CN103613379A - High performance leadless piezoelectric ceramics and preparation technology - Google Patents
High performance leadless piezoelectric ceramics and preparation technology Download PDFInfo
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Abstract
The invention relates to high performance leadless piezoelectric ceramics and its preparation technology, the preparation technology comprises the following steps: burdening titanium dioxide, barium carbonate and stannic oxide according to stoichiometric ratio of 0.89: 1: 0.11, ball milling, pre-burning, performing secondary ball milling, granulation granulating and molding, covering by a crucible finally, putting in a sintering furnace, heating to the temperature of 500 DEG C by a speed of 2 DEG C/min, insulating for 2 hours and dumping, then heating to the temperature of 1400 DEG C at the speed of 4 DEG C/min and insulating for 4 hours, and then cooling in furnace to the room temperature to obtain the required leadless piezoelectric ceramics. The leadless piezoceramic material has high dielectric and piezoelectric performance at quasi four-phase point, the relative dielectric constant of the material can reach 75000 which is 6-7 times of the dielectric constant of pure barium titanate at the Curie temperature, the piezoelectric coefficient d33 can reach 697pC/N which is 5 times of the room temperature piezoelectric coefficient of the pure barium titanate, and the data can be the highest data in that of the leadless piezoceramic material.
Description
Technical field
The present invention relates to piezoelectric ceramic technology field, particularly a kind of high-performance Pb-free piezoelectric ceramics and preparation technology thereof.
Background technology
Piezoelectric and piezoelectric property and 1880 are found by Curie brother, and piezoelectricity refers to that material can form on surface accumulative total electric charge in the situation that of compelling force field, form electric field, or when extra electric field, deformation can occur material.As the bridge transforming between mechanical energy and electric energy, piezoelectric is widely used in detector, transverter and stopper, such as the ink-jet printer using in daily life and mobile microphone, probe supervisory control desk and the supersonic sounding technology such as high-end research Atom force microscope, used again.Recently, piezoelectric is applied to collection of energy and storage especially.
Industrial most widely used piezoelectric is leaded piezoelectric, as Pb-based lanthanumdoped zirconate titanates etc.Because these leaded piezoelectrics not only have good performance at its accurate homotype phase boundary place, and have good temperature stability.But plumbous to human body and environment toxic side effect, so a lot of developed country has forbidden the production of leaded electronic product.Therefore, develop a kind of leadless piezoelectric material material that can substitute leaded system and become extremely urgent.
Summary of the invention
In order to address the deficiencies of the prior art, the object of the present invention is to provide a kind of high-performance Pb-free piezoelectric ceramics and preparation technology thereof, by the solid reaction process of specified conditions, prepared the barium titanate system of barium stannate doping, wherein at 0.89BaTiO
3-0.11BaSnO
3accurate quadruple point place found very high dielectric and piezoelectric properties, the relative permittivity of material reaches ~ 75000, is pure barium titanate at the 6-7 of its Curie temperature place specific inductivity doubly; While piezoelectric coefficient d
33reached 697pC/N, be equivalent to pure barium titanate at 5 times of room temperature piezo-electric modulus, this is also the maximum in current lead-free piezoceramic material.
In order to achieve the above object, technical scheme of the present invention is:
A high-performance Pb-free piezoelectric ceramics, the barium titanate (0.89BaTiO of barium stannate doping
3-0.11BaSnO
3), its feed composition is that mol ratio is by stoichiometric ratio:
Titanium dioxide: barium carbonate: tindioxide=0.89:1:0.11
A preparation technology for high-performance Pb-free piezoelectric ceramics, comprises the following steps:
(1) batching
By raw material titanium dioxide, barium carbonate, tindioxide, by stoichiometric ratio, be that mol ratio is that 0.89:1:0.11 prepares burden, medicine purity is more than 98%;
(2) ball milling
The load weighted raw material of step (1) is put into ball grinder, and ball-milling medium is distilled water and zirconia ball, and the mass ratio of raw material, distilled water, zirconia ball is 1:2:2, ball milling 4 hours, then the compound after ball milling is placed in to 80 ℃, baking oven is dried;
(3) pre-burning
The dried powder of step (2) is inserted in crucible, add a cover, with the speed of 4 ℃/min, be warming up to 1150 ℃, be incubated 4 hours, then cool to room temperature with the furnace;
(4) secondary ball milling
The pre-burned powder of step (3) is carried out to ball milling again, and ball-milling medium is distilled water and zirconia ball, and the mass ratio of raw material, distilled water, zirconia ball is 1:2:2, and now Ball-milling Time is 6 hours, and dries;
(5) granulation
The powder that step (4) is dried grinds, sieves, the additional PVA glue that accounts for its weight 5%, be more fully ground to evenly, cross 60 orders and 100 object screen clothes, get the middle powder of 60 orders and 100 eye mesh screens;
(6) moulding
Powder after step (5) is sieved is put into stainless steel mould, and every 0.5g pressurize 1 minute under the pressure of 100MPa, is pressed into sheet idiosome; In addition, with 2-3g powder, under pressure 100MPa, prepare cylindrical sample;
(7) sintering
The made powder of a little step that tiles on zirconium plate (5), then the idiosome of step (6) is put on powder, with crucible, cover, and put into sintering oven, first with 2 ℃/min, be warmed up to 500 ℃, be incubated 2 hours and carry out binder removal, then with 4 ℃/min, be warmed up to 1400 ℃ and be incubated 4 hours, then cool to room temperature with the furnace, can obtain the leadless piezoelectric ceramics needing.
Advantage of the present invention:
Lead-free piezoceramic material of the present invention has been found very high dielectric and piezoelectric properties at accurate quadruple point place, and the relative permittivity of material reaches ~ 75000, is pure barium titanate at the 6-7 of its Curie temperature place specific inductivity doubly; While piezoelectric coefficient d
33reached 697pC/N, be equivalent to pure barium titanate at 5 times of room temperature piezo-electric modulus, this is also the maximum in current lead-free piezoceramic material.Data show that the performance of material and its phase coexisting state have very close relationship, coexist mutually more, and performance boost is larger, and this leadless piezoelectric material material for exploitation high-performance good stability provides new thinking.
Accompanying drawing explanation
Fig. 1 is the phasor of barium stannate barium titanate doping (BT-xBS) system, and wherein QP refers to 0.89BaTiO
3-0.11BaSnO
3the accurate quadruple point of composition.
Fig. 2 (a) is BT-xBS system piezoelectric constant d
33distribution plan, Fig. 2 (b) is BT-xBS system dielectric temperature spectrum, wherein QP refers to accurate quadruple point.
Fig. 3 is two individual system contrast experiments.Fig. 3 (a1) is barium stannate barium titanate doping (BT-xBS) system phase diagram; Fig. 3 (a2) is calcium titanate barium titanate doping (BT-xCT) system phase diagram; Fig. 3 (b) is the comparison that two individual system Curie temperature are pointed out dielectric properties, and wherein QP represents accurate quadruple point.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in detail,
A kind of high-performance Pb-free piezoelectric ceramics of the present invention, the barium titanate (0.89BaTiO of barium stannate doping
3-0.11BaSnO
3), its feed composition by stoichiometric ratio is:
Titanium dioxide: barium carbonate: tindioxide=0.89:1:0.11
A preparation technology for high-performance Pb-free piezoelectric ceramics, comprises the following steps:
(1) batching
Raw material titanium dioxide, barium carbonate, tindioxide are prepared burden for 0.89:1:0.11 by stoichiometric ratio (mol ratio);
(2) ball milling
The load weighted raw material of step (1) is put into ball grinder, and ball-milling medium is distilled water and zirconia ball, and the mass ratio of raw material, distilled water, zirconia ball is 1:2:2, ball milling 4 hours, then the compound after ball milling is placed in to 80 ℃, baking oven is dried;
(3) pre-burning
The dried powder of step (2) is inserted in crucible, add a cover, with the speed of 4 ℃/min, be warming up to 1150 ℃, be incubated 4 hours, then cool to room temperature with the furnace;
(4) secondary ball milling
The pre-burned powder of step (3) is carried out to ball milling again, and ball-milling medium is distilled water and zirconia ball, and the mass ratio of raw material, distilled water, zirconia ball is 1:2:2, and now Ball-milling Time is 6 hours, and dries;
(5) granulation
The powder that step (4) is dried grinds, sieves, the additional PVA glue that accounts for its weight 5%, be more fully ground to evenly, cross 60 orders and 100 object screen clothes, get the middle powder of 60 orders and 100 eye mesh screens;
(6) moulding
Powder after step (5) is sieved is put into stainless steel mould (diameter 11mm), and every 0.5g pressurize 1 minute under the pressure of 100MPa, is pressed into sheet idiosome; In addition, with 2-3g powder, under pressure 100MPa, can prepare cylindrical sample (diameter 8mm);
(7) sintering
The made powder of a little step that tiles on zirconium plate (5), then the idiosome of step (6) is put on powder, with crucible, cover, and put into sintering oven, first with 2 ℃/min, be warmed up to 500 ℃, be incubated 2 hours and carry out binder removal, then with 4 ℃/min, be warmed up to 1400 ℃ and be incubated 4 hours, then cool to room temperature with the furnace, can obtain the leadless piezoelectric ceramics needing.
The present embodiment gained leadless piezoelectric ceramics is carried out to electrical testing, and the ceramic plate that step (7) need to be made polishes smooth, and then applies silver slurry and makes surface electrode.The slice, thin piece that coats silver slurry is placed on zirconium plate, inserts in retort furnace and be warmed up to 800 ℃ with 4 ℃/min, be incubated 30 minutes, naturally cooling; Take out slice, thin piece and the silver electrode of peripheral side is ground off.
While carrying out piezoelectricity test, the column ceramics sample that step (8) need to be prepared polarizes.The column ceramics sample that step (8) is obtained is inserted in silicone oil, energising polarization 30 minutes, and polarized electric field is the coercive field of 2-3kv/mm or 3 times; After standing 24 hours, carry out performance test.
Fig. 1 has shown the phasor of barium titanate (BT-xBS) material of barium stannate doping.Pure barium titanate phase transformation is sequentially the phase transformation order of Emission in Cubic-Tetragonal-quadrature phase-water chestnut side phase (being C-T-O-R), and special, this three steps phase transformation finally converges to a bit (BT-11BS in phasor, approximately 40 degrees Celsius).This means that these four phases (C-T-O-R) are substantially at 0.89BaTiO
3-0.11BaSnO
3in coexist together, therefore caused 0.89BaTiO
3-0.11BaSnO
3have very excellent performance.
Fig. 2 (a) is BT-xBS system d
33the equal-value map of piezo-electric modulus, can see at 0.89BaTiO
3-0.11BaSnO
3accurate quadruple point place, material d
33reach ~ 700pC/N of piezo-electric modulus is the maximum lead-free ceramics piezoelectric constant of reporting now.Fig. 2 (b) is the dielectric temperature spectrum of BT-xBS, and we are easy to just can find that material is at 0.89BaTiO
3-0.11BaSnO
3accurate quadruple point place obtain great specific inductivity, far away higher than other compositions and temperature.These presentation of results materials are all greatly improved as piezoelectricity and specific inductivity in little the dynamic property at accurate quadruple point place, higher than other phase boundaries and composition.
In order to prove that performance boost in accurate quadruple point derives from accurate four this structural conditions that coexist mutually really, we have been contrast experiment.As shown in Figure 3, we have chosen identical barium titanate matrix, different hotchpotch barium stannates and calcium titanate, and the former is at 0.89BaTiO
3-0.11BaSnO
3form accurate quadruple point and the latter does not have, its phasor as Fig. 3 (a) (b) as shown in.Found that it is barium phthalate base equally, from barium titanate, start to adulterate, BT-xBS system is at 0.89BaTiO
3-0.11BaSnO
3under the leading of accurate quadruple point at place, had a very high dielectric peak, and that BT-xCT system shows because there is no multiphase coexistence point being very mediocre, is very little fluctuating.This experimental results show that 0.89BaTiO
3-0.11BaSnO
3accurate quadruple point be the high performance immediate cause in QP place.
In sum, at 0.89BaTiO
3-0.11BaSnO
3accurate quadruple point place found very high dielectric and piezoelectric properties, the relative permittivity of material reaches ~ 75000, is pure barium titanate at the 6-7 of its Curie temperature place specific inductivity doubly; While piezoelectric coefficient d
33reached 697pC/N, be equivalent to pure barium titanate at 5 times of room temperature piezo-electric modulus, this is also the maximum in current lead-free piezoceramic material.Data show that the performance of material and its phase coexisting state have very close relationship, coexist mutually more, and performance boost is larger, and this leadless piezoelectric material material for exploitation high-performance good stability provides new thinking.
Claims (2)
1. a high-performance Pb-free piezoelectric ceramics, is characterized in that, its feed composition is that mol ratio is by stoichiometric ratio:
Titanium dioxide: barium carbonate: tindioxide=0.89:1:0.11.
2. a preparation technology for high-performance Pb-free piezoelectric ceramics, comprises the following steps:
(1) batching
By raw material titanium dioxide, barium carbonate, tindioxide, by stoichiometric ratio, be that mol ratio is that 0.89:1:0.11 prepares burden;
(2) ball milling
The load weighted raw material of step (1) is put into ball grinder, and ball-milling medium is distilled water and zirconia ball, and the mass ratio of raw material, distilled water, zirconia ball is 1:2:2, ball milling 4 hours, then the compound after ball milling is placed in to 80 ℃, baking oven is dried;
(3) pre-burning
The dried powder of step (2) is inserted in crucible, add a cover, with the speed of 4 ℃/min, be warming up to 1150 ℃, be incubated 4 hours, then cool to room temperature with the furnace;
(4) secondary ball milling
The pre-burned powder of step (3) is carried out to ball milling again, and ball-milling medium is distilled water and zirconia ball, and the mass ratio of raw material, distilled water, zirconia ball is 1:2:2, and now Ball-milling Time is 6 hours, and dries;
(5) granulation
The powder that step (4) is dried grinds, sieves, the additional PVA glue that accounts for its weight 5%, be more fully ground to evenly, cross 60 orders and 100 object screen clothes, get the middle powder of 60 orders and 100 eye mesh screens;
(6) moulding
Powder after step (5) is sieved is put into stainless steel mould, and every 0.5g pressurize 1 minute under the pressure of 100MPa, is pressed into sheet idiosome; In addition, with 2-3g powder, under pressure 100MPa, can prepare cylindrical sample;
(7) sintering
The made powder of a little step that tiles on zirconium plate (5), then the idiosome of step (6) is put on powder, with crucible, cover, and put into sintering oven, first with 2 ℃/min, be warmed up to 500 ℃, be incubated 2 hours and carry out binder removal, then with 4 ℃/min, be warmed up to 1400 ℃ and be incubated 4 hours, then cool to room temperature with the furnace, can obtain the leadless piezoelectric ceramics needing.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106518121A (en) * | 2016-11-10 | 2017-03-22 | 佛山蓝途科技有限公司 | High-Curie-temperature leadless piezoelectric ceramic and preparation method thereof |
| CN108147809A (en) * | 2018-02-06 | 2018-06-12 | 北京元六鸿远电子科技股份有限公司 | Low temperature sintering barium-titanium series microwave dielectric material and preparation method |
| WO2019201353A1 (en) * | 2018-04-21 | 2019-10-24 | 西安交通大学 | Method for obtaining lead-free piezoelectric material, and corresponding lead-free piezoelectric material |
| CN111333413A (en) * | 2020-03-06 | 2020-06-26 | 中国科学院上海硅酸盐研究所 | Bismuth ferrite-lead titanate-barium titano-stannate ternary system high-temperature piezoelectric ceramic material and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106518121A (en) * | 2016-11-10 | 2017-03-22 | 佛山蓝途科技有限公司 | High-Curie-temperature leadless piezoelectric ceramic and preparation method thereof |
| CN108147809A (en) * | 2018-02-06 | 2018-06-12 | 北京元六鸿远电子科技股份有限公司 | Low temperature sintering barium-titanium series microwave dielectric material and preparation method |
| CN108147809B (en) * | 2018-02-06 | 2022-07-12 | 北京元六鸿远电子科技股份有限公司 | Medium-low temperature sintered barium-titanium series microwave dielectric material and preparation method thereof |
| WO2019201353A1 (en) * | 2018-04-21 | 2019-10-24 | 西安交通大学 | Method for obtaining lead-free piezoelectric material, and corresponding lead-free piezoelectric material |
| CN112469682A (en) * | 2018-04-21 | 2021-03-09 | 西安交通大学 | Method for obtaining lead-free piezoelectric material and corresponding lead-free piezoelectric material |
| JP2021522144A (en) * | 2018-04-21 | 2021-08-30 | 西安交通大学 | How to Get Lead-Free Piezoelectric Materials, Corresponding Lead-Free Piezoelectric Materials |
| JP7462275B2 (en) | 2018-04-21 | 2024-04-05 | 西安交通大学 | How to obtain lead-free piezoelectric materials, corresponding lead-free piezoelectric materials |
| CN111333413A (en) * | 2020-03-06 | 2020-06-26 | 中国科学院上海硅酸盐研究所 | Bismuth ferrite-lead titanate-barium titano-stannate ternary system high-temperature piezoelectric ceramic material and preparation method thereof |
| CN111333413B (en) * | 2020-03-06 | 2021-08-06 | 中国科学院上海硅酸盐研究所 | Bismuth ferrite-lead titanate-barium titano-stannate ternary system high-temperature piezoelectric ceramic material and preparation method thereof |
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Application publication date: 20140305 |