CN116606143B - Piezoelectric ceramic material and preparation method thereof - Google Patents
Piezoelectric ceramic material and preparation method thereof Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000000919 ceramic Substances 0.000 claims abstract description 132
- 239000000843 powder Substances 0.000 claims description 106
- 238000000034 method Methods 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 31
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 30
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 30
- 238000000498 ball milling Methods 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 24
- 238000005245 sintering Methods 0.000 claims description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- 238000007873 sieving Methods 0.000 claims description 22
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 21
- 229910052709 silver Inorganic materials 0.000 claims description 21
- 239000004332 silver Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 125000004122 cyclic group Chemical group 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 238000005498 polishing Methods 0.000 claims description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000010583 slow cooling Methods 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 230000005684 electric field Effects 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 abstract description 18
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 abstract description 18
- 230000006872 improvement Effects 0.000 abstract description 5
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005457 optimization Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 229910052738 indium Inorganic materials 0.000 description 15
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 239000012071 phase Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 229910052845 zircon Inorganic materials 0.000 description 9
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 9
- 238000005303 weighing Methods 0.000 description 8
- 244000137852 Petrea volubilis Species 0.000 description 7
- 239000011267 electrode slurry Substances 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
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- 238000011160 research Methods 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910002056 binary alloy Inorganic materials 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
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- 230000028161 membrane depolarization Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
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- 239000011148 porous material Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 239000003292 glue Substances 0.000 description 1
- 229910052451 lead zirconate titanate Inorganic materials 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
- 239000007791 liquid phase Substances 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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Abstract
The invention discloses a piezoelectric ceramic material and a preparation method thereof, wherein the general formula of the piezoelectric ceramic material is Pb (In) 1/ 2 Nb 1/2 ) x (Yb 1/2 Nb 1/2 ) y Ti 1‑x‑y O 3 X is more than or equal to 0.126 and less than or equal to 0.504,0.1, and y is more than or equal to 0.4. According to the preparation method, the piezoelectric ceramic quasi-homotype phase boundary is constructed and regulated by adjusting the proportion of the lead ytterbium niobate and the lead titanate, so that the improvement of the Curie temperature and the optimization of the piezoelectric performance are realized. The piezoelectric ceramic material can balance the relation among Curie temperature, piezoelectric performance and strain hysteresis.
Description
Technical Field
The invention belongs to the technical field of high-temperature piezoelectric ceramic materials, and particularly relates to a piezoelectric ceramic material and a preparation method thereof.
Background
Along with the expansion of the application range of piezoelectric materials, the piezoelectric materials used under ordinary conditions do not meet the requirements of specific conditions, such as the fields with higher temperature requirements for nuclear industry, automobile manufacturing, aerospace, resource exploration and the like, and the development of high-temperature piezoelectric materials is urgent.
The piezoelectric ceramics with the tungsten bronze structure or the bismuth layered structure have higher Curie temperature, but the piezoelectric coefficient is very low, so that the application of the piezoelectric ceramics is limited; piezoelectric ceramics of perovskite structure have relatively high piezoelectric coefficients, but most of them have relatively low curie temperatures or depolarization temperatures, for example, lead zirconate titanate ceramics widely used are difficult to use in the higher temperature field due to depolarization phenomenon. In addition, the strain hysteresis of the piezoelectric ceramic is derived from the domain movement of the piezoelectric ceramic, and the working accuracy of devices such as a piezoelectric actuator can be greatly affected by excessive strain hysteresis. Therefore, the development of novel small hysteresis piezoelectric materials with high curie temperature is a current research hotspot.
Pb(In 1/2 Nb 1/2 )O 3 -PbTiO 3 Piezoelectric ceramics have relatively high piezoelectric coefficient, low cost and relatively simple synthesis process, so Pb (In) 1/2 Nb 1/2 )O 3 -PbTiO 3 Piezoelectric ceramics are a ceramic system with great research and practical application values. However, the curie temperature is still not high enough, which limits the use thereof, and therefore, it is necessary to explore a new modification method of the lead indium niobate-lead titanate binary system to raise the curie temperature thereof. Pb (Yb) 1/2 Nb 1/2 )O 3 -PbTiO 3 Curie temperature T c The ceramic material has higher Curie temperature by adding the new lead ytterbium niobate component to modify the ceramic. However, in the process of pursuing a high curie temperature, it is found that performance parameters such as piezoelectric performance and strain hysteresis exist in a trade-off with each other, which limits the application field of lead-based perovskite piezoelectric materials. Therefore, the search for novel high-temperature piezoelectric ceramics with excellent comprehensive performance has important research significance and application value.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to overcome the defects in the prior art and provide a piezoelectric ceramic material and a preparation method thereof, and the relationship among Curie temperature, piezoelectric performance and strain hysteresis is balanced.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a piezoelectric ceramic material has a general formula Pb (In) 1/2 Nb 1/2 ) x (Yb 1/2 Nb 1/2 ) y Ti 1-x-y O 3 ，0.126≤x≤0.504，0.1≤y≤0.4。
Further, x=0.126, y=0.4.
Furthermore, the piezoelectric ceramic material has a quasi-isomorphic phase boundary region, and the piezoelectric performance is a small signal piezoelectric coefficient d 33 =151 to 274pC/N; large signal piezoelectric coefficient d 33 * =182 to 333pm/V; curie temperature T c =315 to 369 ℃; dielectric loss is tan delta=1.04 to 3.79%; coefficient of planar electromechanical coupling k p =0.25 to 0.36; mechanical quality factor Q m =28 to 47; residual polarization intensity P r ＝14.1～20.3μC/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Coercive field strength E c =12.2 to 18.9kV/cm; strain s=0.09% -0.13%; the strain hysteresis is 21% -26%.
The preparation method of the piezoelectric ceramic material is characterized in that the piezoelectric ceramic quasi-homotype phase boundary is constructed and regulated by adjusting the proportion of lead ytterbium niobate and lead titanate, so that the improvement of the Curie temperature and the optimization of the piezoelectric performance are realized.
Further, a preparation method of the piezoelectric ceramic material comprises the following steps:
s1, yb is added 2 O 3 Powder and Nb 2 O 5 Powder, in 2 O 3 Powder and Nb 2 O 5 Respectively mixing the powder, sequentially performing ball milling, drying and briquetting, then heating to 1100-1200 ℃, and preserving heat to obtain YbNbO 4 And InNbO 4 A precursor;
s2, according to Pb (In) 1/2 Nb 1/2 ) x (Yb 1/2 Nb 1/2 ) y Ti 1-x-y O 3 Is to weigh YbNbO respectively 4 、InNbO 4 Excessive PbO, tiO 2 Mixing the raw materials, performing ball milling for one time to obtain mixed powder, and drying and grinding, wherein 0.126% or lessx≤0.504，0.1≤y≤0.4；
S3, presintering the mixed powder obtained in the step S2, and cooling to room temperature after presintering is finished to obtain presintering powder;
s4, sequentially performing secondary ball milling, drying, grinding, granulating and sieving on the presintered powder obtained in the step S3 to obtain powder with uniform particles;
s5, standing the powder with uniform particles obtained in the step S4, and then compacting to obtain a green body, and removing organic matters in the green body to obtain a ceramic green body;
s6, burying the green body treated in the step S5 into a platinum crucible filled with powder material with the same components as the ceramic green body, loading the platinum crucible into an alumina crucible, and sintering by using a cyclic temperature rise and reduction method: raising the temperature to 950-1000 ℃ from room temperature at 3-5 ℃/min, then raising the temperature to 1050-1100 ℃ at 10-30 ℃/min, and then slowly lowering the temperature to 950-1000 ℃ at 1-3 ℃/min; then, the rapid heating and slow cooling processes are circulated, and sintering is carried out for 2-4 h; naturally cooling to room temperature along with a furnace to obtain piezoelectric ceramics with high Curie temperature and small hysteresis;
s7, polishing the sintered piezoelectric ceramic, coating silver paste on the upper and lower surfaces of the ceramic, and naturally cooling the ceramic to room temperature after sintering the silver paste;
and S8, applying a direct current electric field to the ceramic coated with the silver paste to fully polarize the ceramic to obtain the piezoelectric ceramic material.
Further, the medium during ball milling in the steps S1, S2 and S4 is absolute ethyl alcohol, and the mass ratio of the material to the zirconium balls to the absolute ethyl alcohol is 1:2: (0.5-1.0).
Further, the drying temperatures in the steps S1, S2 and S4 are all 50-80 ℃.
Further, in the step S4, the granulating is carried out by adding polyvinyl alcohol aqueous solution accounting for 6-10% of the mass of the mixture; the mass concentration of the polyvinyl alcohol is 2% -5%.
Further, in the step S5, the powder with uniform particles is pressed into a green body under the pressure of 10 MPa-15 MPa.
Further, in step S5, the process of removing the organic matters in the blank is as follows: heating the green body to 500-600 ℃ at a speed of 3-5 ℃/min, preserving heat for 1-3 h, and removing organic matters in the green body.
Compared with the prior art, the invention has at least the following beneficial technical effects:
(1) The invention provides a novel ternary lead indium niobate-lead ytterbium niobate-lead titanate piezoelectric ceramic material, which is prepared by adding lead ytterbium niobate into a binary system of lead indium niobate-lead titanate, and has high Curie temperature, small strain hysteresis and relatively excellent piezoelectric performance. Specifically, it is obtained by test analysis: (1) the Curie temperature of the high-temperature piezoelectric ceramic system is not lower than 315 ℃ and can reach 369 ℃ at most; (2) the strain hysteresis of the high-temperature piezoelectric ceramic system is not higher than 26%, and the minimum strain hysteresis can reach 21%. (3) The piezoelectric coefficient of the high-temperature piezoelectric ceramic system is not lower than 151pC/N, and can reach 274pC/N at most; (4) the remnant polarization strength of the high-temperature piezoelectric ceramic system is not less than 14.1 mu C/cm 2 Up to 20.3. Mu.C/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the (5) The coercive field strength of the high-temperature piezoelectric ceramic system is not lower than 12.2kV/cm, and can reach 18.9kV/cm at most.
(2) The invention provides a preparation method of the material, which can successfully prepare a single perovskite phase, and the ceramic prepared by the method has uniform particle size and high density. The preparation process is simple, the sintering temperature is low, the method is suitable for large-scale industrial production, and the method has wide application prospect in the field of high-temperature piezoelectric devices.
The ceramic preparation method provided by the invention uses the platinum crucible to strengthen heat transfer, so that the temperature change of the ceramic powder is more sensitive; an alumina crucible is used to enhance the seal and provide a more stable lead atmosphere. Through the cooperation of the two types of crucibles, proper sintering conditions are provided for the piezoelectric ceramics, and the piezoelectric performance of the final product is improved.
The cyclic temperature increasing and reducing method provided by the invention can enable the ceramic to be rapidly activated at a higher temperature, and promote the migration and the diffusion of grain boundaries; the slow cooling process can provide a wider temperature range for the ceramic, adjust the relative speed of migration and diffusion of the ceramic grain boundary, avoid the generation of pores due to the overquick growth of grains on the basis of maintaining activation, promote the densification of the ceramic, and reduce the volatilization of lead; in the high-temperature sintering process, excessive PbO can promote liquid phase sintering of the ceramic, is beneficial to densification of the ceramic, and can supplement volatilization loss.
Further, the medium during ball milling is absolute ethyl alcohol, and the mass ratio of the material to the zirconium balls to the absolute ethyl alcohol is 1:2: (0.5-1.0), the ball milling speed is 300 revolutions per minute, and the ball milling time is 12-18 hours. The method can obtain powder with high uniformity, smaller particle size and uniform distribution. Further, the temperatures adopted in the steps S1, S2 and S4 are 50-80 ℃, and the conditions have efficiency and safety.
Further, in the step S4, the granulating is carried out by adding a polyvinyl alcohol aqueous solution (PVA) accounting for 6-10% of the mass of the granules; the mass concentration of PVA is 2% -5%. This condition helps to obtain a higher green strength subsequently.
Further, in step S4, the number of the screened meshes is 40 meshes and 80 meshes, and the intermediate homogeneous material is pressed into a green body under the pressure of 10-15 MPa. This condition helps to obtain a green body of higher strength.
Further, in the step S5, the process of removing the organic matters in the blank is as follows: heating the green body to 500-600 ℃ at a speed of 3-5 ℃/min, preserving heat for 1-3 h, and removing organic matters in the green body; the condition can thoroughly exclude the polyvinyl alcohol added by granulation so as to obtain the ceramic with higher density.
Further, the temperature rising rate in the steps S1 and S3 is 3-5 ℃/min. The conditions give consideration to both production efficiency and equipment life.
Drawings
FIG. 1 is an XRD diffraction pattern of lead indium niobate-lead ytterbium niobate-lead titanate piezoelectric ceramic samples prepared in comparative examples 1 to 2 and examples 1 to 4.
FIG. 2 is a scanning electron microscope image of a sample of the lead indium niobate-lead ytterbium niobate-lead titanate piezoelectric ceramic prepared in examples 1 to 4.
FIG. 3 is a graph showing the hysteresis curves of the lead indium niobate-lead ytterbium niobate-lead titanate piezoelectric ceramic samples prepared in comparative examples 1 to 2 and examples 1 to 4 at a frequency of 1Hz at room temperature.
FIG. 4 is a graph showing the dielectric temperature profile of the lead indium niobate-lead ytterbium niobate-lead titanate piezoelectric ceramic samples prepared in comparative examples 1 to 2 and examples 1 to 4.
Fig. 5 is a unipolar strain curve of the lead indium niobate-lead ytterbium niobate-lead titanate piezoelectric ceramic samples prepared in examples 1 to 4.
FIG. 6 is a graph showing changes in Curie temperature and piezoelectric coefficient of lead indium niobate-lead ytterbium niobate-lead titanate piezoelectric ceramic samples prepared in comparative examples 1 to 2 and examples 1 to 4.
Detailed Description
In order to make the purpose and technical scheme of the invention clearer and easier to understand. The present invention will now be described in further detail with reference to the drawings and examples, which are given for the purpose of illustration only and are not intended to limit the invention thereto.
Aiming at the situation that the Curie temperature and the comprehensive electrical property of the existing piezoelectric ceramic can not meet specific indexes at the same time, a collaborative strategy of adding the solid solution proportion of the lead ytterbium niobate and the lead titanate is added to construct and regulate the quasi-homotype phase boundary of the piezoelectric ceramic, so that the Curie temperature is improved and the piezoelectric property is optimized. On the basis of further improving the Curie temperature, the synergistic strategy obtains the piezoelectric ceramic material with higher piezoelectric performance, smaller strain hysteresis and excellent comprehensive performance, and provides a new thought for the application of the lead-based perovskite structure material in high-temperature piezoelectric devices. Specifically, the chemical components of the piezoelectric ceramic material with high Curie temperature and small hysteresis conform to the chemical general formula: pb (In) 1/2 Nb 1/2 ) x (Yb 1/2 Nb 1/2 ) y Ti 1-x-y O 3 Wherein x=0.126 to 0.504 and y=0.1 to 0.4. Preferably, x=0.126, 0.252, 0.378 or 0.504, y=0.4, 0.3, 0.2, 0.1.
The invention adopts the composition and regulates the quasi-homotype phase boundary, realizes better balance between Curie temperature, piezoelectric performance and strain hysteresis, obtains higher Curie temperature (315-369 ℃) and lower strain hysteresis (21-26%), meets the requirement of high-temperature piezoelectric ceramic components on high-temperature piezoelectric ceramic materials, and is Wen Ling high-temperature piezoelectric ceramic materialsThe application of the field plays a powerful role in pushing, and is expected to be used for high-temperature piezoelectric devices with the temperature of 200-300 ℃. In some examples, the high temperature piezoelectric ceramic has a room temperature piezoelectric coefficient of 151 to 274pC/N (preferably 244 to 274 pC/N), d 33 * =182 to 333pm/V (preferably 278 to 333 pm/V), curie temperature is 315 to 369 ℃. This is combined with unmodified PIN-37PT (T C ＝304℃、d 33 ＝517pC/N、d 33 * =543 pm/V) and PYN-50PT (T C ＝367℃、d 33 ＝222pC/N、d 33 * =238 pm/V), the overall properties of the material are significantly improved.
The invention also provides a preparation method of the piezoelectric ceramic material with high Curie temperature and small hysteresis, which comprises the steps of synthesizing YbNbO at first 4 And InNbO 4 The precursor is synthesized into lead indium niobate-lead ytterbium niobate-lead titanate solid solution ceramic powder, and the lead indium niobate-lead ytterbium niobate-lead titanate solid solution ceramic powder is sintered by adopting a cyclic temperature rising and reducing method to prepare the lead indium niobate-lead ytterbium niobate-lead titanate high-temperature piezoelectric ceramic material with high piezoelectric performance, which comprises the following steps:
S1、YbNbO 4 、InNbO 4 preparing a precursor: yb is processed into 2 O 3 Powder and Nb 2 O 5 Powder, in 2 O 3 Powder and Nb 2 O 5 The powder is prepared from the following components in percentage by mole: 1, mixing, sequentially ball milling, drying and briquetting, then heating to 1100-1200 ℃ at a heating rate of 3-5 ℃/min, and preserving heat for 4-6 h to obtain YbNbO 4 And InNbO 4 A precursor;
S2、Pb(In 1/2 Nb 1/2 ) x (Yb 1/2 Nb 1/2 ) y Ti 1-x-y O 3 preparation of piezoelectric ceramic material: pbO powder and TiO 2 Powder and YbNbO obtained in step S1 4 、InNbO 4 The powder is used as raw material, and the molar ratio is 1.02: (1-x-y): y: weighing, namely weighing the full ingredients, the zircon ball and the absolute ethyl alcohol according to the mass ratio of 1:2: (0.5-1.0) mixing, ball milling for 12-18 h at 300-400 rpm, drying, grinding, briquetting, heating to 800 at 3-5 ℃/minPreserving heat for 2-4 h at the temperature of 900 ℃ and then cooling to room temperature to obtain presintered powder, wherein the conditions are conducive to obtaining a pure-phase perovskite structure, thereby obtaining higher piezoelectric performance. Wherein x=0.126-0.504, y=0.1-0.4, and the excess of PbO is 2mol%, so as to compensate the volatilization loss of PbO in the high-temperature sintering process.
S3, grinding the presintered powder obtained in the step S2, and then mixing the presintered powder with zirconium ball stone and absolute ethyl alcohol according to the mass ratio of 1:2: (0.5-1.0) and then carrying out secondary ball milling for 12-18 h; grinding the dried materials and sieving the ground materials with a 120-mesh sieve, adding a polyvinyl alcohol aqueous solution (PVA) accounting for 6 to 10 percent of the mass of the ground materials, and granulating the ground materials, wherein the mass concentration of the PVA is 2 to 5 percent; granulating, sieving with a 40-mesh sieve and a 80-mesh sieve to obtain uniform powder, standing for 12-24 h, pressing the uniform powder under the pressure of 10-15 MPa, placing in a muffle furnace, heating to 500-600 ℃ at 3-5 ℃/min, preserving heat for 1-3 h, and discharging glue to obtain a ceramic blank for later use; the conditions can thoroughly exclude the polyvinyl alcohol added by granulation so as to obtain a ceramic sample with higher density.
S4, burying the blank body treated in the step S3 into powder with the same components as the blank body, placing the powder into a platinum crucible, loading the platinum crucible into an alumina crucible, and sintering in air by using a circulating temperature rise and drop method: raising the temperature to 950-1000 ℃ from room temperature at 3-5 ℃/min, then raising the temperature to 1050-1100 ℃ at 8-10 ℃/min, and then slowly lowering the temperature to 950-1000 ℃ at 1-3 ℃/min; and then the rapid heating and slow cooling processes are circulated, and sintering is carried out for 2-4 h. Then naturally cooling to room temperature along with a furnace to obtain the piezoelectric ceramic material with high Curie temperature and small hysteresis;
s5, polishing the sintered ceramic sheet by sand paper with different granularity to obtain a thin ceramic sheet with a bright and smooth surface, uniformly coating silver electrode slurry on the front and back sides of the sample, and preserving heat at 500-600 ℃ for 10-30 minutes to burn silver, so as to obtain good ohmic contact; and (3) placing the ceramic coated with the silver paste at an oil bath temperature of 120-150 ℃ and applying a direct current electric field of 30-40 kV/cm to fully polarize for 20-40 min, thereby obtaining the piezoelectric ceramic material with high Curie temperature and small hysteresis.
In order to make the objects, technical solutions and advantages of the present invention more clear, only a few preferred embodiments are selected below, and the present invention will be further described in detail with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Comparative example 1:
the chemical composition of the piezoelectric ceramic was 0.63Pb (In 1/2 Nb 1/2 )O 3 -0.37PbTiO 3 The method comprises the following steps:
step 1, pbO powder and TiO powder 2 Powder and InNbO 4 Powder according to the mole ratio of 1.02:0.37:0.63, and then weighing the full ingredients, the zircon ball and the absolute ethyl alcohol according to the mass ratio of 1:2:0.6, ball milling for 15 hours after mixing, drying, sieving and briquetting in sequence, and preserving heat for 4 hours at 800 ℃ to obtain presintered powder;
step 2, grinding the presintered powder obtained in the step 1, and then mixing the presintered powder, the zircon ball and the absolute ethyl alcohol according to the mass ratio of 1:2: mixing 0.6, and performing secondary ball milling for 15 hours; drying, grinding, sieving with 120 mesh sieve, adding polyvinyl alcohol aqueous solution (PVA) accounting for 8% of the mass of the powder, and granulating, wherein the mass concentration of the PVA is 5%; sieving with 40 mesh and 80 mesh sieve to obtain uniform powder, standing for 14 hr, pressing to form powder at 15MPa, heating to 600deg.C at 5deg.C/min in muffle furnace, and maintaining for 1 hr to obtain ceramic blank;
step 3, covering the ceramic blank body treated in the step 2 with powder with the same components, placing the ceramic blank body in an alumina crucible, heating to 1075 ℃ at a speed of 5 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature along with a furnace; after sintering, 0.63Pb (In) 1/2 Nb 1/2 )O 3 -0.37PbTiO 3 A piezoelectric ceramic material;
and 4, polishing the sintered ceramic sheet by sand paper with different granularity to obtain a thin ceramic sheet with a bright and smooth surface, uniformly coating silver electrode slurry on the front and back sides of the sample, and carrying out silver burning at 500 ℃ for 10min to obtain the ceramic element. And measuring the electrical properties of the obtained piezoelectric ceramic element.
Comparative example 2:
the chemical composition of the piezoelectric ceramic is 0.5Pb (Yb 1/2 Nb 1/2 )O 3 -0.5PbTiO 3 The method comprises the following steps:
step 1, pbO powder and TiO powder 2 Powder and YbNbO 4 Powder according to the mole ratio of 1.02:0.5:0.5, and then weighing the full ingredients, the zircon ball and the absolute ethyl alcohol according to the mass ratio of 1:2:0.6, ball milling for 15 hours after mixing, drying, sieving and briquetting in sequence, and preserving heat for 4 hours at 800 ℃ to obtain presintered powder;
step 2, grinding the presintered powder obtained in the step 1, and then mixing the presintered powder, the zircon ball and the absolute ethyl alcohol according to the mass ratio of 1:2: mixing 0.6, and performing secondary ball milling for 15 hours; drying, grinding, sieving with 120 mesh sieve, adding polyvinyl alcohol aqueous solution (PVA) accounting for 8% of the mass of the powder, and granulating, wherein the mass concentration of the PVA is 5%; sieving with 40 mesh and 80 mesh sieve to obtain uniform powder, standing for 14 hr, pressing to form powder at 15MPa, heating to 600deg.C at 5deg.C/min in muffle furnace, and maintaining for 1 hr to obtain ceramic blank;
step 3, covering the ceramic blank body treated in the step 2 with powder with the same components, placing the ceramic blank body in an alumina crucible, heating to 1050 ℃ at 5 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature along with a furnace; after sintering, 0.5Pb (Yb) 1/2 Nb 1/2 )O 3 -0.5PbTiO 3 A piezoelectric ceramic material;
and 4, polishing the sintered ceramic sheet by sand paper with different granularity to obtain a thin ceramic sheet with a bright and smooth surface, uniformly coating silver electrode slurry on the front and back sides of the sample, and carrying out silver burning at 500 ℃ for 10min to obtain the ceramic element. And measuring the electrical properties of the obtained piezoelectric ceramic element.
Example 1:
the piezoelectric ceramic has a chemical composition of Pb (In) 1/2 Nb 1/2 ) 0.504 (Yb 1/2 Nb 1/2 ) 0.1 Ti 0.396 O 3 The method comprises the following steps:
s1, pbO powder and TiO powder 2 Powder, ybNbO 4 Powder and InNbO 4 Powder according to the mole ratio of 1.02:0.396:0.1:0.504, and then weighing the full ingredients, the zircon ball and the absolute ethyl alcohol according to the mass ratio of 1:2:0.6, ball milling for 15 hours after mixing, sequentially drying, sieving and briquetting, wherein the drying temperature is 50 ℃, the temperature is increased to 800 ℃ at the heating rate of 3 ℃/min, and the heat is preserved for 4 hours to obtain presintered powder;
s2, grinding the presintered powder obtained in the step S1, and then mixing the presintered powder with zirconium ball stone and absolute ethyl alcohol according to the mass ratio of 1:2: mixing 0.6, and performing secondary ball milling for 15 hours; drying, grinding, sieving with 120 mesh sieve, adding polyvinyl alcohol aqueous solution (PVA) accounting for 8% of the mass of the powder, and granulating, wherein the mass concentration of the PVA is 5%; sieving with 40 mesh and 80 mesh sieve to obtain uniform powder, standing for 14 hr, pressing to form powder at 15MPa, heating to 600deg.C at 5deg.C/min in muffle furnace, and maintaining for 1 hr to obtain ceramic blank;
s3, burying the blank body treated in the step S2 into a platinum crucible filled with powder with the same components as the blank body, filling the crucible into an alumina crucible, and sintering in air by using a cyclic temperature increasing and reducing method: raising the temperature to 1000 ℃ from room temperature at 5 ℃/min, then raising the temperature to 1075 ℃ at 10 ℃/min, and then slowly lowering the temperature to 1000 ℃ at 2 ℃/min; and then, the rapid heating and slow cooling processes are circulated, and sintering is carried out for 2 hours. Naturally cooling to room temperature along with the furnace to obtain Pb (In) 1/2 Nb 1/2 ) 0.504 (Yb 1/ 2 Nb 1/2 ) 0.1 Ti 0.396 O 3 A high curie temperature piezoelectric ceramic material;
and S4, polishing the sintered ceramic sheet by sand paper with different granularity to obtain a thin ceramic sheet with a bright and smooth surface, uniformly coating silver electrode slurry on the front and back sides of the sample, and carrying out silver burning at 500 ℃ for 10min to obtain the ceramic element. The obtained piezoelectric ceramic element was polarized, and then the electrical properties were measured.
Example 2:
the piezoelectric ceramic has a chemical composition of Pb (In) 1/2 Nb 1/2 ) 0.378 (Yb 1/2 Nb 1/2 ) 0.2 Ti 0.422 O 3 The method comprises the following steps:
s1, pbO powder and TiO powder 2 Powder, ybNbO 4 Powder and InNbO 4 Powder according to the mole ratio of 1.02:0.422:0.2:0.378, then weighing the full ingredients, the zircon ball and the absolute ethyl alcohol according to the mass ratio of 1:2:0.5, ball milling for 12 hours, sequentially drying, sieving and briquetting, wherein the drying temperature is 65 ℃, the temperature is raised to 850 ℃ at the heating rate of 4 ℃/min, and the heat is preserved for 3 hours to obtain presintered powder;
s2, grinding the presintered powder obtained in the step S1, and then mixing the presintered powder with zirconium ball stone and absolute ethyl alcohol according to the mass ratio of 1:2: mixing 0.6, and performing secondary ball milling for 15 hours; drying, grinding, sieving with 120 mesh sieve, adding polyvinyl alcohol aqueous solution (PVA) accounting for 6% of the mass of the powder, and granulating, wherein the mass concentration of the PVA is 2%; sieving with 40 mesh and 80 mesh sieve to obtain uniform powder, standing for 14 hr, pressing to form powder at 10MPa, heating to 500 deg.C at 5 deg.C/min in muffle furnace, and maintaining for 2 hr to obtain ceramic blank;
s3, burying the blank body treated in the step S2 into a platinum crucible filled with powder with the same components as the blank body, filling the crucible into an alumina crucible, and sintering in air by using a cyclic temperature increasing and reducing method: raising the temperature to 950 ℃ from room temperature at 3 ℃/min, then raising the temperature to 1050 ℃ at 12 ℃/min, and then slowly lowering the temperature to 950 ℃ at 1 ℃/min; and then, the rapid heating and slow cooling processes are circulated, and sintering is carried out for 4 hours. Naturally cooling to room temperature along with the furnace to obtain Pb (In) 1/2 Nb 1/2 ) 0.378 (Yb 1/2 Nb 1/2 ) 0.2 Ti 0.422 O 3 A high curie temperature piezoelectric ceramic material;
and S4, polishing the sintered ceramic sheet by sand paper with different granularity to obtain a thin ceramic sheet with a bright and smooth surface, uniformly coating silver electrode slurry on the front and back sides of the sample, and carrying out silver burning at 500 ℃ for 10min to obtain the ceramic element. The obtained piezoelectric ceramic element was polarized, and then the electrical properties were measured.
Example 3:
the piezoelectric ceramic has a chemical composition of Pb (In) 1/2 Nb 1/2 ) 0.252 (Yb 1/2 Nb 1/2 ) 0.3 Ti 0.448 O 3 The method comprises the following steps:
s1, pbO powder and TiO powder 2 Powder, ybNbO 4 Powder and InNbO 4 Powder according to the mole ratio of 1.02:0.448:0.3:0.252, and then weighing the full ingredients, the zircon ball and the absolute ethyl alcohol according to the mass ratio of 1:2:1, mixing, ball milling for 18 hours, sequentially drying, sieving, briquetting, and heating to 900 ℃ at a heating rate of 5 ℃/min at a drying temperature of 80 ℃ for 2 hours to obtain presintered powder;
s2, grinding the presintered powder obtained in the step S1, and then mixing the presintered powder with zirconium ball stone and absolute ethyl alcohol according to the mass ratio of 1:2: mixing 0.6, and performing secondary ball milling for 15 hours; drying, grinding, sieving with 120 mesh sieve, adding 10% polyvinyl alcohol aqueous solution (PVA) for granulating, wherein the mass concentration of PVA is 3%; sieving with 40 mesh and 80 mesh sieve to obtain uniform powder, standing for 14 hr, press molding under 12MPa, heating to 550deg.C at 5deg.C/min in muffle furnace, and maintaining for 1.5 hr to obtain ceramic blank;
s3, burying the blank body treated in the step S2 into a platinum crucible filled with powder with the same components as the blank body, filling the crucible into an alumina crucible, and sintering in air by using a cyclic temperature increasing and reducing method: heating to 975 ℃ from room temperature at 4 ℃/min, then heating to 1150 ℃ at 15 ℃/min, and then cooling to 975 ℃ at 2 ℃/min; and then, the rapid heating and slow cooling processes are circulated, and sintering is carried out for 3 hours. Naturally cooling to room temperature along with the furnace to obtain Pb (In) 1/2 Nb 1/2 ) 0.252 (Yb 1/2 Nb 1/2 ) 0.3 Ti 0.448 O 3 A high curie temperature piezoelectric ceramic material;
and S4, polishing the sintered ceramic sheet by sand paper with different granularity to obtain a thin ceramic sheet with a bright and smooth surface, uniformly coating silver electrode slurry on the front and back sides of the sample, and carrying out silver burning at 500 ℃ for 10min to obtain the ceramic element. The obtained piezoelectric ceramic element was polarized, and then the electrical properties were measured.
Example 4:
the piezoelectric ceramic has a chemical composition of Pb (In) 1/2 Nb 1/2 ) 0.126 (Yb 1/2 Nb 1/2 ) 0.4 Ti 0.474 O 3 The method comprises the following steps:
s1, pbO powder and TiO powder 2 Powder, ybNbO 4 Powder and InNbO 4 Powder according to the mole ratio of 1.02:0.474:0.4:0.126, and then weighing the full ingredients, the zircon ball and the absolute ethyl alcohol according to the mass ratio of 1:2:0.6, ball milling for 15 hours after mixing, sequentially drying, sieving and briquetting, wherein the drying temperature is 70 ℃, and the temperature is raised to 800 ℃ at a heating rate of 4 ℃/min, and the pre-sintered powder is obtained;
s2, grinding the presintered powder obtained in the step S1, and then mixing the presintered powder with zirconium ball stone and absolute ethyl alcohol according to the mass ratio of 1:2: mixing 0.6, and performing secondary ball milling for 15 hours; drying, grinding, sieving with 120 mesh sieve, adding polyvinyl alcohol aqueous solution (PVA) accounting for 8% of the mass of the powder, and granulating, wherein the mass concentration of the PVA is 5%; sieving with 40 mesh and 80 mesh sieve to obtain uniform powder, standing for 14 hr, pressing to form powder at 15MPa, heating to 600deg.C at 5deg.C/min in muffle furnace, and maintaining for 1 hr to obtain ceramic blank;
s3, burying the blank body treated in the step S2 into a platinum crucible filled with powder with the same components as the blank body, filling the crucible into an alumina crucible, and sintering in air by using a cyclic temperature increasing and reducing method: raising the temperature to 1000 ℃ from room temperature at 5 ℃/min, then raising the temperature to 1050 ℃ at 10 ℃/min, and then slowly lowering the temperature to 1000 ℃ at 2 ℃/min; and then, the rapid heating and slow cooling processes are circulated, and sintering is carried out for 2 hours. Naturally cooling to room temperature along with the furnace to obtain Pb (In) 1/2 Nb 1/2 ) 0.126 (Yb 1/ 2 Nb 1/2 ) 0.4 Ti 0.474 O 3 A high curie temperature piezoelectric ceramic material;
and S4, polishing the sintered ceramic sheet by sand paper with different granularity to obtain a thin ceramic sheet with a bright and smooth surface, uniformly coating silver electrode slurry on the front and back sides of the sample, and carrying out silver burning at 500 ℃ for 10min to obtain the ceramic element. The obtained piezoelectric ceramic element was polarized, and then the electrical properties were measured.
FIG. 1 shows Pb (In) In accordance with the present invention 1/2 Nb 1/2 ) x (Yb 1/2 Nb 1/2 ) y Ti 1-x-y O 3 X-ray diffraction (XRD) pattern of high temperature piezoceramic. As can be seen from fig. 1, the above piezoelectric ceramic prepared by the cyclic temperature increase and decrease method exhibits a single perovskite structure, and no significant second phase appears. For Pb (In) 1/2 Nb 1/2 ) x (Yb 1/2 Nb 1/2 ) y Ti 1-x-y O 3 (x=0.126-0.504, y=0.1-0.4) ceramic, it can be seen that the phase structure of the ceramic sample is a perovskite structure with coexisting three-phase and tetragonal phase, and the ceramic sample shows the characteristic of a quasi-homotype phase boundary (MPB).
FIG. 2 is a scanning electron microscope image of the high temperature piezoelectric ceramics of examples 1-4 in the embodiment of the present invention. As seen from FIG. 2, pb (In 1/2 Nb 1/2 ) x (Yb 1/2 Nb 1/2 ) y Ti 1-x-y O 3 (x=0.126-0.504, y=0.1-0.4) ceramic surface pores are less, grain boundaries are clear, and grains are uniform and compact.
FIG. 3 shows the hysteresis loop of the lead indium niobate-lead ytterbium niobate-lead titanate high temperature piezoelectric ceramic of the present invention at a frequency of 1Hz at room temperature. For Pb (In) 1/2 Nb 1/2 ) x (Yb 1/2 Nb 1/2 ) y Ti 1-x-y O 3 (x=0.063 to 0.567 and y=0.05 to 0.45) ceramic, and the ceramic is fully polarized, it can be seen that as the content of the PYN increases, the coercive electric field of the high-temperature piezoelectric ceramic system increases, and the residual polarization intensity tends to be gradually improved, which also shows that the improvement of the PYN content of the ceramic system contributes to the improvement of the piezoelectric performance of the ceramic to a certain extent.
FIG. 3 shows the hysteresis loops of the high temperature piezoceramics of examples 1-4 of the present invention at room temperature and 1Hz frequency.
FIG. 4 shows dielectric thermograms of comparative examples 1-2 and examples 1-4 of high temperature piezoceramics according to an embodiment of the present invention. It can be seen that the lower curie temperature of the PIN-PT ceramic of comparative example 1 limits its use at high temperatures. With the addition of the new PYN component, the Curie temperature of the ceramic is effectively improved, and the Curie temperature of the high-temperature piezoelectric ceramic is above 315 ℃ and can reach 360 ℃ at most, so that the invention can meet the related requirements of specific high-temperature environments.
FIG. 5 is a unipolar strain curve of the high temperature piezoelectric ceramic of examples 1-4 in accordance with an embodiment of the present invention. As can be seen from FIG. 5, the high-temperature ceramic system has relatively small strain hysteresis, the maximum is 26%, and the minimum is only 21%, so that the system ceramic has good application prospect in the field of high-temperature piezoelectric brakes.
FIG. 6 is a graph showing changes in Curie temperatures and piezoelectric coefficients of different components of the high temperature piezoelectric ceramics of comparative examples 1-2 and examples 1-4 in the embodiment of the present invention. It can be seen that the curie temperature of the high temperature piezoelectric ceramic of the present invention is increased relative to the PIN-PT ceramic of comparative example 1, and the curie temperature of the ceramic is gradually increased as the PYN content is increased; on the other hand, compared with the PYN-PT ceramic of comparative example 2, the piezoelectric performance of the lead indium niobate-lead ytterbium niobate-lead titanate high-temperature piezoelectric ceramic is improved, and meanwhile, the higher Curie temperature is reserved, so that the PYN-PT ceramic has important significance for high-temperature piezoelectric device application.
The main performance parameters of the high temperature piezoelectric ceramic samples prepared in comparative examples and examples 1 to 4 are shown in Table 1
TABLE 1 principal Properties of the high temperature piezoelectric ceramic samples prepared in comparative examples 1-2 and examples 1-4
As shown in Table 1, the Curie temperature of the high-temperature piezoelectric ceramic material prepared by the invention is 315-369 ℃, the strain hysteresis is 21-26%, the piezoelectric coefficient can reach 151-274 pC/N, and the inverse piezoelectric coefficient can reach 182-333 pm/V.
According to the invention, through adding new component modification and material composition design, the novel high-temperature piezoelectric material with higher Curie temperature and smaller strain hysteresis is prepared by a cyclic temperature rise and drop method, and the lead indium niobate-lead ytterbium niobate-lead titanate high-temperature piezoelectric ceramic meets the higher requirements of devices working in a high-temperature environment on the piezoelectric material, and has the advantages of simple preparation process, lower cost and better repeatability.
Industrial applicability: the high-temperature piezoelectric ceramic material prepared by the invention can be used for preparing devices such as high-temperature piezoelectric actuators, high-temperature piezoelectric sensors and the like, and has good application prospects.
The invention belongs to the field of high-temperature piezoelectric ceramic materials, and particularly relates to a piezoelectric ceramic material with high Curie temperature and small hysteresis. The chemical general formula of the piezoelectric ceramic material is Pb (In) 1/2 Nb 1/2 ) x (Yb 1/2 Nb 1/2 ) y Ti 1-x-y O 3 X is more than or equal to 0.126 and less than or equal to 0.504,0.1, and y is more than or equal to 0.4. The preparation method of the ceramic material adopts a two-step solid-phase sintering method. The system was determined to be of perovskite structure by X-ray powder diffraction. The piezoelectric ceramic material balances the relation among Curie temperature, strain hysteresis and piezoelectric performance, further improves the Curie temperature of the piezoelectric ceramic while maintaining better piezoelectric performance and smaller strain hysteresis, has the highest Curie temperature of 369 ℃, meets the requirements of high-temperature piezoelectric devices on piezoelectric functional materials, has simple preparation process and low cost, is suitable for large-scale industrial production, and has wide application prospects in the aspects of high-temperature piezoelectric sensors, high-temperature piezoelectric actuators and the like.
The foregoing description of the preferred embodiments of the invention will be clearly understood to be more clearly understood to mean the following description of the preferred embodiments of the invention, but not limited to, any modifications, equivalents, improvements made within the principles of the invention.
Claims (8)
1. A piezoelectric ceramic material is characterized in that,the piezoelectric ceramic material has a general formula of Pb (In 1/2 Nb 1/2 ) x (Yb 1/ 2 Nb 1/2 ) y Ti 1-x-y O 3 ，x＝0.126，y＝0.4。
2. A piezoelectric ceramic material according to claim 1, wherein the piezoelectric ceramic material has a quasi-isomorphic phase boundary region, and the piezoelectric property is a small signal piezoelectric coefficient d 33 =274 pC/N; large signal piezoelectric coefficient d 33 * =333 pm/V; curie temperature T c =369 ℃; dielectric loss is tan δ=3.79%; coefficient of planar electromechanical coupling k p =0.33; mechanical quality factor Q m =46.7; strain s=0.09%; the strain hysteresis was 17%.
3. A method for producing the piezoelectric ceramic material according to claim 1, comprising the steps of:
s1, yb is added 2 O 3 Powder and Nb 2 O 5 Powder, in 2 O 3 Powder and Nb 2 O 5 Respectively mixing the powder, sequentially performing ball milling, drying and briquetting, then heating to 1100-1200 ℃, and preserving heat to obtain YbNbO 4 And InNbO 4 A precursor;
s2, according to Pb (In) 1/2 Nb 1/2 ) x (Yb 1/2 Nb 1/2 ) y Ti 1-x-y O 3 Is to weigh YbNbO respectively 4 、InNbO 4 Excessive PbO, tiO 2 Mixing the raw materials, performing ball milling for the first time to obtain mixed powder, and drying and grinding, wherein x=0.126 and y=0.4;
s3, presintering the mixed powder obtained in the step S2, and cooling to room temperature after presintering is finished to obtain presintering powder;
s4, sequentially performing secondary ball milling, drying, grinding, granulating and sieving on the presintered powder obtained in the step S3 to obtain powder with uniform particles;
s5, standing the powder with uniform particles obtained in the step S4, and then compacting to obtain a green body, and removing organic matters in the green body to obtain a ceramic green body;
s6, burying the green body treated in the step S5 into a platinum crucible filled with powder material with the same components as the ceramic green body, loading the platinum crucible into an alumina crucible, and sintering by using a cyclic temperature rise and reduction method: raising the temperature to 1000 ℃ from room temperature at 5 ℃/min, then raising the temperature to 1050 ℃ at 10 ℃/min, and then slowly lowering the temperature to 1000 ℃ at 2 ℃/min; then, the rapid heating and slow cooling processes are circulated, and sintering is carried out for 2 hours; naturally cooling to room temperature along with a furnace to obtain piezoelectric ceramics with high Curie temperature and small hysteresis;
s7, polishing the sintered piezoelectric ceramic, coating silver paste on the upper and lower surfaces of the ceramic, and naturally cooling the ceramic to room temperature after sintering the silver paste;
and S8, applying a direct current electric field to the ceramic coated with the silver paste to fully polarize the ceramic to obtain the piezoelectric ceramic material.
4. The method for preparing a piezoelectric ceramic material according to claim 3, wherein the media during ball milling in the steps S1, S2 and S4 are all absolute ethyl alcohol, and the mass ratio of the materials, zirconium balls and absolute ethyl alcohol during ball milling in the steps S2 and S4 is 1:2:0.6.
5. a method for producing a piezoelectric ceramic material according to claim 3, wherein the baking temperature in step S2 is 70 ℃.
6. The method according to claim 3, wherein the granulating in the step S4 is performed by adding an aqueous solution of polyvinyl alcohol accounting for 8% of the mass of the granules; the mass concentration of the polyvinyl alcohol is 5%.
7. A method for producing a piezoelectric ceramic material according to claim 3, wherein in the step S5, the powder having uniform particles is pressed into a green body under a pressure of 15 MPa.
8. The method for preparing a piezoelectric ceramic material according to claim 3, wherein in the step S5, the process of removing the organic matters in the green body is as follows: heating the green body to 600 ℃ at a speed of 5 ℃/min, preserving heat for 1h, and removing organic matters in the green body.
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