CN114292102A - Bismuth ferrite-barium titanate-based lead-free piezoelectric ceramic material and preparation method thereof - Google Patents
Bismuth ferrite-barium titanate-based lead-free piezoelectric ceramic material and preparation method thereof Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 49
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 45
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000000919 ceramic Substances 0.000 claims description 45
- 239000000463 material Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
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- 238000003786 synthesis reaction Methods 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 8
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- -1 bismuth iron-barium Chemical compound 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
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- 238000000465 moulding Methods 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 230000007704 transition Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229910000859 α-Fe Inorganic materials 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 6
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910002112 ferroelectric ceramic material Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
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- 229910002902 BiFeO3 Inorganic materials 0.000 description 1
- 229910000805 Pig iron Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- FMLWLDBXOUNLIV-UHFFFAOYSA-N [Mg].[Zr].[Bi] Chemical compound [Mg].[Zr].[Bi] FMLWLDBXOUNLIV-UHFFFAOYSA-N 0.000 description 1
- SXIPTACWBUDBIK-UHFFFAOYSA-N [O-2].[Mg+2].[Bi+3].[Hf+4] Chemical compound [O-2].[Mg+2].[Bi+3].[Hf+4] SXIPTACWBUDBIK-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 229910001451 bismuth ion Inorganic materials 0.000 description 1
- SKKNACBBJGLYJD-UHFFFAOYSA-N bismuth magnesium Chemical compound [Mg].[Bi] SKKNACBBJGLYJD-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
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- 239000000118 hair dye Substances 0.000 description 1
- 239000003676 hair preparation Substances 0.000 description 1
- 229910052742 iron 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
- 239000011812 mixed powder Substances 0.000 description 1
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- 238000009659 non-destructive testing Methods 0.000 description 1
- ZBSCCQXBYNSKPV-UHFFFAOYSA-N oxolead;oxomagnesium;2,4,5-trioxa-1$l^{5},3$l^{5}-diniobabicyclo[1.1.1]pentane 1,3-dioxide Chemical compound [Mg]=O.[Pb]=O.[Pb]=O.[Pb]=O.O1[Nb]2(=O)O[Nb]1(=O)O2 ZBSCCQXBYNSKPV-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
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- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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Abstract
The invention relates to a bismuth ferrite-barium titanate-based lead-free piezoelectric ceramic material and a preparation method thereof. The chemical composition of the bismuth ferrite-barium titanate-based lead-free piezoelectric ceramic material is xBiFeO3‑yBaTiO3‑zBi(Mg0.5Hf0.5)O3(ii) a Wherein x + y + z =1, x = 0.6-0.85, y = 0.15-0.35, and z = 0-0.05.
Description
Technical Field
The invention relates to a high-Curie temperature, high-resistivity and large-electrical-strain bismuth ferrite-barium titanate-based lead-free piezoelectric ceramic and a preparation method thereof, belonging to the field of lead-free piezoelectric ceramic materials.
Background
Based on the characteristic that piezoelectric ceramics can realize the interconversion of electric signals and mechanical strain, the piezoelectric ceramics are already made into devices such as sensors, piezoelectric transducers, drivers and the like, and are widely applied to aerospace and underwater acoustic detectionThe method has the advantages that the method can be applied to various fields such as testing and nondestructive testing, but has higher performance requirements on the piezoelectric ceramic material when being applied in extreme environments such as high-temperature and high-pressure environments. At present, the high-temperature piezoelectric ceramics mainly comprise four major types of tungsten bronze structures, perovskite structures, bismuth layer structures, perovskite-like structures and the like. Bismuth ferrite (BiFeO)3) The high-temperature piezoelectric ceramic belongs to perovskite, and has not only higher Curie temperature but also high piezoelectric performance compared with other three types. But BiFeO3The higher leakage current and lower high temperature resistivity limit their applications. BiFeO is subjected to3In barium titanate (BaTiO)3) The binary system after compounding can well reduce the leakage current of the material and improve the piezoelectric performance, but the Curie temperature is reduced along with the reduction of the material. How to balance the relationship among Curie temperature, high-temperature resistivity and piezoelectric performance, obtain components with excellent performance and meet the requirements of production and application is a key problem to be solved urgently.
In general, a transition from ferroelectric to relaxor ferroelectric occurs in a ferroelectric material through solid solution of relaxor ferroelectric, and the transition component is referred to as a second type of morphotropic phase boundary. While ferroelectric relaxor ceramic materials in this range tend to exhibit excellent piezoelectric properties, for example, lead magnesium niobate (PMN) can achieve large electrostriction in lead zirconate titanate (PZT). In the relaxor ferroelectric material, the relaxation degree of Bismuth Magnesium Hafnium (BMH) is stronger than that of common relaxor ferroelectrics such as Bismuth Magnesium Titanate (BMT) and Bismuth Magnesium Zirconium (BMZ). BMH is compounded in bismuth ferrite-barium titanate (BF-BT), and the proportion of BF and BT is adjusted, so that a transition component from ferroelectric to relaxor ferroelectric can be obtained, and the lead-free piezoelectric ceramic material with high Curie temperature, large electrostriction and high resistivity is obtained.
Disclosure of Invention
In order to obtain high Curie temperature, high resistivity and large strain value in the lead-free piezoelectric ceramic material at the same time, the invention provides a solid solution bismuth hafnium magnesium acid-bismuth ferrite-barium titanate ceramic material with high Curie temperature, high resistivity and large strain and a preparation method thereof.
On one hand, the invention provides a bismuth ferrite-barium titanate-based lead-free piezoelectric ceramic material, and the chemical composition of the bismuth ferrite-barium titanate-based lead-free piezoelectric ceramic material is xBiFeO3-yBaTiO3-zBi(Mg0.5Hf0.5)O3(ii) a Wherein x + y + z is 1, x is 0.6-0.85, y is 0.15-0.35, and z is 0-0.05.
The key point of the invention is to adjust the proportion of bismuth ferrite and barium titanate to reduce leakage current and improve resistivity, and the inventor shows through research that the resistivity can be improved by reducing the content of bismuth ferrite in the formula and the ferroelectric-relaxation phase transition can be generated. On the basis, hafnium-magnesium Bismuth (BMH) with high relaxation degree is further selected for doping, the disorder degree of the components is increased, the ferroelectric-relaxation phase transition is completed on the premise of ensuring higher Curie temperature, and the relaxation ferroelectric ceramic material with large strain value is obtained.
Preferably, x is 0.25 to 0.35, and y is 0.05.
Preferably, the resistivity of the bismuth ferrite-barium titanate-based lead-free piezoelectric ceramic material at 300 ℃ is more than 104Preferably > 106。
Preferably, the Curie temperature of the bismuth ferrite-barium titanate-based lead-free piezoelectric ceramic material is more than 300 ℃.
Preferably, the electrical strain of the bismuth ferrite-barium titanate-based lead-free piezoelectric ceramic material is more than or equal to 0.02 percent, and preferably more than 2 percent.
On the other hand, the invention provides a preparation method of the bismuth ferrite-barium titanate-based piezoelectric ceramic material, which uses Fe2O3、Bi2O3、BaCO3、TiO2、MgO、HfO2The powder is used as a raw material and has xBiFeO according to the chemical composition of the bismuth ferrite-barium titanate based lead-free piezoelectric ceramic material3-yBaTiO3-zBi(Mg0.5Hf0.5)O3And (3) carrying out material mixing, synthesis, fine grinding, granulation, molding, plastic discharge and sintering to obtain the bismuth ferrite-barium titanate-based lead-free piezoelectric ceramic material.
Preferably, the mixing and fine grinding mode is wet ball milling; wherein, the raw materials: ball milling medium: the mass ratio of the deionized water is 1: (1.6-2.4): (0.8-1.2) and performing planetary ball milling and mixing for 2-6 hours at the rotating speed of 300-400 rpm, wherein the preferred ball milling medium is agate balls.
Preferably, the synthesis temperature is 700-850 ℃, and the synthesis time is 4-6 hours; preferably, the temperature rise rate of the synthesis is 4-6 ℃/min.
Preferably, a binder accounting for 5-10% of the mass of the synthesized ceramic powder is added in the granulation process for granulation; preferably, the binder is a polyvinyl alcohol solution with a concentration of 4-8 wt.%.
Preferably, the temperature of the plastic discharging is 600-800 ℃, and the temperature is kept for 3 hours; preferably, the temperature rise rate of the plastic discharge is not higher than 2 ℃/min.
Preferably, the sintering temperature is 980-1030 ℃ and the sintering time is 2-5 hours.
Preferably, the obtained bismuth ferrite-barium titanate-based lead-free piezoelectric ceramic material is subjected to electrode preparation; preferably, the electrode is a silver paste electrode, the sintering condition of the electrode is 700-800 ℃, and the temperature is kept for less than 60 minutes.
Has the advantages that:
in the present invention, the resistivity can be increased by reducing the bismuth ferrite content in the formulation, and a pig iron electro-relaxation phase transition occurs. On the basis, hafnium-magnesium Bismuth (BMH) with high relaxation degree is further selected for doping, the disorder degree of the components is increased, the ferroelectric-relaxation phase transition is completed on the premise of ensuring higher Curie temperature, and the relaxation ferroelectric ceramic material with large strain value is obtained. Specifically, the traditional solid phase hair preparation method is adopted to obtain the solid phase hair dye with Curie temperature of more than 300 ℃ and resistivity of more than 10 at 300 DEG C6And a piezoelectric ceramic having a large strain characteristic. The piezoelectric ceramic material has the characteristics of high Curie temperature, high resistivity and large strain value, and is suitable for being used as a high-temperature driver material.
Drawings
FIGS. 1a to 1d are dielectric thermograms of bismuth ferrite-barium titanate-based lead-free piezoelectric ceramics prepared in examples 1 to 4, respectively;
FIGS. 2a to 2d are the hysteresis loop and the strain, respectively, of the bismuth ferrite-barium titanate-based lead-free and lead-free piezoelectric ceramics prepared in examples 1 to 4;
FIG. 3 is a graph showing the temperature swing resistivity of the bismuth ferrite-barium titanate-based lead-free piezoelectric ceramics prepared in examples 1 to 4;
FIG. 4 is the hysteresis loop and strain of bismuth ferrite-barium titanate-based lead-free piezoelectric ceramics prepared in example 5, example 6 and example 7;
FIG. 5 is a graph showing the hysteresis loop and strain of the bismuth ferrite-barium titanate-based lead-free piezoelectric ceramics prepared in comparative examples 1 to 2;
FIG. 6 is a graph showing the temperature change resistivity of the bismuth ferrite-barium titanate-based lead-free piezoelectric ceramics according to comparative examples 1 to 2.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the field, the bismuth ferrite-based ceramic material has high electric leakage due to volatilization of high-temperature bismuth ions and valence change of iron ions, and further application of the bismuth ferrite-based ceramic material is limited by high-temperature low resistivity. The introduction of barium titanate can reduce the content of iron element in the formula, reduce leakage current and improve resistivity. However, the Curie temperature is also reduced due to the reduction of the content of bismuth ferrite, so that the search for an optimal composition with high Curie temperature and high resistivity is very important.
For this reason, the present inventors inventively: during the process of reducing the content of bismuth ferrite and increasing the content of barium titanate, the composition undergoes a phase transition process from ferroelectric to relaxation. Meanwhile, the relaxation ferroelectric material bismuth magnesium hafnium oxide can be doped, so that the disorder degree of the material can be further improved, the activation energy of domain deflection is reduced, the ferroelectric-relaxation phase transition is completed on the premise of ensuring high Curie temperature, and excellent electrostriction performance is obtained.
In the invention, the chemical composition of the lead-free piezoceramic material with high Curie temperature, high resistivity and large strain is xBiFeO3-yBaTiO3-zBi(Mg0.5Hf0.5)O3Wherein x + y + z is 1, x is 0.6 to 0.85, y is 0.15 to 0.35, y is 0 to 0.05, preferably x is 0.6 to 0.7, y is 0.25 to 0.35, and z is 0.05. If the value of y is lower, the piezoelectric ceramic will have a lower resistance(ii) a If the y content is too high, the piezoelectric ceramic has a reduced complete relaxation strain. If the value of z is low, the strain rise is not obvious; if the z content is too high, the material will relax completely and lose the piezoelectric properties.
In an alternative embodiment, the lead-free piezoelectric ceramic has a curie temperature greater than 300 ℃; the electrical strain of the leadless piezoelectric ceramic is at least 0.03%, preferably 0.16-0.24%; the lead-free piezoelectric ceramic material has a resistivity of at least 5.4 x 10 at 300 DEG C4Preferably 5.7X 105～3.8×106。
In one embodiment of the invention, the bismuth ferrite-barium titanate-based lead-free piezoelectric ceramic material with high Curie temperature, high resistivity and large electrostrictive strain is prepared by adopting a traditional solid phase method, the preparation method is simple, easy to popularize and wide in prospect, and the preparation method specifically comprises the steps of material preparation, material mixing, synthesis, fine grinding, granulation, molding, plastic discharge, sintering and electrode preparation, and is provided by the invention. The following is an exemplary method for preparing the bismuth ferrite-barium titanate-based lead-free piezoelectric ceramic material.
Preparing ceramic powder by a solid phase method. With Fe2O3、Bi2O3、BaCO3、TiO2、MgO、HfO2The powder is used as a raw material, is prepared according to a stoichiometric ratio, is mixed and dried, and the dried raw material (namely, mixed powder) is obtained. Pressing the dried raw materials into blocks, synthesizing the blocks in an alumina crucible by a solid phase method, heating the blocks to 700-850 ℃ at a heating rate of 4-6 ℃/min, performing heat preservation and synthesis for 4-6 hours to obtain ceramic powder, and then cooling the ceramic powder to room temperature along with the furnace temperature to obtain the ceramic powder.
The ceramic powder is mechanically crushed, finely ground and dried to obtain the synthetic powder. Preferably, the fine grinding conditions and mode are consistent with the mixing.
Adding a binder accounting for 5 to 10 percent of the mass of the synthetic powder for grinding and granulating. Preferably, the binder is a polyvinyl alcohol solution of 4 to 8 wt.%.
The powder was pressed into a green body using simple mechanical pressing. Preferably, the molding pressure is 1-2 MPa. Preferably, the size of the blank is 12-14 mm in diameter and 1-2 mm in thickness. Heating the green body to 600-800 ℃ at a heating rate of not higher than 2 ℃/min, and preserving heat for less than 3 hours to carry out plastic removal treatment.
And (3) placing the green body subjected to plastic removal into a crucible, sintering for 2-5 hours at 980-1030 ℃, and cooling to room temperature along with the furnace temperature to obtain the bismuth ferrite-barium titanate piezoelectric ceramic. And preparing an electrode on the surface of the ceramic by screen printing, and sintering at 700-800 ℃ for less than 60min, wherein the electrode is preferably a platinum electrode.
The bismuth ferrite-barium titanate-based lead-free piezoelectric ceramic material prepared by the method has the characteristics of high Curie temperature, high resistivity and large electrostrictive strain, and can be widely applied to drivers and displacement brakes.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
The preparation component is 0.8BiFeO3-0.15BaTiO3-0.05Bi(Mg0.5Hf0.5)O3The lead-free piezoelectric ceramic material is prepared by the following steps:
to analytically pure BaCO3、TiO2、Bi2O3、Fe2O3、MgO、HfO2The raw materials are mixed and blended according to the target chemical composition, and are uniformly mixed and dried by adopting wet ball milling, wherein the raw materials comprise the following components in percentage by weight: agate ball: deionized water 1: 2: mixing at a ratio of 0.6-0.8, and performing planetary ball milling for 4-6 hours. Drying at 100 ℃, sieving with a 40-mesh sieve, and molding under the pressure of 3 MPa. Then placing the mixture in an alumina crucible and synthesizing the mixture by a solid phase method, heating the mixture to 800 ℃ at the speed of 5 ℃/min, preserving the heat for 5 hours, and cooling the mixture to room temperature along with the furnace temperature. The synthetic raw material is processedMechanically crushing, sieving with a 40-mesh sieve, and finely grinding by the same process as the mixing. Then adding a binder (polyvinyl alcohol PVA) accounting for 6% of the mass of the synthetic powder for granulation, forming under the pressure of 5MPa, aging for 24 hours, sieving by a 40-mesh sieve, and pressing under the pressure of 200MPa to prepare a green body. Heating the green body to 650 ℃ at the speed of 2 ℃/min, and preserving heat for 2 hours for plastic removal. After plastic removal, heating to 1000 ℃ at a speed of 5 ℃/min, keeping the temperature for 200min, sintering, and cooling to room temperature along with the furnace to obtain the lead-free piezoelectric ceramic material. And processing and cleaning the obtained ceramic wafer, preparing a double-sided silver paste electrode by screen printing, raising the temperature to 750 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 30 minutes for sintering.
The dielectric temperature spectrum, the hysteresis loop and the strain loop spectrum, and the temperature-change resistivity of the lead-free piezoelectric ceramic material prepared in this example 1 are shown in fig. 1, fig. 2 and fig. 3, respectively. The lead-free piezoelectric ceramic material has Curie temperature of 653 deg.c, electric strain of 0.03% and resistivity of 5.4 x 10 at 300 deg.c4Ω·cm。
Example 2
The preparation component is 0.75BiFeO3-0.2BaTiO3-0.05Bi(Mg0.5Hf0.5)O3The lead-free piezoelectric ceramic of (1) was prepared in the same manner as in example 1.
The dielectric temperature spectrum, the electrical hysteresis loop, the strain loop and the temperature-change resistivity of the lead-free piezoelectric ceramic material prepared in the embodiment 2 are respectively shown in fig. 1, fig. 2 and fig. 3. The obtained leadless piezoelectric ceramic has Curie temperature of 630 deg.C, electrostrictive strain of 0.06%, and resistivity of 1 × 10 at 300 deg.C5Ω·cm。
Example 3
The preparation component is 0.7BiFeO3-0.25BaTiO3-0.05Bi(Mg0.5Hf0.5)O3The lead-free piezoelectric ceramic of (1) was prepared in the same manner as in example 1.
The dielectric temperature spectrum, the electrical hysteresis loop, the strain loop and the temperature-change resistivity of the lead-free piezoelectric ceramic material prepared in this example 3 are respectively shown in fig. 1, fig. 2 and fig. 3. The obtained leadless piezoelectric ceramic has Curie temperature of 616 deg.C, electrostriction of 0.16%, and resistivity of 5.7 × 10 at 300 deg.C5Ω·cm。
Example 4
The preparation component is 0.6BiFeO3-0.35BaTiO3-0.05Bi(Mg0.5Hf0.5)O3The lead-free piezoelectric ceramic of (1) was prepared in the same manner as in example 1.
The dielectric temperature spectrum, the electrical hysteresis loop, the strain loop and the temperature-change resistivity of the lead-free piezoelectric ceramic material prepared in this example 4 are respectively shown in fig. 1, fig. 2 and fig. 3. The obtained lead-free piezoelectric ceramic has Curie temperature of 350 deg.C, electrostriction of 0.24%, and resistivity of 3.8 × 10 at 300 deg.C6And omega cm, compared with the piezoelectric ceramics prepared in the embodiments 1-3 and the comparative example 1, the resistivity and the electrostrictive strain are both obviously improved.
Example 5
The preparation component is 0.693BiFeO3-0.297BaTiO3-0.01Bi(Mg0.5Hf0.5)O3The lead-free piezoelectric ceramic of (1) was prepared in the same manner as in example 1.
The hysteresis loop and the strain loop 4a of the lead-free piezoelectric ceramic material prepared in this example 5 are shown. The electrical strain of the obtained lead-free piezoelectric ceramic is 0.17%, and compared with the piezoelectric ceramic prepared in examples 6 and 7 and the piezoelectric ceramic prepared in comparative example 2, the electrical strain is obviously improved, which shows that the electrical strain of the material can be improved by doping a proper amount of BMH. But the electrostrictive strain was small as compared with the piezoelectric ceramic prepared in example 4.
Example 6
The preparation component is 0.686BiFeO3-0.294BaTiO3-0.02Bi(Mg0.5Hf0.5)O3The lead-free piezoelectric ceramic of (1) was prepared in the same manner as in example 1.
The hysteresis loop and the strain loop 4b of the lead-free piezoelectric ceramic material prepared in this example 6 are shown. The electrical strain of the obtained lead-free piezoelectric ceramic is 0.16%, and compared with the piezoelectric ceramic prepared in the comparative example 2, the electrical strain is obviously improved.
Example 7
The preparation component is 0.679BiFeO3-0.291BaTiO3-0.03Bi(Mg0.5Hf0.5)O3The lead-free piezoelectric ceramic of (1) was prepared in the same manner as in example 1.
The hysteresis loop and the strain loop 4c of the lead-free piezoelectric ceramic material prepared in this example 7 are shown. The electrical strain of the obtained lead-free piezoelectric ceramic is 0.14%, and compared with the piezoelectric ceramic prepared in the comparative example 2, the electrical strain is slightly improved.
Comparative example 1
The preparation component is 0.75BiFeO3-0.25BaTiO3The preparation method of the piezoelectric ceramic material undoped with BMH is the same as that of example 1. The electrical return and strain are shown in figure 5 a.
Comparative example 2
The preparation component is 0.7BiFeO3-0.3BaTiO3The preparation method of the piezoelectric ceramic material undoped with BMH is the same as that of example 1, and the ferroelectric hysteresis loop and strain are shown in FIG. 5 b.
Table 1 shows the composition and performance parameters of the bismuth ferrite-barium titanate-based lead-free piezoelectric ceramic material:
the temperature-variable resistivity data is obtained by combining a German Novocontrol Technologies impedance analyzer with Novotherm-HT, the electric loop and the strain are obtained by adopting a German TFAnalyzer2000 ferroelectric analyzer, and the dielectric temperature data is obtained by connecting an Agilent precision impedance analyzer with a GJW-1 high-temperature dielectric temperature spectrum testing system.
Claims (10)
1. The bismuth ferrite-barium titanate-based lead-free piezoelectric ceramic material is characterized in that the chemical composition of the bismuth ferrite-barium titanate-based lead-free piezoelectric ceramic material is xBiFeO3-yBaTiO3-zBi(Mg0.5Hf0.5)O3(ii) a Wherein x + y + z =1, x = 0.6-0.85, y = 0.15-0.35, and z = 0-0.05.
2. The bismuth ferrite-barium titanate-based lead-free piezoelectric ceramic material according to claim 1, wherein x =0.25 to 0.35.
3. The bismuth iron-barium titanate-based lead-free piezoelectric ceramic material according to claim 1, wherein the resistivity of the bismuth iron-barium titanate-based lead-free piezoelectric ceramic material at 300 ℃ is greater than 104Preferably > 106；
The Curie temperature of the bismuth ferrite-barium titanate-based lead-free piezoelectric ceramic material is more than 300 ℃;
the electrical strain of the bismuth ferrite-barium titanate-based lead-free piezoelectric ceramic material is more than or equal to 0.02 percent, preferably more than 2 percent.
4. A method for preparing a bismuth ferrite-barium titanate-based piezoelectric ceramic material according to any one of claims 1 to 3, wherein Fe is used2O3、Bi2O3、BaCO3、TiO2、MgO、HfO2The powder is used as a raw material, and the chemical composition (0.95-x-y) BiFeO of the bismuth ferrite-barium titanate-based lead-free piezoelectric ceramic material is adopted3-xBaTiO3-yBi(Mg0.5Hf0.5)O3And (3) carrying out material mixing, synthesis, fine grinding, granulation, molding, plastic discharge and sintering to obtain the bismuth ferrite-barium titanate-based lead-free piezoelectric ceramic material.
5. The preparation method according to claim 4, characterized in that the mixing and fine grinding are performed by wet ball milling; wherein, the raw materials: ball milling medium: the mass ratio of the deionized water is 1: (1.6-2.4): (0.8-1.2) and performing planetary ball milling and mixing for 2-6 hours at the rotating speed of 300-400 rpm, wherein the preferred ball milling medium is agate balls.
6. The preparation method according to claim 4, wherein the synthesis temperature is 700-850 ℃ and the synthesis time is 4-6 hours; preferably, the temperature rise rate of the synthesis is 4-6 ℃/min.
7. The preparation method according to claim 4, characterized in that a binder accounting for 5-10% of the mass of the synthesized ceramic powder is added in the granulation process for granulation; preferably, the binder is a polyvinyl alcohol solution with a concentration of 4-8 wt.%.
8. The preparation method according to claim 4, wherein the temperature of the plastic discharge is 600-800 ℃, and the temperature is kept for 3 hours; preferably, the temperature rise rate of the plastic discharge is not higher than 2 ℃/min.
9. The preparation method according to claim 4, wherein the sintering temperature is 980-1030 ℃ and the sintering time is 2-5 hours.
10. The production method according to any one of claims 4 to 9, wherein the obtained bismuth ferrite-barium titanate-based lead-free piezoelectric ceramic material is subjected to electrode production; preferably, the electrode is a silver paste electrode, the sintering condition of the electrode is 700-800 ℃, and the temperature is kept for less than 60 minutes.
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