CN104402425B - A kind of preparation method of low-loss bismuth ferrite-barium titanate base piezoelectric ceramic - Google Patents
A kind of preparation method of low-loss bismuth ferrite-barium titanate base piezoelectric ceramic Download PDFInfo
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Abstract
The invention discloses a kind of low-loss BiFeO3‑BaTiO3Based leadless piezoelectric ceramics and preparation method thereof, its composition formula is: (1x)(Bi1‑t La t )FeO3‑xBa(Ti1‑u Sn u )O3+0.5%BiMnO3+yBa(Cu1/3Nb2/3)O3+zLiBiO3+mBa(W1/2Cu1/2)O3, whereint、x、u、y、z、mExpression molar fraction, and 0 <t≤ 0.02,0.15≤x≤ 0.30,0 <u<0.05,0<y<0.05,0<z< 0.05,0 <m<0.05.The technology such as the operations such as its preparation method includes by forming formula dispensing, ball milling, molding element sheet, binder removal, sintering, use and reduce sintering temperature, rapid temperature rise and drop, hyperbaric oxygen, reduce Bi element evaporation, suppression Lacking oxygen generation, prevent Fe in temperature-fall period3+Ion appraises at the current rate, thus reduces the purpose of dielectric loss, has prepared the dielectric loss high-temp leadless piezoelectric ceramics less than 0.5%, has made this system can be applied to high-temperature piezoelectric field.
Description
Technical field
The present invention relates to the preparation method of a kind of leadless piezoelectric ceramics, under the conditions of hyperbaric oxygen, specifically use low temperature liquid phase
The preparation method of low-loss high-performance bismuth ferrite prepared by Fast Sintering-barium phthalate base high-temp leadless piezoelectric ceramics.
Background technology
Piezoelectric ceramics is at information, laser, navigation, electronic technology, communication, gauge check, Precision Machining and sensing technology etc.
High-tech sector is widely used.Bismuth ferrite-Barium metatitanate. system piezoelectric ceramics is because it is unleaded, sintering temperature is low, high-curie temperature, height
Depolarization temperature and good piezoelectric property are received of great interest, 2009, Serhiy O. Leontsev and
Richard E. Eitel etc. report this system obtainable piezoelectric constant d under sintering condition in oxygen atmosphere33=116pC/N, move back
Poling temperature Td=469oThe piezoelectric ceramics of C, but owing to the dielectric loss of this system is the highest, the dielectric loss under 1KHZ is
4.6%, seriously limit the application of its actual development, the most how to reduce the dielectric loss of this system, be that this system is able at high temperature
The key technology of field application.
BiFeO3-BaTiO3The dielectric loss of system is mainly caused by the factor of the following aspects: (1) is due to pure
BiFeO3Sintering temperature be about 750 degree, and BaTiO3Sintering temperature be about 1450 degree, both reach 700 at differenceoC,
Therefore, in order to improve BiFeO3-BaTiO3The consistency of ceramic systems and performance, the sintering temperature of biphase solid solution is 1000oC
Above, and Bi element at high temperature highly volatile, hence in so that the stoichiometric proportion of sintered products off-design；(2) Fe3+From
Appraising at the current rate, at temperature-fall period, Fe of son3+Ion has part can be transformed into Fe2+Ion.In order to maintain quantivalence to balance, both because of
Element all can cause the generation of a large amount of Lacking oxygen, and the dielectric loss finally making sample is higher, polarization difficulty.Therefore this system is at height
That temperature and pressure electrical domain is applied it is crucial that how to control the dielectric loss of this system.
Summary of the invention
It is an object of the invention to for BiFeO3-BaTiO3Deficiency existing for system, and a kind of low-loss ferrous acid is provided
The preparation method of bismuth-barium titanate base piezoelectric ceramic.Dielectric loss is effectively reduced to less than 1.0% by this piezoelectric ceramic energy,
Make it can apply at high-temperature field.
The technical scheme realizing the object of the invention is:
A kind of low-loss bismuth ferrite-barium titanate base piezoelectric ceramic, its composition formula is: (1-x) (Bi1-tLat)FeO3-xBa
(Ti1-uSnu)O3+0.5%BiMnO3+yBa(Cu1/3Nb2/3)O3+zLiBiO3+mBa(W1/2Cu1/2)O3, wherein t, x, u, y, z, m table
Show molar fraction, and 0 < t≤0.02,0.15≤x≤0.30,0 <u < 0.05,0 < y < 0.05,0 < z < 0.05,0 < m < 0.05.
The preparation method of a kind of low-loss bismuth ferrite-barium titanate base piezoelectric ceramic, comprises the steps:
(1) with analytical pure Fe2O3、Bi2O3、BaCO3、TiO2、La2O3、SnO2、MnCO3、CuO、WO3、Nb2O5、Li2CO3For
Raw material, according to (1-x) (Bi1-tLat)FeO 3-xBa(Ti1-uSnu)O3+ zLiBiO3
+0.5%BiMnO3+yBa(Cu1/3Nb2/3)O3+mBa(W1/2Cu1/2)O3Carry out dispensing (wherein 0 < t≤0.02,0.15
≤ x≤0.30,0 <u < 0.05,0 < y < 0.05,0 < z < 0.05,0 < m < 0.05), with dehydrated alcohol for medium ball milling 24 hours,
Dried at 100 DEG C/12 hours, sieve, put in high alumina crucible and add a cover, place in airtight oxygen-supplying tube formula stove with 250 DEG C/h's
Heating rate to 800 DEG C, the oxygen that adds high pressure, to 20MPa, is incubated synthesis in 4 hours, and cooling down is taken out after less than 200 degree.
(2) (1-x) (Bi step 1 synthesized1-tLat)FeO3-xBa(Ti1-uSnu)O3+0.5%BiMnO3+yBa(Cu1/ 3Nb2/3)O3+zLiBiO3 +mBa(W1/2Cu1/2)O3(wherein 0 < t≤0.02,0.15≤x≤0.30,0 <u < 0.05,0 < y <
0.05,0 < z < 0.05,0 < m < 0.05) carry out secondary ball milling, with dehydrated alcohol for medium ball milling 24 hours, be dried, sieve；
(3) powder after sieving adds 5%PVA solution pelletize, compressing under 100MPa, in mould in punching block
Diameter is about 1cm；
(4) the plain sheet of molding is to slowly warm up to 600 DEG C with the heating rate of 30 DEG C/h, is incubated 6h binder removal, after furnace cooling
Take out standby；
(5) the plain sheet of binder removal is directly pushed in 750 degree of tube furnaces leading to pure oxygen, seal, with the intensification of 20 DEG C/min
Speed to 840-860 DEG C, oxygenation high pressure is to 20MPa simultaneously, is incubated 30min, blood pressure lowering, opens tube furnace, directly take out sample extremely
Air cools down；
(6) sample after sintering is processed into that two sides is smooth, the thin slice of thickness about 1mm, drapes over one's shoulders silver electrode, 600oC/30min
After silver ink firing standby；
(7) piezoelectric ceramic piece of preparation is polarized in silicone oil, polarized electric field 6000V/mm, temperature 150 DEG C, the time 30 points
Clock, keeps electric field to be cooled to room temperature.
The positive effect of the present invention is:
Preparation method of the present invention is successfully on the basis of keeping excellent properties, and (1) reduces burning by adding sintering aid
Junction temperature and employing are rapidly heated, and reduce the volatilization in sintering process of the Bi element, it is ensured that the balance of stoichiometric proportion；(2)
Use hyperbaric oxygen condition, the generation of suppression Lacking oxygen；(3) use the sintering technology of chilling, and use element doping inhibition of sintering
Fe in knot temperature-fall period3+Ion transit is Fe2+Ion, the generation of suppression Lacking oxygen.By the combination of these three technology, will be situated between
Electrical loss is down to can be less than the 1.0% of high-temperature field application, and this is for BiFeO3-BaTiO3For system piezoelectric ceramics, from
Technically see there is important breakthrough and technical innovation, and there is practicality.
Detailed description of the invention
Embodiment 1:
Composition formula: 0.75 (Bi0.99La0.01)FeO3-0.25Ba(Ti0.98Sn0.02)O3-0.5%BiMnO3+ 0.6%
LiBiO3+0.6%Ba(Cu1/3Nb2/3)O3+0.5% Ba(W1/2Cu1/2)O3, preparation method comprises the steps:
(1) with analytical pure Fe2O3、Bi2O3、BaCO3、TiO2、La2O3、SnO2、MnCO3、CuO、WO3、Nb2O5、Li2CO3For
Raw material, according to 0.75 (Bi0.99La0.01)FeO3-0.25Ba(Ti0.98Sn0.02)O3-
0.5%BiMnO3+0.8%LiBiO3+0.6%Ba(Cu1/3Nb2/3)O3+0.5% Ba(W1/2Cu1/2)O3, carry out dispensing,
With dehydrated alcohol for medium ball milling 24 hours, dried at 100 DEG C/12 hours, sieve, put in high alumina crucible and add a cover, place into
With the heating rate to 800 DEG C of 250 DEG C/h in airtight oxygen-supplying tube formula stove, the oxygen that adds high pressure, to 20MPa, is incubated synthesis in 4 hours, and drops
Temperature is taken out after being cooled to less than 200 degree.
(2) 0.75 (Bi step 1 synthesized0.99La0.01)FeO3-0.25Ba(Ti0.98Sn0.02)O3-0.5%BiMnO3+
0.8%LiBiO3+0.6%Ba(Cu1/3Nb2/3)O3+0.5% Ba(W1/2Cu1/2)O3Carry out secondary ball milling, with dehydrated alcohol as medium
Ball milling 24 hours, is dried；
(3) powder after sieving adds 5%PVA solution pelletize, compressing under 100MPa, in mould in punching block
Diameter is about 1cm；
(4) the plain sheet of molding is to slowly warm up to 600 DEG C with the heating rate of 30 DEG C/h, is incubated 6h binder removal, after furnace cooling
Take out standby；
(5) the plain sheet of binder removal is directly pushed in 750 degree of tube furnaces leading to pure oxygen, seal, with the intensification of 20 DEG C/min
Speed is rapidly heated 860 DEG C, and oxygenation high pressure is to 20MPa simultaneously, is incubated 30min, blood pressure lowering, opens tube furnace, directly take out sample
Product cool down to air；
(6) sample after sintering is processed into that two sides is smooth, the thin slice of thickness about 1mm, drapes over one's shoulders silver electrode, 600oC/30min
After silver ink firing standby；
(7) piezoelectric ceramic piece of preparation is polarized in silicone oil, polarized electric field 6000V/mm, temperature 150 DEG C, the time 30 points
Clock, keeps electric field to be cooled to room temperature.
Performance measurements is as follows:
| d33(pC/N) | Qm | kp | εr | tanδ(%) |
| 161 | 43.2 | 0.31 | 788 | 0.913 |
Embodiment 2:
Composition: 0.75 (Bi0.99La0.01)FeO3-0.25Ba(Ti0.99Sn0.01)O3-0.5%BiMnO3+0.6%LiBiO3+
0.6%Ba(Cu1/3Nb2/3)O3+0.8% Ba(W1/2Cu1/2)O3
Preparation method is with embodiment 1.
Performance measurements is as follows:
| d33(pC/N) | Qm | kp | εr | tanδ(%) |
| 157 | 41 | 0.30 | 764 | 0.961 |
Embodiment 3:
Composition: 0.75 (Bi0.99La0.01)FeO3-0.25Ba(Ti0.99Sn0.01)O3-0.5%BiMnO3+ 0.8%LiBiO3+
0.6%Ba(Cu1/3Nb2/3)O3+1.0% Ba(W1/2Cu1/2)O3Preparation method, with embodiment 1, except for the difference that sinters temperature
850 DEG C/4h of degree
Performance measurements is as follows:
| d33(pC/N) | Qm | kp | εr | tanδ(%) |
| 138 | 37 | 0.296 | 730 | 0.984 |
Embodiment 4:
Composition: 0.80 (Bi0.99La0.01)FeO3-0.20Ba(Ti0.98Sn0.02)O3-0.5%BiMnO3+0.8%LiBiO3+
0.9%Ba(Cu1/3Nb2/3)O3+1.0% Ba(W1/2Cu1/2)O3
Preparation method with embodiment 1, except for the difference that sintering temperature 840 DEG C.
Performance measurements is as follows:
| d33(pC/N) | Qm | kp | εr | tanδ(%) |
| 136 | 29 | 0.25 | 429 | 0.99 |
The bound of the composition cited by the present invention, interval value and the bound of technological parameter, interval value can
Realize the present invention, enforcement numerous to list herein.
Claims (2)
1. low-loss bismuth ferrite-barium titanate base piezoelectric ceramic, is characterized in that: its composition formula is: (1-x) (Bi1-tLat)
FeO3-xBa(Ti1-uSnu)O3+0.5%BiMnO3+yBa(Cu1/3Nb2/3)O3+zLiBiO3+mBa(W1/2Cu1/2)O3, wherein t, x,
U, y, z, m represent molar fraction, and 0 < t≤0.02,0.15≤x≤0.30,0 <u < 0.05,0 < y < 0.05,0 < z < 0.05,0 <
m<0.05。
2. a preparation method for low-loss bismuth ferrite-barium titanate base piezoelectric ceramic, is characterized in that: comprise the steps:
(1) with analytical pure Fe2O3、Bi2O3、BaCO3、TiO2、La2O3、SnO2、MnCO3、CuO、WO3、Nb2O5、Li2CO3For raw material,
According to (1-x) (Bi1-tLat)FeO 3-xBa(Ti1-uSnu)O3+ zLiBiO3
+0.5%BiMnO3+yBa(Cu1/3Nb2/3)O3+mBa(W1/2Cu1/2)O3Carry out dispensing, with dehydrated alcohol for medium ball milling 24
Hour, dried at 100 DEG C/12 hours, sieve, put in high alumina crucible and add a cover, place in airtight oxygen-supplying tube formula stove with 250
DEG C/heating rate to 800 DEG C of h, the oxygen that adds high pressure, to 20MPa, is incubated synthesis in 4 hours, and cooling down takes after less than 200 degree
Go out, wherein 0 < t≤0.02,0.15≤x≤0.30,0 <u < 0.05,0 < y < 0.05,0 < z < 0.05,0 < m < 0.05；
(2) (1-x) (Bi step 1 synthesized1-tLat)FeO3-xBa(Ti1-uSnu)O3+0.5%BiMnO3+yBa(Cu1/3Nb2/3)
O3+ zLiBiO3 + mBa(W1/2Cu1/2)O3Carry out secondary ball milling, with dehydrated alcohol for medium ball milling 24 hours, be dried, sieve,
Wherein 0 < t≤0.02,0.15≤x≤0.30,0 <u < 0.05,0 < y < 0.05,0 < z < 0.05,0 < m < 0.05；
(3) powder after sieving adds 5%PVA solution pelletize, compressing under 100MPa in punching block, mould interior diameter
It is about 1cm；
(4) the plain sheet of molding is to slowly warm up to 600 DEG C with the heating rate of 30 DEG C/h, is incubated 6h binder removal, takes out after furnace cooling
Standby；
(5) the plain sheet of binder removal is directly pushed in 750 degree of tube furnaces leading to pure oxygen, seal, with the heating rate of 20 DEG C/min
To 840-860 DEG C, oxygenation high pressure is to 20MPa simultaneously, is incubated 30min, blood pressure lowering, opens tube furnace, directly take out sample to air
Middle cooling；
(6) sample after sintering is processed into that two sides is smooth, the thin slice of thickness about 1mm, drapes over one's shoulders silver electrode, 600oAfter C/30min silver ink firing
Standby；
(7) piezoelectric ceramic piece of preparation is polarized in silicone oil, polarized electric field 6000V/mm, temperature 150 DEG C, 30 minutes time,
Electric field is kept to be cooled to room temperature.
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| CN108947514B (en) * | 2018-09-28 | 2020-03-31 | 东北大学 | Ferroelectric material with excellent temperature stability and preparation method and application thereof |
| CN109336185A (en) * | 2018-12-03 | 2019-02-15 | 广东先导稀材股份有限公司 | The production method of micron order mangaic acid bismuth meal body |
| CN109503152B (en) * | 2018-12-29 | 2021-06-15 | 内蒙古大学 | Solid solution film with meta-aggregated particles and preparation method thereof |
| JP7206941B2 (en) * | 2019-01-22 | 2023-01-18 | Tdk株式会社 | Piezoelectric composition and piezoelectric element |
| CN110272286B (en) * | 2019-07-23 | 2020-10-27 | 中国科学技术大学 | Method for improving ferromagnetic and magnetoelectric coupling coefficient of bismuth ferrite-based ceramic |
| CN111138177A (en) * | 2020-01-09 | 2020-05-12 | 桂林电子科技大学 | Bismuth ferrite-bismuth zinc titanate high-temperature lead-free piezoelectric ceramic with high-temperature stability and preparation method thereof |
| CN114262225B (en) * | 2021-12-29 | 2022-10-21 | 湖南省嘉利信陶瓷科技有限公司 | High-purity nano electronic ceramic and preparation method thereof |
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| CN102584194A (en) * | 2012-02-14 | 2012-07-18 | 桂林电子科技大学 | Perovskite leadless piezoelectric ceramic used at high temperature and preparation method thereof |
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| CN102584194A (en) * | 2012-02-14 | 2012-07-18 | 桂林电子科技大学 | Perovskite leadless piezoelectric ceramic used at high temperature and preparation method thereof |
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