3, wherein in step S103, the powder is placed in a corundum crucible, and the corundum crucible is pre-sintered at 700-1200 ℃ for 2-3 hours to obtain a dry powder.
9. The method for producing an anionically modified piezoelectric ceramic according to claim 3, wherein the polyvinyl alcohol aqueous solution in step S104 is 6wt% to 8wt%.
10. The method for preparing an anionically modified piezoelectric ceramic according to claim 3, wherein in step S104, the specific pressing process is as follows: pressing the powder into a sheet shape by using an isostatic press; the pressure of the isostatic press was 250MPa.
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