CN100361932C - Bismuth-sodium titanate base lead-free piezoelectric ceramic - Google Patents

Bismuth-sodium titanate base lead-free piezoelectric ceramic Download PDF

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CN100361932C
CN100361932C CNB2006100190815A CN200610019081A CN100361932C CN 100361932 C CN100361932 C CN 100361932C CN B2006100190815 A CNB2006100190815 A CN B2006100190815A CN 200610019081 A CN200610019081 A CN 200610019081A CN 100361932 C CN100361932 C CN 100361932C
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sintering
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CN1850718A (en
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吕文中
范桂芬
汪小红
梁飞
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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Abstract

The present invention relates to bismuth-sodium titanate group leadless piezoelectric ceramics, which belongs to piezoelectric ceramic materials. The present invention has the purposes of lowering coercive fields and improving piezoelectric properties. The present invention has the component expression of (1-x-y)(Bi<1/2>Na<1/2>)TiO3-x(Bi<1/2>K<1/2>)TiO3-yKNbO3, wherein x is more than or equal to 0 and less than 1, y is more than 0 and less than 0.2, and x plus y is more than 0 and less than 1. The present invention is prepared by the method: (1) weighing Bi2O3, Na2CO3, (COOK)2. H2O, TiO2 and Nb2O5 according to the stoichiometric ratio of the expression to be used as raw materials, and using pure alcohol as media to carry out ball milling; (2) after ball milling, baking the powdery materials, presintering the powdery materials at 800 to 850 DEG C for 2 hours, and adding adhesive agents for forming; (3) sintering the powdery materials at 1100 to 1180 DEG C for 2 to 3 hours; (4) preparing silver electrodes on ceramic sheets after sintering, and polarizing the ceramic sheets for 10 to 15 minutes under the voltage of 4 to 5 kV/mm in silicon oil at 30 to 60 DEG C. d33 of the piezoelectric ceramic composition of the present invention can reach more than 190 pC/N, and Kp can reach more than 0.37. The present invention has stable technology, and is suitable for be applied to the fields of piezoelectric vibrators, ultrasonic transducers, etc.

Description

A kind of bismuth-sodium titanate base lead-free piezoelectric ceramic
Technical field
The invention belongs to piezoceramic material, be specifically related to a kind of perovskite structure lead-free piezoelectric ceramic composition, be fit to be applied to fields such as piezoelectric vibrator and ultrasonic transducer.
Background technology
Piezoelectric ceramics is a kind of the power that changes is converted to electricity or electricity is converted to the new function stupalith of vibration, all is widely used in technical fields such as information, space flight, laser and biologies.But the piezoceramic material of large-scale application mainly is based on the lead base piezoelectric ceramics, and wherein the content of plumbous oxide accounts for 70% of raw material total amount, this just cause produce, use and the process of discarded aftertreatment in bring serious harm for the mankind and ecotope.Therefore, in recent years, the research of lead-free piezoceramic material and application becomes focus gradually.In four kinds of leadless piezoelectric ceramics systems of research at present, bismuth-sodium titanate base lead-free piezoelectric ceramic is considered to the most promising lead-free piezoceramic material.(Bi 1/2Na 1/2) TiO 3Be that the A position is by compound ion Bi 0.5Na 0.5The ABO that constitutes 3Type uhligite ferroelectrics.Simple (Bi 1/2Na 1/2) TiO 3The pottery coercive field is big (73kV/mm), and the polarization difficulty is difficult to practicability.In order to address this problem, recent two decades comes, to (Bi 1/2Na 1/2) TiO 3Carry out a series of study on the modification and reduced coercive field, improved piezoelectric property.Common method of modifying is partly to replace A position compound ion Bi with+2 alkaline-earth metal ions at present 0.5Na 0.5Or partly replace the Na ion with+1 alkalimetal ion.Document 1, T Takanaka, K I Maruyama, " Na 0.5Bi O.5TO 3-BaTiO 3System for lead-free piezoelectric ceramic ", Jpn.J.Appl.Phys., 1991,30 (9B): 2236-2239; Document 2, just treasured advances, Li Guorong, the river is to equality, " Bi 1/2Na 1/2TiO 3-BaTiO 3Be piezoelectric ceramics and relaxation phase research ", Journal of Inorganic Materials, 2000,15 (5): 815-821. has reported and has consisted of (1-x) (Bi 1/2Na 1/2) TiO 3-xBaTiO 3The leadless piezoelectric ceramics body, its piezoelectric constant d 33=125pC/N, radially electromechanical coupling factor kp=0.29.Document 3, Wu Yugong, Ma Jinyi, Dong Xianghong etc., " Na 0.5Bi 0.5TiO 3-SrTiO 3The dielectric of leadless piezoelectric ceramics, piezoelectric property ", piezoelectricity and acousto-optic, 2000,22 (6): 370-372 has reported and has consisted of (1-x) (Bi 1/2Na 1/2) TiO 3-xSrTiO 3The leadless piezoelectric ceramics system, its piezoelectric constant d 33=100pC/N, thickness electromechanical coupling coefficient kt=0.45.Document 4, Wang Tianbao, Wang Liee, Lu Yongkang, kingly way roc, " Na 0.5Bi 0.5TiO 3-K 0.5Bi O.5TiO 3Be the electric Study on Physical of rich sodium district pottery sosoloid ", silicate journal, 1986,14 (1): 14-22 has reported and has consisted of (1-x) (Bi 1/2Na 1/2) TiO 3-x (Bi 1/2K 1/2) TiO 3The leadless piezoelectric ceramics system, its piezoelectric constant d 33=100pC/N, radially electromechanical coupling factor kp=0.28.Document 5, D M Lin, D Q Xiao, etal. " Synthesis and piezoelectric properties of lead-free piezoelectric[Bi 0.5(Na 1-x-yK xLi y) O.5] TiO 3Ceramic " .Mater.Lett., 2004,58:615-618 has reported and has consisted of [Bi 0.5(Na 1-x-yK xLi y) 0.5] TiO 3The leadless piezoelectric ceramics system, its piezoelectric constant d 33=180pC/N, radially electromechanical coupling factor kp=0.35.
Summary of the invention
The invention provides a kind of bismuth-sodium titanate base lead-free piezoelectric ceramic, purpose is further to reduce coercive field, improves piezoelectric property, to adapt to commercial application.
A kind of bismuth-sodium titanate base lead-free piezoelectric ceramic of the present invention, its base-material comprises (Bi 1/2Na 1/2) TiO 3, (Bi 1/2K 1/2) TiO 3And KNbO 3The structural compounds of three kinds of uhligites and sintering aid M aO b, its mol ratio and composition expression formula are:
(1-x-y) (Bi 1/2Na 1/2) TiO 3-x (Bi 1/2K 1/2) TiO 3-yKNbO 3+ uM aO b, 0≤x in the formula＜1,0＜y＜0.2,0＜(x+y)＜1, u=0.3～1.4wt%, M aO bBe oxide compound Na 2O, Li 2O, CuO, MnO 2, ZnO 2, V 2O 5, B 2O 3In one or more, a and b are positive integer, respectively the atomicity of M and oxygen in the relevant oxide compound of expression; And adopt following method preparation: (1) takes by weighing analytical pure or commercially pure Bi by the stoichiometric ratio of described composition expression formula 2O 3, Na 2CO 3, (COOK) 2H 2O, TiO 2, Nb 2O 5Be raw material, use straight alcohol as the medium ball milling; (2) 800 ℃～850 ℃ pre-burning 2h of alumina crucible that pack into after the powder behind the ball milling oven dry, the powder doping mass ratio after the pre-burning is the oxide M of u aO bAs sintering aid,, add the tackiness agent moulding through ball milling; (3) sintering 2～3 hours between 1100 ℃～1180 ℃; (4) prepare silver electrode on the ceramic plate behind the sintering, in 30 ℃～60 ℃ silicone oil, under the voltage of 4～5kV/mm, polarized 10～15 minutes.
Among the present invention, under the room temperature, (Bi 1/2Na 1/2) TiO 3Be the ferroelectrics of trigonal crystal structure, (Bi 1/2K 1/2) TiO 3Be the ferroelectrics of tetragonal, KNbO 3Be the ferroelectrics of orthohormbic structure, three kinds of different ferroelectricss of structure are solid-solubilized in together, determine their accurate homotype phase boundary, can find best piezoelectric property.Because (Bi 1/2Na 1/2) TiO 3-(Bi 1/2K 1/2) TiO 3-KNbO 3Higher (sintering range is very narrow under 〉=18mol%) the situation, adds one or more M at potassium content for pottery aO bOxide compound can make this ceramic systems regulate sintering temperature between 1100 ℃～1180 ℃ and also can obtain piezoelectric property preferably.
Three component system leadless piezoelectric ceramics of the present invention has good piezoelectric property.Show the piezoelectric constant d of this system through performance test 33Can reach more than the 190pC/N, radially electromechanical coupling factor kp can reach more than 0.37, has reached the level of practicability, is mainly used in piezoelectric vibrator and ultrasonic transducer.The advantage of this ceramic systems is to make and process stabilizing with traditional ceramic preparation technology, and sintering temperature is between 1100 ℃～1180 ℃, and is more much lower than leaded sintering temperature of piezoelectric ceramics.
Description of drawings
Fig. 1 is leadless piezoelectric ceramics of the present invention ferroelectric hysteresis loop figure at normal temperatures.
Embodiment
The prescription of leadless piezoelectric ceramics of the present invention and performance index are as shown in the Examples:
Embodiment 1:
The stoichiometric ratio (mol ratio) that reaches formula by following component list takes by weighing analytical pure or commercially pure Bi 2O 3, Na 2CO 3, (COOK) 2H 2O, TiO 2, Nb 2O 5Be raw material:
0.83(Bi 1/2Na 1/2)TiO 3-0.16(Bi 1/2K 1/2)TiO 3-0.01KNbO 3
With straight alcohol as the medium ball milling, 800 ℃～850 ℃ pre-burning 2h of alumina crucible that pack into after the oven dry, the powder after the pre-burning adds the tackiness agent moulding, sintering is 2～3 hours between 1100 ℃～1180 ℃; Two surface preparation silver electrodes on the ceramic plate behind the sintering in 30 ℃～60 ℃ silicone oil, polarized under the voltage of 4～5kV/mm 10～15 minutes.
Performance:
d 33(pC/N) kp(％) tanδ(％) ε 33/ε 0 Qm Np
152 33 3.2 830 165 2620
Embodiment 2:
The preparation method is with embodiment 1, the composition expression formula:
0.79(Bi 1/2Na 1/2)TiO 3-0.2(Bi 1/2K 1/2)TiO 3-0.01KNbO 3
Performance:
d 33(pC/N) kp(％) tanδ(％) ε 33/ε 0 Qm Np
182 31 4.0 1350 89 2650
Embodiment 3:
The preparation method is with embodiment 1, the composition expression formula:
0.82(Bi 1/2Na 1/2)TiO 3-0.16(Bi 1/2K 1/2)TiO 3-0.02KNbO 3
Performance:
d 33(pC/N) kp(％) tanδ(％) ε 33/ε 0 Qm Np
192 36 5.1 1430 97 2660
Embodiment 4:
The preparation method is with embodiment 1, the composition expression formula:
0.87(Bi 1/2Na 1/2)TiO 3-0.1(Bi 1/2K 1/2)TiO 3-0.03KNbO 3
Performance:
d 33(pC/N) kp(％) tanδ(％) ε 33/ε 0 Qm Np
138 38 5.7 691 30 2715
Embodiment 5:
The preparation method is with embodiment 1, the composition expression formula:
0.92(Bi 1/2Na 1/2)TiO 3-0.04(Bi 1/2K 1/2)TiO 3-0.04KNbO 3
Performance:
d 33(pC/N) kp(％) tanδ(％) ε 33/ε 0 Qm Np
125 26 2.5 702 197 2725
Embodiment 6:
The preparation method is with embodiment 1, but the powder doping mass ratio after the pre-burning is 0.3% oxide M nO 2, through ball milling, add the tackiness agent moulding after, sintering again, the composition expression formula:
0.83(Bi 1/2Na 1/2)TiO 3-0.16(Bi 1/2K 1/2)TiO 3-0.01KNbO 3+0.3wt％MnO 2
Performance:
d 33(pC/N) kp(％) tanδ(％) ε 33/ε 0 Qm Np
168 35 2.7 685 256 2745
Embodiment 7:
The preparation method is with embodiment 6, but the powder doping mass ratio after the pre-burning is 1.2% oxide compound CuO, the composition expression formula:
0.82(Bi 1/2Na 1/2)TiO 3-0.16(Bi 1/2K 1/2)TiO 3-0.02KNbO 3+1.2wt％CuO
Performance:
d 33(pC/N) kp(％) tanδ(％) ε 33/ε 0 Qm Np
183 32 2.1 630 184 2546
Embodiment 8:
The preparation method is with embodiment 6, but the powder doping mass ratio after the pre-burning is 0.3% oxide compound ZnO 2, the composition expression formula:
0.83(Bi 1/2Na 1/2)TiO 3-0.16(Bi 1/2K 1/2)TiO 3-0.01KNbO 3+0.3wt％ZnO 2
Performance:
d 33(pC/N) kp(％) tanδ(％) ε 33/ε 0 Qm Np
175 32 2.7 685 256 2745
Embodiment 9:
The preparation method is with embodiment 6, is 0.2% oxide M nO but the powder doping mass ratio after the pre-burning is 1.2% oxide compound CuO and mass ratio 2, the composition expression formula:
0.82(Bi 1/2Na 1/2)TiO 3-0.16(Bi 1/2K 1/2)TiO 3-0.02KNbO 3+1.2wt％CuO+0.2wt％MnO 2
Performance:
d 33(pC/N) kp(％) tanδ(％) ε 33/ε 0 Qm Np
199 37 2.9 724 178 2632

Claims (1)

1. bismuth-sodium titanate base lead-free piezoelectric ceramic, its base-material comprises (Bi 1/2Na 1/2) TiO 3, (Bi 1/2K 1/2) TiO 3And KNbO 3The structural compounds of three kinds of uhligites and sintering aid M aO b, its mol ratio and composition expression formula are:
(1-x-y) (Bi 1/2Na 1/2) TiO 3-x (Bi 1/2K 1/2) TiO 3-yKNbO 3+ uM aO b, 0≤x in the formula＜1,0＜y＜0.2,0＜(x+y)＜1, u=0.3～1.4wt%, M aO bBe oxide compound Na 2O, Li 2O, CuO, MnO 2, ZnO 2, V 2O 5, B 2O 3In one or more, a and b are positive integer, respectively the atomicity of M and oxygen in the relevant oxide compound of expression; And adopt following method preparation: (1) takes by weighing analytical pure or commercially pure Bi by the stoichiometric ratio of described composition expression formula 2O 3, Na 2CO 3, (COOK) 2H 2O, TiO 2, Nb 2O 5Be raw material, use straight alcohol as the medium ball milling; (2) 800 ℃～850 ℃ pre-burning 2h of alumina crucible that pack into after the powder behind the ball milling oven dry, the powder doping mass ratio after the pre-burning is the oxide M of u aO bAs sintering aid,, add the tackiness agent moulding through ball milling; (3) sintering 2～3 hours between 1100 ℃～1180 ℃; (4) prepare silver electrode on the ceramic plate behind the sintering, in 30 ℃～60 ℃ silicone oil, under the voltage of 4～5kV/mm, polarized 10～15 minutes.
CNB2006100190815A 2006-05-16 2006-05-16 Bismuth-sodium titanate base lead-free piezoelectric ceramic Expired - Fee Related CN100361932C (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108147812A (en) * 2018-01-15 2018-06-12 陕西科技大学 A kind of BT-KBT-NN based high energy storage densities ceramics and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101229930B (en) * 2008-01-24 2010-06-02 浙江大学 Nickel doped bismuth sodium titanate multiferroics and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85100426A (en) * 1985-04-01 1986-08-13 中国科学院上海硅酸盐研究所 The piezoceramic material of the ultrasonic usefulness of bismuth sodium potassium titanate series
CN1381425A (en) * 2001-04-18 2002-11-27 日本特殊陶业株式会社 Piezoelectric ceramic material
CN1197823C (en) * 2000-11-21 2005-04-20 Tdk株式会社 Piezoelectric ceramic

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85100426A (en) * 1985-04-01 1986-08-13 中国科学院上海硅酸盐研究所 The piezoceramic material of the ultrasonic usefulness of bismuth sodium potassium titanate series
CN1197823C (en) * 2000-11-21 2005-04-20 Tdk株式会社 Piezoelectric ceramic
CN1381425A (en) * 2001-04-18 2002-11-27 日本特殊陶业株式会社 Piezoelectric ceramic material

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108147812A (en) * 2018-01-15 2018-06-12 陕西科技大学 A kind of BT-KBT-NN based high energy storage densities ceramics and preparation method thereof

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