CN1546427A - Doped lead antimony manganese zirconia titanate piezoelectric ceramic materials suitable for industrial production and method for preparing same - Google Patents

Doped lead antimony manganese zirconia titanate piezoelectric ceramic materials suitable for industrial production and method for preparing same Download PDF

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CN1546427A
CN1546427A CNA2003101091387A CN200310109138A CN1546427A CN 1546427 A CN1546427 A CN 1546427A CN A2003101091387 A CNA2003101091387 A CN A2003101091387A CN 200310109138 A CN200310109138 A CN 200310109138A CN 1546427 A CN1546427 A CN 1546427A
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lead antimony
zirconia titanate
doped lead
antimony manganese
piezoelectric ceramic
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CN1260175C (en
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李国荣
朱志刚
殷庆瑞
郑嘹赢
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention relates to a doping lead antimony manganese zirconia titanate piezoelectric ceramic material suitable for industrial mass production which comprises, charging silicon oxide, cerium oxide and chromium oxide as additive to lead antimony manganese zirconia titanate (PMS-PZT) piezo-electric ceramic material, wherein the sintering temperature being 1200 deg. C - 1600 deg. C. The ceramic material is especially suitable for use as the multilayer co-combustion ceramic device for internal electrodes in large power ceramic devices and Ag/Pd.

Description

Be fit to doped lead antimony manganese zirconia titanate piezoceramic material of suitability for industrialized production and preparation method thereof
Technical field
The present invention relates to doped lead antimony manganese zirconia titanate piezoceramic material of a kind of suitable suitability for industrialized production and preparation method thereof, belong to the piezoceramic material field.
Background technology
The PZT pottery is one of present the most widely used commercial electronic material.In recent years, application development at the high-power aspects of using down such as piezoelectric ceramic actuator, transformer, micro positioner, motor and various ultrasonic transducers is very rapid, this just requires piezoceramic material can export bigger power under free state or tension stress, has high electromechanical coupling factor K p, the mechanical quality factor Q m, piezoelectric constant d 33And low dielectric loss Tan δ, should possess high physical strength and time, temperature stability simultaneously.
The sintering temperature of leaded PZT pottery is generally 1200-1300 ℃ and since sintering temperature when too high lead volatile, cause the nonstoichiometry ratio, cause ceramic performance to be difficult to control; And plumbous volatilization causes environmental pollution, healthy very harmful to the mankind.Widely used in recent years piezoceramic multilayer device (as piezoelectric actuator, piezoelectric transformer etc.) because its sintering temperature height all uses precious metals such as platinum, palladium as interior electrode usually, has improved use cost greatly.Therefore, at the piezoelectric property that does not reduce material (high K p, Q m, ε 33 T) and the situation of physical strength under, by mixing or modification reduces the sintering temperature of high power piezoelectric ceramic material, to the preparation of material and use particularly that the application of multilayer co-firing piezoelectric ceramic devices has very important significance.
Clear 42-25276 of Japanese Patent and 42-66779 have introduced the Pb (Mn that different ingredients is formed 1/3Sb 2/3) O 3-PbTiO 3-PbZrO 3The piezoelectric property of stupalith, but its sintering temperature is all between 1200-1300 ℃, and this is restricted their application in the multilayer co-firing piezoelectric ceramic devices.
Guo Xiaobo, Meng Zhongyan etc. (silicate journal 2,002 30 (1) 125-127) have studied Pb 1-xSr x(Mn 1/3Sb 2/3) aZr bTi cO 3The piezoelectric property of material, this material is piezoelectric property the best when 1200 ℃ of sintering, but when temperature when being lower than this temperature, K p, Q m, ε 33 TDescend significantly Deng all having, wherein Q mValue has only 850 when burning till for 1150 ℃.It is narrow and unstable that this material can satisfy the sintering range of performance requriements, and significant discomfort is used for the application of suitability for industrialized production.In addition, because its sintering temperature is higher relatively, need to use the very high even interior electrode of precious metal 100% of Pd.
Chinese patent 85100051 reported in the PZT two component system and to have added B-Bi-Cd low-melting-point glass material, develops 960-1000 ℃ of following low-temperature sintering and has the material of good piezoelectric property.Chinese patent 86108741 has reported that niobium nickel lead zirconate titanate piezoelectric material adds SiO 2, MnO 2And excessive PbO, sintering temperature can be reduced to 840-1000 ℃, and has good piezoelectric property.Above two China patent report under the prerequisite that does not reduce piezoelectric property, can reduce the sintering temperature of stupalith, but the mechanical quality factor of these materials has only 800-1000, and does not illustrate and reduce the influence of ceramic sintering temperature ceramic machinery intensity.
For high power piezoelectric ceramic material, its amplitude when the resonance working order is bigger, must have high physical strength.Therefore, how when reducing the stupalith sintering temperature, take into account piezoelectric property, machinery and electrical losses and the physical strength of material, just become a great problem anxious to be solved.
Summary of the invention
The object of the present invention is to provide a kind of piezoceramic material with middle low temperature (1100-1200 ℃) sintering characteristic, this material has higher piezoelectric constant d 33, electromechanical coupling factor K p, the mechanical quality factor Q m, DIELECTRIC CONSTANT 33 T, and physical strength, can use at the high-power piezoelectric ceramic device and in the piezoceramic multilayer common burning porcelain device of Ag/Pd as interior electrode.
Specifically, low temperature sintering piezoelectric ceramics provided by the invention consists of
Pb 1-aSr a(Mn 1/3Sb 2/3) bZr cTi dO 3+N?wt％M xO y，
Wherein: 0≤a≤0.1,0＜b≤0.1,0.4≤c≤0.5,0.4≤d≤0.5,0.01≤N≤1, b+c+d=1.This doping oxide MxOy is SiO 2, CeO 2, Cr 2O 3In a kind of, two or three, the material after the doping still keeps cubic phase perovskite structure.
Preparation technology of the present invention is with chemical pure Pb 3O 4, SrCO 3, MnCO 3, Sb 2O 3, ZrO 2, TiO 2, SiO 2, Cr 2O 3, CeO 2Be raw material,, mix back ball milling, drying, 850-900 ℃ of pre-synthetic 1-2h according to the accurate weighing of stoichiometric.Pulverize the back fine grinding, the fineness of powder is at 0.5-1 μ m.The oven dry back adds 5-10%PVA as binding agent, granulation, at 1-2T/cm 2Pressure under dry-pressing formed be the rectangular of the disk of φ 12 * 1mm and 36 * 4 * 3mm.The plastic removal temperature is 800-850 ℃, insulation 1-2h.Sintering temperature is 1100-1200 ℃, insulation 1-2h.Disk is machined to 0.5mm, cleans the two-sided silver electrode that plates in back, and the 20-30min that polarizes in 130 ℃ silicone oil, polarized electric field are 2.5-3.5KV/mm.Polarized sample is tested every performance after placing 24h.Rectangularly be used for doing bending strength test.
The characteristics of this piezoceramic material are:
1. material can use 70Ag/30Pd even lower Pd ratio as interior electrode at densified sintering product under the lower temperature (1100-1200 ℃), greatly reduces cost; And the material property of sintering preparation is stable in this temperature range, can overcome temperature deviation to effect of material performance, is fit to very much need of industrial production.
2. material has good piezoelectric property: d 33=300-400 PC/N, K p=0.5-0.6, Q m=1500-1800, ε 33 T=1100-1400, Tan δ≤0.5%;
3. the mechanical property of material satisfies the actual needs that use: bending strength is at 70-110MPa.
4. be applicable to the sintering range of broad, performance index difference is less behind 1100-1200 ℃ of following sintering, can satisfy the actual needs of suitability for industrialized production.
Description of drawings
Fig. 1 is the piezoceramic material typical X RD collection of illustrative plates that the present invention proposes, and as can be seen from the figure, the material after the doping still keeps cubic phase perovskite structure.
Embodiment
Further set forth characteristics of the present invention below by embodiment, but content of the present invention is not limited thereto.
Embodiment 1
With Pb 3O 4, SrCO 3, MnCO 3, Sb 2O 3, ZrO 2, TiO 2, SiO 2, CeO 2, (chemical pure) be raw material, presses Pb 0.95Sr 0.05(Mn 1/3Sb 2/3) 0.03Zr 0.50Ti 0.47O 3+ 0.2wt%SiO 2+ 0.5wt%CeO 2The stoichiometry weighing, adopt general ceramic preparation technology to prepare burden, synthetic in advance after ball milling, mixing, the oven dry (850 ℃/2h), fine grinding 10h, drying, adding additives, moulding (forming pressure 2T/cm 2), plastic removal (850 ℃/1h), sintering (1100-1200 ℃/2h).Form the as above piezoceramic material of the cubic phase perovskite structure of prescription.
Table 1 is embodiment 1 piezoelectric property of (1100-1200 ℃) under differing temps.
Table 1
Sintering temperature (℃) ????K p ???Q m ???d 33?(PC/N) ?ε 33 T ?tanδ(％) ????ρ ??(g/cm 3)
??1100 ??0.535 ??1756 ??310 ??1122 ????0.7 ???7.49
??1120 ??0.548 ??1704 ??318 ??1183 ????0.7 ???7.52
??1140 ??0.550 ??1635 ??326 ??1271 ????0.5 ???7.65
??1160 ??0.567 ??1605 ??339 ??1320 ????0.5 ???7.72
??1180 ??0.581 ??1548 ??356 ??1375 ????0.4 ???7.81
??1200 ??0.596 ??1497 ??364 ??1406 ????0.4 ???7.89
Embodiment 2
By prescription Pb 0.97Sr 0.03(Mn 1/3Sb 2/3) 0.05Zr 0.48Ti 0.47O 3+ 0.2wt%SiO 2+ 0.6wt%CeO 2+ 0.5wt%Cr 2O 3Accurate proportioning, preparation technology is with embodiment 1, and sintering temperature is 1140 ℃, and its piezoelectric property is: ε 33 T=1356, K p=0.576, Q m=1750, d 33=341PC/N, tan δ=0.7%.
Embodiment 3
By prescription Pb 0.99Sr 0.01(Mn 1/3Sb 2/3) 0.08Zr 0.46Ti 0.46O 3+ 0.8wt%SiO 2+ 0.5wt%CeO 2+ 0.6wt%Cr 2O 3Accurate proportioning, preparation technology is with embodiment 1, and sintering temperature is 1140 ℃, and its piezoelectric property is: ε 33 T=1324, K p=0.568, Q m=1678, d 33=352PC/N, tan δ=0.4%.
Table 2 is the piezoelectric property of embodiment 1-3 and the comparison of mechanical property.
Table 2
????K p ????Q m ???d 33?(PC/N) ?ε 33 T ??tanδ ??(％) Bending strength (MPa)
Embodiment 1 ???0.550 ??1635 ??326 ??1271 ???0.5 ????86
Embodiment 2 ???0.576 ??1750 ??341 ??1356 ???0.7 ????94
Embodiment 3 ???0.568 ??1678 ??352 ??1324 ???0.4 ????103
(sintering temperature is 1140 ℃, insulation 2h)
As can be seen, (1100-1200 ℃) can both sintering in quite wide firing temperature for material, and has piezoelectricity and mechanical property preferably from table 1, table 2.Illustrating that this material can adapt in high-power piezoelectric ceramic device and piezoceramic multilayer common burning porcelain device uses, and is very suitable for industrial production.

Claims (4)

1, the doped lead antimony manganese zirconia titanate piezoceramic material that is fit to suitability for industrialized production is characterized in that the Pb that consists of of material 1-aSr a(Mn 1/3Sb 2/3) bZr cTidO 3+ Nwt%M xO y, wherein: 0≤a≤0.1,0＜b≤0.1,0.4≤c≤0.5,0.4≤d≤0.5,0.01≤N≤1, b+c+d=1, M xO yBe SiO 2, CeO 2, Cr 2O 3In a kind of, two or three.
2, by the preparation method of the doped lead antimony manganese zirconia titanate piezoceramic material of the described suitable suitability for industrialized production of claim 1, comprise batching, mixings, synthesize in advance, moulding, sintering, it is characterized in that:
(1) presses Pb 1-aSr a(Mn 1/3Sb 2/3) bZr cTi dO 3+ Nwt%M xO yThe proportioning raw material, wherein: 0≤a≤0.1,0＜b≤0.1,0.4≤c≤0.5,0.4≤d≤0.5,0.01≤N≤1, b+c+d=1, M xO yBe SiO 2, CeO 2, Cr 2O 3In a kind of, two or three;
(2) raw material that uses is Pb 3O 4, SrCO 3, MnCO 3, Sb 2O 3, ZrO 2, TiO 2, SiO 2, Cr 2O 3, CeO 2
(3) sintering temperature is 1100-1200 ℃, insulation 1-2h.
3, press the preparation method of the doped lead antimony manganese zirconia titanate piezoceramic material of the described suitable suitability for industrialized production of claim 2, fine grinding after the raw material pulverizing after it is characterized in that synthesizing in advance, the fineness of powder is controlled at 0.5-1 μ m.
4, press the preparation method of the doped lead antimony manganese zirconia titanate piezoceramic material of the described suitable suitability for industrialized production of claim 2, it is characterized in that used raw material is an analytical pure.
CN 200310109138 2003-12-05 2003-12-05 Doped lead antimony manganese zirconia titanate piezoelectric ceramic materials suitable for industrial production and method for preparing same Expired - Fee Related CN1260175C (en)

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EP1875526A1 (en) * 2005-04-11 2008-01-09 Piezotech, LLC Compositions for high power piezoelectric ceramics
CN100422110C (en) * 2007-04-26 2008-10-01 浙江大学 Seepage type Ag-PbTiO3 composite ceramic film and preparation method therefor
CN101885611A (en) * 2010-07-29 2010-11-17 西安理工大学 Method for preparing piezoelectric material for roads by spraying technology
CN101913866A (en) * 2010-08-18 2010-12-15 郴州功田电子陶瓷技术有限公司 Gas ignition piezoelectric ceramics and manufacture process thereof
CN101948309A (en) * 2010-08-20 2011-01-19 暨南大学 PPSMZT-doped piezoelectric ceramic, preparation method thereof and use thereof
CN102260079A (en) * 2010-05-31 2011-11-30 中国科学院上海硅酸盐研究所 PZT-Pb (Sb2/3Mn1/3) ternary system piezoelectric ceramic material with dual usage of receiving/sending and its preparation method
CN101767994B (en) * 2010-01-18 2012-05-09 哈尔滨理工大学 Method for preparing modified lead zirconate titanate (PZT) piezoelectric ceramics powder
CN103467090A (en) * 2013-09-03 2013-12-25 瑞声精密制造科技(常州)有限公司 Piezoelectric ceramic material, sintered body and preparation method thereof, and piezoelectric ceramic device
CN104152997A (en) * 2013-05-14 2014-11-19 中国科学院上海硅酸盐研究所 Quaternary relaxation piezoelectric single crystal material and growing method thereof
CN106518070A (en) * 2016-10-19 2017-03-22 常州大学 Multicomponent-system high-piezoelectric-activity piezoelectric ceramic material and preparation method therefor
CN107226698A (en) * 2017-06-15 2017-10-03 华中科技大学 A kind of piezoceramic material and preparation method applied to underwater acoustic transducer
CN111704461A (en) * 2020-05-22 2020-09-25 江苏波速传感器有限公司 Formula and preparation method of high Curie point low temperature co-fired piezoelectric ceramic
CN114075073A (en) * 2020-08-17 2022-02-22 中国科学院上海硅酸盐研究所 PZT-Pb (Sb)1/2Nb1/2) Ternary system piezoelectric ceramic material and preparation method and application thereof
CN115417671A (en) * 2022-07-07 2022-12-02 南京航空航天大学 Lead zirconate titanate based piezoelectric ceramic for high-power scene and preparation method thereof

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EP1875526A4 (en) * 2005-04-11 2011-01-05 Piezotech Llc Compositions for high power piezoelectric ceramics
EP1875526A1 (en) * 2005-04-11 2008-01-09 Piezotech, LLC Compositions for high power piezoelectric ceramics
CN100422110C (en) * 2007-04-26 2008-10-01 浙江大学 Seepage type Ag-PbTiO3 composite ceramic film and preparation method therefor
CN101767994B (en) * 2010-01-18 2012-05-09 哈尔滨理工大学 Method for preparing modified lead zirconate titanate (PZT) piezoelectric ceramics powder
CN102260079B (en) * 2010-05-31 2013-10-02 中国科学院上海硅酸盐研究所 PZT-Pb (Sb2/3Mn1/3) ternary system piezoelectric ceramic material with dual usage of receiving/sending and its preparation method
CN102260079A (en) * 2010-05-31 2011-11-30 中国科学院上海硅酸盐研究所 PZT-Pb (Sb2/3Mn1/3) ternary system piezoelectric ceramic material with dual usage of receiving/sending and its preparation method
CN101885611A (en) * 2010-07-29 2010-11-17 西安理工大学 Method for preparing piezoelectric material for roads by spraying technology
CN101885611B (en) * 2010-07-29 2013-04-17 西安理工大学 Method for preparing piezoelectric material for roads by spraying technology
CN101913866A (en) * 2010-08-18 2010-12-15 郴州功田电子陶瓷技术有限公司 Gas ignition piezoelectric ceramics and manufacture process thereof
CN101913866B (en) * 2010-08-18 2012-08-01 郴州功田电子陶瓷技术有限公司 Gas ignition piezoelectric ceramics and manufacture process thereof
CN101948309A (en) * 2010-08-20 2011-01-19 暨南大学 PPSMZT-doped piezoelectric ceramic, preparation method thereof and use thereof
CN104152997A (en) * 2013-05-14 2014-11-19 中国科学院上海硅酸盐研究所 Quaternary relaxation piezoelectric single crystal material and growing method thereof
CN104152997B (en) * 2013-05-14 2018-07-20 中国科学院上海硅酸盐研究所 Quaternary system relaxation type monocrystalline piezoelectric material and its growing method
CN103467090A (en) * 2013-09-03 2013-12-25 瑞声精密制造科技(常州)有限公司 Piezoelectric ceramic material, sintered body and preparation method thereof, and piezoelectric ceramic device
CN106518070A (en) * 2016-10-19 2017-03-22 常州大学 Multicomponent-system high-piezoelectric-activity piezoelectric ceramic material and preparation method therefor
CN106518070B (en) * 2016-10-19 2019-06-04 常州大学 A kind of polynary system high-voltage electricity active piezoelectric ceramic material and preparation method thereof
CN107226698A (en) * 2017-06-15 2017-10-03 华中科技大学 A kind of piezoceramic material and preparation method applied to underwater acoustic transducer
CN107226698B (en) * 2017-06-15 2018-04-20 华中科技大学 A kind of piezoceramic material and preparation method applied to underwater acoustic transducer
CN111704461A (en) * 2020-05-22 2020-09-25 江苏波速传感器有限公司 Formula and preparation method of high Curie point low temperature co-fired piezoelectric ceramic
CN114075073A (en) * 2020-08-17 2022-02-22 中国科学院上海硅酸盐研究所 PZT-Pb (Sb)1/2Nb1/2) Ternary system piezoelectric ceramic material and preparation method and application thereof
CN115417671A (en) * 2022-07-07 2022-12-02 南京航空航天大学 Lead zirconate titanate based piezoelectric ceramic for high-power scene and preparation method thereof

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