CN1562877A - Doped and modified piezoelectric ceramic of potassium sodium bismuth titanate and preparation method - Google Patents

Doped and modified piezoelectric ceramic of potassium sodium bismuth titanate and preparation method Download PDF

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Publication number
CN1562877A
CN1562877A CN 200410017308 CN200410017308A CN1562877A CN 1562877 A CN1562877 A CN 1562877A CN 200410017308 CN200410017308 CN 200410017308 CN 200410017308 A CN200410017308 A CN 200410017308A CN 1562877 A CN1562877 A CN 1562877A
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Prior art keywords
bismuth titanate
piezoelectric ceramics
preparation
sodium potassium
titanate piezoelectric
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CN100360466C (en
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王东
李永祥
陆毅青
王天宝
殷庆瑞
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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

Composed general formula of this kind of materials is Bi0.5NaxK0.5-xTiO3 (x=0.40-0.495). One or two kind of modified insition are mixed in the material for increasing material performance. The insitions includes Fe2O3, Cr2O3, La2O3, MnO2, CeO2, Nb2O5 and Sb2O3, mixed weight percentage ratio is 0.2-3. Traditional ceramics firing technology is utilized to do ball-milling to precomposed porcelain powder (precomposing temp. is 850-1000 deg.C, temp.-keeping time si 2-4 hours) until that particle size is in range of 400-800 nm, then to do firming 2-4 hours in temp. 1100-1200 deg.C. Said kind of material has characteristicsof high Kt value, large Kt/Kp value, high frequency constant Nt, moderate mechanical quality factor Qmt, smaller volume density and dielectric consant sigma 33T.

Description

A kind of doping vario-property sodium potassium bismuth titanate piezoelectric ceramics and preparation method thereof
Technical field
The present invention relates to a kind of doping vario-property sodium potassium bismuth titanate piezoelectric ceramics and preparation method thereof, belong to the piezoelectric ceramics field.
Background technology
The piezoelectricity ferro pottery has obtained to use widely in fields such as ultrasonic transduction, sensing, nondestructive testing and communications as the important composition of light, electricity, heat, force sensitive device.Traditional piezoelectricity ferro pottery all is plumbiferous ferroelectric ceramic(s) (as Pb-based lanthanumdoped zirconate titanates, lead lanthanum zirconate titanate, PMNT and a niobium zinc lead titanate etc.), and they all can give environment and the human infringement that brings to a certain degree in preparation and use.
In recent years, along with the demand of environment protection and human social, novel environmental close friend's ferroelectric piezoelectric ceramics has become one of focus material that world developed country endeavours to research and develop.Calendar year 2001, Europe parliament passed through the decree about " limiting objectionable impurities in electrical equipment and the electronics ", and implemented due to 2008.Wherein in the material that is limited to use, just comprise plumbiferous piezoelectric device.The U.S., Japan and China electronics and information industry portion also prepare by similar decree in succession, and have improved the supporting dynamics to development leadless piezoelectric ceramics project year by year.
The leadless piezoelectric ferroelectric ceramic(s) system of the report of various countries' research at present mainly contains: BaTiO 3Based leadless piezoelectric ceramics, Bi 0.5Na 0.5TiO 3(BNT) based leadless piezoelectric ceramics, niobate base lead-free piezoelectric ceramic, tungsten bronze structure leadless piezoelectric ceramics and bismuth laminated leadless piezoelectric ceramic etc., the system that application prospect is wherein arranged most is exactly the BNT based leadless piezoelectric ceramics.
People such as R.Jaffe had delivered Bi in 1971 0.5Na 0.5TiO 3(BNT) piezoelectric ferroelectric data of single constituent element pottery, after 2 years Tanaka wise man Lang Fabiao Bi 0.5K 0.5TiO 3(BKT) piezoelectric ferroelectric data of single constituent element pottery.Because the polarization of the single constituent element pottery of BNT and BKT is difficulty very, all can't obtain practical application.Robot systems such as Wang Tianbao had been studied Bi in 1985 0.5Na xK 0.5-xTiO 3The piezoelectricity ferro performance of the piezoelectric ceramics of compound system has obtained certain progress, but reasons such as the sign that can't polarize owing to preparation technology and preparation back sample do not make such piezoceramic material being applied in actual production.
Summary of the invention
The present invention is directed to Bi 0.5Na xK 0.5-xTiO 3The crystalline structure characteristics of series piezoelectric ceramic material and piezoelectric property characteristics, by the preparation technology of optimization material, and autotelic doped F e 2O 3, Cr 2O 3, La 2O 3, MnO 2, CeO 2, Nb 2O 5And Sb 2O 3Deng modified materials, make such material have high K t, big K t/ K pValue, high frequency constant N t, moderate mechanical quality factor Q m tAnd less DIELECTRIC CONSTANT 33 TAnd volume density.Thereby at the effect in fields such as industrial non-destructive test(ing)(NDT), thickness measuring, range finding and medical supersonic diagnosis significantly better than traditional Pb-based lanthanumdoped zirconate titanates (PZT) material.In existing document, still find no the report that closes this respect at present.
The composition general formula of novel lead-free piezoceramic material provided by the invention is Bi 0.5Na xK 0.5-xTiO 3(wherein x=0.40～0.495) mixes Fe simultaneously 2O 3, Cr 2O 3, La 2O 3, MnO 2, CeO 2, Nb 2O 5And Sb 2O 3Wait one or both modified materialses, the weight ratio of mixing is 0.2%～3%.Be x=0.42～0.47 best the composition, and mixing weight ratio simultaneously is 0.3%～1.5% one or both modified materialses.
The present invention realizes by being prepared as follows technology: select anhydrous sodium carbonate, Anhydrous potassium carbonate, bismuth oxide, titanium dioxide and Fe for use 2O 3, Cr 2O 3, La 2O 3, MnO 2, CeO 2, Nb 2O 5And Sb 2O 3Or the like one or both modified materialses make raw material, press the compositing formula weighing, be that with the dehydrated alcohol medium ball milling mixed 3 hours, the crucible of packing into behind 50 mesh sieves is crossed in discharging and oven dry, carries out synthetic in advance in 2～4 hours 850～1000 ℃ of insulations.After will synthesizing back powder piece (grog) grinding and crossing 20 mesh sieves still will be that the levigate powder particle size that is milled to of medium ball is between 400nm～800nm with the dehydrated alcohol.The discharging drying, and add the binding agent (can be polyvinyl alcohol, glycerine etc.) of 8～25wt% and cross 50 mesh sieves, precompressed granulation, dry-pressing or rolling formation.Base substrate after the moulding is warming up to 400-600 ℃ with the speed with 1-5 ℃/min, is incubated and is warming up to 1100～1200 ℃ after 0.5-3 hour, in atmosphere, opened wide sintering 2～4 hours.
To burn till sample two-sided by behind the electrode in silicone oil making alive polarize, press the piezoelectric property that ieee standard is measured sample.Table 1 has been listed the prescription and the performance thereof of 5 different x values and additive.Table 2 has been listed various ferroelectric, the piezoelectric property of representative formula.
As can be seen from Table 1, Bi 0.5Na xK 0.5-xTiO 3The common feature of (wherein x=0.40～0.495) series lead-free piezoelectric ceramic material is: have high thickness electromechanical coupling coefficient K t, relatively low planar electromechanical coupling factor K p, big K t/ K pValue, high thickness vibration frequency constant N tWith high Curie temperature T C, moderate mechanical quality factor Q m tAnd less DIELECTRIC CONSTANT 33 TBy above-mentioned system is carried out a spot of ion doping (as Fe 2O 3, MnO 2, CeO 2Deng), make it be fit to the application of concrete ultrasonic transducer more.X ray and electric Study on Physical to this system find that x=0.405 is its three parts-cubic phase boundary.
As can be seen from Table 2, this piezoceramic material has big K t/ K pValue has bigger anisotropy characteristics than general PZT pottery.During as the oscillator of thickness vibration, can reduce and remove unwanted vibration interference.The probe of the same race that single probe of making of its and PZT pottery commonly used are done is compared, and it is simple, clear to have a waveform, and no higher harmonic, the narrow and resolving power advantages of higher of ripple begins.The DIELECTRIC CONSTANT of this stupalith 33 TLower with volume density, make the not only easy and circuit coupling of probe with it, and help the specific acoustic resistance coupling.The aging resistance of this stupalith and temperature stability are all better in addition, can satisfy the needs of practical application.
Pottery of the present invention is produced as a trial on existing production line, production is the result show: sintering temperature is lower about 100 ℃ than PZT, and component volatilization is minimum, therefore can in air, open wide sintering, and do not need sealing or bury powder sintering, thereby technological process is simpler, and the consistence of sample performance is better.
Embodiment
Further specify substantive distinguishing features of the present invention and marked improvement below in conjunction with embodiment.Be noted that the present invention is not limited to following embodiment.
Embodiments of the invention are that x is prescription-Bi of 0.435 0.5Na 0.435K 0.065TiO 3, mix 0.5wt% (weight) CeO simultaneously 2, preparation process as previously mentioned.Pre-synthesis condition is 950 ℃ of insulations 3 hours, grog is levigate to the 700nm, in 1140 ℃～1180 ℃ atmosphere, opened wide sintering 3 hours then, the base sample is made the disk of ф 20 * 1mm, two-sided by silver, making alive polarizes in silicone oil, measures its piezoelectric property by ieee standard, and detailed results sees Table 3.
Table 1 Bi 0.5Na xK 0.5-xTiO 3Series piezoelectric ceramic prescription and salient features thereof
Prescription is formed ????K t ????K p ????ε 33 T/ε 0 ????Q m t ????T C????℃ ????N t???Hz·m
????Bi 0.5Na 0.405K 0.095TiO 3 ????0.40 ????0.33 ????782 ????62 ????289 ????2380
????Bi 0.5Na 0.435K 0.065TiO 3 ????0.44 ????0.24 ????527 ????80 ????290 ????2413
????Bi 0.5Na 0.465K 0.035TiO 3 ????0.42 ????0.18 ????393 ????149 ????290 ????2409
????Bi 0.5Na 0.435K 0.065TiO 3+2wt％Fe 2O 3 ????0.42 ????0.22 ????216 ????382 ????286 ????2463
????Bi 0.5Na 0.435K 0.065TiO 3+2wt％CeO 2 ????0.46 ????0.20 ????494 ????98 ????292 ????2450
????Bi 0.5Na 0.435K 0.065TiO 3+2wt％MnO 2 ????0.44 ????0.22 ????343 ????259 ????288 ????2427
Ferroelectric, the piezoelectric property of table 2 representative formula
Electromechanical coupling factor K p 0.18
K t 0.48
Piezoelectric constant d 33×10 -12C/N 110
g 33×10 -3V·m/N 22.5
Frequency constant N r?Hz·m 3106
N t?Hz·m 2427
Specific inductivity ε 33 T/ε 0 552
The mechanical quality factor Q m r 283
Q m t 62
Dielectric loss tgδ％ 1.7
Curie temperature T C??℃ 290
Remnant polarization P r??μC/cm 2 29.6
Coercive field is strong E C??V/mm 2381
Volume density ρ v?g/cm 3 5.86
Bending strength Kg/cm 2 1596
Temperature factor ε 33 T?×10 -6??1/℃ +7800
K t????×10 -6??1/℃ -29
N t????×10 -6??1/℃ -236
Ageing rate per decade ε 33 T％ +2.3
K t％ -0.18
N t％ -0.11
The piezoelectric property of table 3 embodiment pottery
Embodiment Firing temperature ????K p ????K t ????ε 33 T/ε 0 ????Q m t ????tgδ ?????????％ ????d 33????×10 -12C/N ????ρ v????g/cm 3
Embodiment 1 ?1180℃ ????0.20 ????0.465 ????567 ????78 ????1.5 ????117 ????5.84
Embodiment 2 ?1160℃ ????0.20 ????0.44 ????556 ????69 ????1.6 ????115 ????5.75
Embodiment 3 ?1140℃ ????0.18 ????0.39 ????519 ????61 ????2.2 ????101 ????5.52

Claims (6)

1, a kind of doping vario-property sodium potassium bismuth titanate piezoelectric ceramics, it is characterized in that forming general formula is Bi 0.5Na xK 0.5-xTiO 3, x=0.40～0.495 is mixed Fe simultaneously 2O 3, Cr 2O 3, La 2O 3, MnO 2, CeO 2, Nb 2O 5And Sb 2O 3Wait one or both modified materialses, the weight ratio of mixing is 0.2%～3%.
2, by the described a kind of doping vario-property sodium potassium bismuth titanate piezoelectric ceramics of claim 1, it is characterized in that be x=0.42～0.47 best the composition, mixing weight ratio simultaneously is 0.3%～1.5%.
3, by the preparation method of claim 1 or 2 described a kind of doping vario-property sodium potassium bismuth titanate piezoelectric ceramics, comprise batch mixes, pre-synthetic, fine grinding, moulding, plastic removal sintering, it is characterized in that:
(1) selects anhydrous sodium carbonate, Anhydrous potassium carbonate, bismuth oxide, titanium dioxide and Fe for use 2O 3, Cr 2O 3, La 2O 3, MnO 2, CeO 2, Nb 2O 5And Sb 2O 3Wait one or both modified materialses to make raw material, press compositing formula and doping weighing;
(2) the plastic removal sintering schedule is that the speed of 1-5 ℃/min is warming up to 400-600 ℃, is incubated and is warming up to 1100～1200 ℃ with 1-5 ℃/min after 0.5-3 hour, opens wide sintering 2～4 hours in atmosphere.
4,, it is characterized in that diameter of particle after the fine grinding process is between 400nm～800nm by the preparation method of the described a kind of doping vario-property sodium potassium bismuth titanate piezoelectric ceramics of claim 3.
5,, it is characterized in that synthetic in advance system is 850～1000 ℃ of insulations 2～4 hours by the preparation method of claim 3 or 4 described a kind of doping vario-property sodium potassium bismuth titanate piezoelectric ceramics.
6, by the preparation method of claim 3 or 4 described a kind of doping vario-property sodium potassium bismuth titanate piezoelectric ceramics, it is characterized in that moulding process is dry-pressing or rolling formation.
CNB2004100173083A 2004-03-30 2004-03-30 Doped and modified piezoelectric ceramic of potassium sodium bismuth titanate and preparation method Expired - Fee Related CN100360466C (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100347123C (en) * 2005-12-30 2007-11-07 中国科学院上海硅酸盐研究所 High dielectric contant flexible piezoelectric ceramic material and preparation process thereof
CN101229930B (en) * 2008-01-24 2010-06-02 浙江大学 Nickel doped bismuth sodium titanate multiferroics and preparation method thereof
CN102167585A (en) * 2011-01-18 2011-08-31 北京科技大学 Multielement-doped bismuth titanate group lead-free piezoceramic material and preparation method thereof
CN102249674A (en) * 2011-05-26 2011-11-23 天津大学 Lanthanum-doped lead zinc niobate-lead zirconate titanate (PZN-PZT) piezoelectric ceramic
CN102471166A (en) * 2009-07-31 2012-05-23 埃普科斯股份有限公司 Piezo-electric ceramic composition, method for producing the composition, and electric component comprising the composition
CN103708829A (en) * 2013-12-19 2014-04-09 桂林电子科技大学 Abnormal piezoelectric anisotropy lead-free piezoelectric ceramic and texturing preparation method thereof
CN104009670A (en) * 2014-06-19 2014-08-27 厦门大学 Flexible lead-free piezoelectric sodium bismuth titanate potassium nano power generation device and manufacturing method thereof
CN106554202A (en) * 2016-11-14 2017-04-05 山东大学 A kind of bismuth laminated bismuth-sodium titanate high temperature piezoceramics and preparation method thereof
CN107117960A (en) * 2017-05-22 2017-09-01 天津大学 A kind of bismuth-sodium titanate bismuth potassium titanate based leadless piezoelectric ceramics and preparation method thereof
CN107263701A (en) * 2017-07-25 2017-10-20 苏州雾联医疗科技有限公司 A kind of preparation method of piezoelectric ceramics
CN107382306A (en) * 2017-06-28 2017-11-24 天津大学 Applying acceptor cooperates with substitution to prepare ultrahigh Q-value microwave dielectric material
CN108358626A (en) * 2018-03-13 2018-08-03 中国科学院上海硅酸盐研究所 A kind of unleaded pyroelectric ceramic material of BNT bases and preparation method thereof

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JPH11217262A (en) * 1998-01-30 1999-08-10 Tokin Corp Piezoelectric porcelain composition

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100347123C (en) * 2005-12-30 2007-11-07 中国科学院上海硅酸盐研究所 High dielectric contant flexible piezoelectric ceramic material and preparation process thereof
CN101229930B (en) * 2008-01-24 2010-06-02 浙江大学 Nickel doped bismuth sodium titanate multiferroics and preparation method thereof
CN102471166B (en) * 2009-07-31 2015-07-22 埃普科斯股份有限公司 Piezo-electric ceramic composition, method for producing the composition, and electric component comprising the composition
CN102471166A (en) * 2009-07-31 2012-05-23 埃普科斯股份有限公司 Piezo-electric ceramic composition, method for producing the composition, and electric component comprising the composition
CN102167585A (en) * 2011-01-18 2011-08-31 北京科技大学 Multielement-doped bismuth titanate group lead-free piezoceramic material and preparation method thereof
CN102249674B (en) * 2011-05-26 2013-01-23 天津大学 Lanthanum-doped lead zinc niobate-lead zirconate titanate (PZN-PZT) piezoelectric ceramic
CN102249674A (en) * 2011-05-26 2011-11-23 天津大学 Lanthanum-doped lead zinc niobate-lead zirconate titanate (PZN-PZT) piezoelectric ceramic
CN103708829B (en) * 2013-12-19 2016-04-06 桂林电子科技大学 A kind of unusual Piezoelectric Anisotropy leadless piezoelectric ceramics and texturing preparation method thereof
CN103708829A (en) * 2013-12-19 2014-04-09 桂林电子科技大学 Abnormal piezoelectric anisotropy lead-free piezoelectric ceramic and texturing preparation method thereof
CN104009670A (en) * 2014-06-19 2014-08-27 厦门大学 Flexible lead-free piezoelectric sodium bismuth titanate potassium nano power generation device and manufacturing method thereof
CN104009670B (en) * 2014-06-19 2016-06-15 厦门大学 A kind of flexible leadless piezoelectric bismuth sodium potassium titanate nanometer generating device and manufacture method thereof
CN106554202A (en) * 2016-11-14 2017-04-05 山东大学 A kind of bismuth laminated bismuth-sodium titanate high temperature piezoceramics and preparation method thereof
CN107117960A (en) * 2017-05-22 2017-09-01 天津大学 A kind of bismuth-sodium titanate bismuth potassium titanate based leadless piezoelectric ceramics and preparation method thereof
CN107382306A (en) * 2017-06-28 2017-11-24 天津大学 Applying acceptor cooperates with substitution to prepare ultrahigh Q-value microwave dielectric material
CN107382306B (en) * 2017-06-28 2020-09-18 天津大学 Preparation of ultra-high Q value microwave dielectric material by synergistic substitution of donor and acceptor
CN107263701A (en) * 2017-07-25 2017-10-20 苏州雾联医疗科技有限公司 A kind of preparation method of piezoelectric ceramics
CN108358626A (en) * 2018-03-13 2018-08-03 中国科学院上海硅酸盐研究所 A kind of unleaded pyroelectric ceramic material of BNT bases and preparation method thereof

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