CN1994966B - Laminated structure bismuth piezoelectric ceramic material stably used under high temperature and its preparation method - Google Patents

Laminated structure bismuth piezoelectric ceramic material stably used under high temperature and its preparation method Download PDF

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CN1994966B
CN1994966B CN200610147892A CN200610147892A CN1994966B CN 1994966 B CN1994966 B CN 1994966B CN 200610147892 A CN200610147892 A CN 200610147892A CN 200610147892 A CN200610147892 A CN 200610147892A CN 1994966 B CN1994966 B CN 1994966B
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ceramic material
laminated structure
piezoelectric ceramic
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temperature
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CN1994966A (en
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李玉臣
包绍明
周志勇
姚烈
董显林
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention discloses a bismuth-layer shaped structure piezo-electric ceramic material and making method under high temperature, whose general chemical formula is Bi2O22+ (Am-1BmO3m+1)2, wherein the relative chemical formula of CaBi4Ti4O15 is (Bi2O2)2+ (CaBi2Ti4O13)2+; the position A is Ca2+, Bi3+ ; the position B is Ti4+; m is 4. The invention can shape kinds of piezo-electric ceramic element with epsilon33T/epsilon0 at130, tan delta at 0.10%, Tc at 782 deg. c,d33 at 19pC/N, rho v(480DEG C) at 1*109 omega.cm, which can be used repeatedly when the indoor temperature is 480 DEG C.

Description

Laminated structure bismuth piezoelectric ceramic material that a kind of high temperatures uses and preparation method thereof
Technical field
The present invention relates to laminated structure bismuth piezoelectric ceramic material of a kind of high temperatures use and preparation method thereof, belong to the piezoelectric ceramics field.
Background technology
To the detection of vibratory magnitude, almost relate to each engineering field.Detect the just essential vibration-measuring sensor of vibration, piezoelectric accelerometer is wherein to use one of the widest, that kind is maximum transmitter.In the vibration detection of visual plants such as thermoelectricity power unit, metallurgical rolling mill and steel plate rolling machine, aircraft engine, naval vessel high-speed diesel engine and other large-scale running device, all be unable to do without the high-temperature piezoelectric jerkmeter.Wherein usage quantity is maximum is 300 ℃~500 ℃ high-temperature piezoelectric jerkmeter, and what wherein airline needed is 480 ℃ of high-temperature piezoelectric jerkmeters.But at home, do not have still at present that performance is good, use temperature is higher than 300 ℃ high-temperature piezoelectric product sensor.Even also have only only a few producers such as U.S. Endevco company, Denmark B&K company and Switzerland Kistler company can produce this type device abroad; Therefore price is very expensive; So that China has to spend a large amount of foreign exchanges every year from external import high-temperature piezoelectric jerkmeter; Be used for the state-detection and the monitoring of minority key equipment, and these companies often carry out strict product embargo and technical know-how to China.
The high-temperature piezoelectric stupalith is the basis and the core parts of high-temperature piezoelectric jerkmeter.China just actively develops the research and development to the high-temperature piezoelectric jerkmeter from the end of the seventies; But, develop to the technology platform more than 400 ℃ thereby limited the high-temperature piezoelectric jerkmeter because of the research work of wherein the most key core parts-high-temperature piezoelectric stupalith does not obtain substantive breakthroughs.This has proposed higher requirement to piezoceramic material: (1) at high temperature has higher body resistivity; (2) at high temperature has certain high piezoelectricity (common d 33>=10pc/N); (3) electric capacity is little with variation of temperature, has good performance temperature stability.In order to satisfy the requirements at the higher level that practical application proposes, we have carried out more deep research to material.
Summary of the invention
The object of the present invention is to provide a kind of piezoceramic material that can at high temperature stablize use.When component design, take all factors into consideration Several Factors: 1, (Na, Bi) Ca of compound replacing section are adopted in the A position 2+2, reduce Ca 2+Content forms A position Ca 2+Ion vacancy; 3, Nb is adopted in the B position 5+, W 6+Replace Ti Deng high valence ion 4+4, add CeO 2, Sb 2O 3With one or more the compound additives among the CoO; 5, the improvement of technology.
Concrete preparation method is: with Ca (OH) 2(CP), Bi 2O 3(high-purity), TiO 2(electrical condenser specification), Na 2CO 3(CP), CoO (CP), Sb 2O 3(CP), CeO 2(CP), Nb 2O 5(technical pure), WO 3(CP) is raw material, presses Ca 1-x-a(NaBi) X/2Bi 4Ti 4-y-zNb yW zO 15+ bmol%CeO 2+ cmol%Sb 2O 3The stoichiometry weighing of+dmol%CoO, wherein 0.0≤x≤0.8,0.0≤y≤0.8; 0.0≤z≤0.8,0.0≤a≤0.2,0.0≤b≤5; 0.0≤c≤2.0,0.0≤d≤2.0, with alcohol as medium; Through planetary ball mill 1~6 hour; The unlimited powder of 700-900 ℃ then/1-4 hour is synthetic, again through planet fine grinding, oven dry, adding additives, moulding (forming pressure is 150~200MPa), plastic removal (800 ℃/1 hour), sintering (1000~1350 ℃/1~4 hour), cold working, ultrasonic cleaning, top electrode, polarization (80~200 ℃, 6~16kv/mm; 10~30 minutes), carry out performance test at last, can obtain the piezo ceramic element that supply to use.
Effect of the present invention is: obtained a kind of DIELECTRIC CONSTANTS 33 T/ ε 0=130 ± 10, dielectric loss tan δ≤0.10%, Tc T c=782 ℃, piezoelectric coefficient d 33=19 ± 1pC/N, body resistivity ρ V (480 ℃)=1 * 10 9The high temperature high Stability Piezoelectric Ceramic Materials of Ω cm.
Table 1 is ceramic component of the present invention electrical capacity C and piezoelectric coefficient d after thermal treatment 33Variation.
Table 1
Figure GSB00000442138900031
Can find out that from table 1 ceramic component of the present invention is through long pyroprocessing, electrical capacity C and piezoelectric coefficient d 33Almost do not change, and the body resistivity of stupalith of the present invention under high temperature (480 ℃) reaches 1 * 10 9Ω cm is that a kind of good pyrostat is used piezoceramic material.
Table 2 is Shanghai silicate institute (core parts use this patent material) and U.S. Endevco company piezoelectric transducer probe performance comparison table.
Table 2
The U.S. 2273AM1 of Endevco company type GYD-1
Output sensitivity (pC/g) 10 10~20
Frequency response (Hz) 1~6000 ~5000
Impact linear (ms -2) 3000 3000
Weight (g) 32 ~40
Use temperature (℃) -55~482 Normal temperature~480
Error (300 ℃ time maximum) 8% (480 ℃ of maximums) 5.35%
Resistance (normal temperature) >1GΩ >1GΩ
Resistance (480 ℃) >100KΩ >100KΩ
Description of drawings
Fig. 1 is the dielectric temperature spectral curve of this patent material.
Embodiment
Embodiments of the invention are following:
With Ca (OH) 2(CP), Bi 2O 3(high-purity), TiO 2(electrical condenser specification), Na 2CO 3(CP), CoO (CP), Sb 2O 3(CP), CeO 2(CP), Nb 2O 5(technical pure), WO 3(CP) is raw material, presses Ca 1-x-a(NaBi) X/2Bi 4Ti 4-y-zNb yW zO 15+ bmol%CeO 2+ cmol%Sb 2O 3The stoichiometry weighing of+dmol%CoO is as x=0.12,0.10,0.08,0.12,0.10,0.08; Y=0.06, a=0.01, b=0.5, c=0.4, d=0.6; Z=0.05,0.05,0.05,0.1,0.1,0.1 prepares burden respectively; With alcohol as medium; Wasted 1~6 hour through the planet ball; The unlimited powder of 700-900 ℃ then/1-4 hour is synthetic, again through planet fine grinding, oven dry, adding additives, moulding (forming pressure is 150~200MPa), plastic removal (800 ℃/1 hour), sintering (1000~1350 ℃/1~4 hour), cold working, ultrasonic cleaning, top electrode, polarization (80~200 ℃, 6~16kv/mm; 10~30 minutes), carry out performance test at last, can obtain the piezo ceramic element that supply to use.
Table 3 has been listed the prescription and the result of present embodiment.
Table 3
Figure GSB00000442138900041

Claims (3)

1. the laminated structure bismuth piezoelectric ceramic material that uses of a high temperatures, its prescription is Ca 1-x- a(NaBi) X/2Bi 4Ti 4-y-zNb yW zO 15+ bmol%CeO 2+ cmol%Sb 2O 3+ dmol%CoO, wherein 0.0<x≤0.8,0.0<y≤0.8,0.0<z≤0.8,0.0<a≤0.2,0.0<b≤5,0.0<c≤2.0,0.0<d≤2.0 is characterized in that Na and the compound replacement portion C of Bi a are adopted in the A position 2+Reduce Ca 2+Content forms A position Ca 2+Ion vacancy.
2. the preparation method of the laminated structure bismuth piezoelectric ceramic material that uses by the described a kind of high temperatures of claim 1 comprises ball-milling technology, synthetic, sintering, polarization process, it is characterized in that:
(1) adopts planetary ball mill technology;
(2) opening wide calcined powder synthesizes;
(3) sintering temperature is 1000-1350 ℃, is incubated 0.5-4 hour;
(4) polarization condition: temperature 80-200 ℃, voltage 6-16kV/mm, time 10-30 minute.
3. the preparation method of the laminated structure bismuth piezoelectric ceramic material that uses by the described a kind of high temperatures of claim 2 comprises ball-milling technology, synthetic, sintering, polarization process, it is characterized in that the synthetic powder condition is 700-900 ℃ of calcining 1-4 hour.
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CN104529435B (en) * 2014-12-26 2018-03-30 中国科学院声学研究所 Laminated structure bismuth piezoelectric ceramic material and preparation method thereof
CN104725078B (en) * 2015-03-12 2016-08-24 中国科学院上海硅酸盐研究所 Improve piezoelectric property and the method for its temperature stability of laminated structure bismuth piezoelectric ceramic material
CN105837200A (en) * 2016-04-05 2016-08-10 四川大学 Manganese-doped cerium lithium calcium titanoniobate-based ceramic material and preparation method thereof
CN109369174B (en) * 2018-11-01 2021-04-16 中国科学院上海硅酸盐研究所 Bismuth layer-structured high-temperature piezoelectric ceramic material and preparation method thereof
CN111362691A (en) * 2020-03-14 2020-07-03 杭州电子科技大学 Bismuth calcium titanate high-temperature piezoelectric ceramic material with bismuth layer-structured structure and preparation method thereof
CN114455944B (en) * 2022-01-28 2022-11-11 厦门乃尔电子有限公司 Bismuth layer-structured piezoelectric ceramic material and preparation method thereof

Citations (4)

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Publication number Priority date Publication date Assignee Title
CN1226539A (en) * 1998-12-18 1999-08-25 中国科学院上海硅酸盐研究所 Laminated ceramical composition containing composite substituted bismuth and preparation thereof
JP2000178068A (en) * 1998-12-17 2000-06-27 Matsushita Electric Ind Co Ltd Piezoelectric porcelain composition
CN1424283A (en) * 2002-12-27 2003-06-18 中国科学院上海硅酸盐研究所 High-temperature piezoelectric ceramic compositions
JP2003176176A (en) * 2001-12-12 2003-06-24 Foundation For The Promotion Of Industrial Science Bismuth layer structure ferroelectric, method of producing the same, memory element and dielectric/ electrostrictive element using the ferroelectric

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
JP2000178068A (en) * 1998-12-17 2000-06-27 Matsushita Electric Ind Co Ltd Piezoelectric porcelain composition
CN1226539A (en) * 1998-12-18 1999-08-25 中国科学院上海硅酸盐研究所 Laminated ceramical composition containing composite substituted bismuth and preparation thereof
JP2003176176A (en) * 2001-12-12 2003-06-24 Foundation For The Promotion Of Industrial Science Bismuth layer structure ferroelectric, method of producing the same, memory element and dielectric/ electrostrictive element using the ferroelectric
CN1424283A (en) * 2002-12-27 2003-06-18 中国科学院上海硅酸盐研究所 High-temperature piezoelectric ceramic compositions

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