CN104291817B - PZT piezoceramic material of high-curie temperature and preparation method thereof - Google Patents

PZT piezoceramic material of high-curie temperature and preparation method thereof Download PDF

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CN104291817B
CN104291817B CN201310300467.3A CN201310300467A CN104291817B CN 104291817 B CN104291817 B CN 104291817B CN 201310300467 A CN201310300467 A CN 201310300467A CN 104291817 B CN104291817 B CN 104291817B
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curie temperature
deionized water
piezoceramic material
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CN104291817A (en
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孙兆海
马涛
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ZIBO YUHAI ELECTRONIC CERAMIC CO Ltd
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Abstract

The invention belongs to piezoceramic material field, PZT piezoceramic material being specifically related to a kind of high-curie temperature and preparation method thereof.The composition formula of material is Pb [(Sn 1/3nb 2/3) xzr yti 1-x-y] O 3, 1.02 ~ 1.75%MnO of additional mass percent 2, wherein 0.04≤x≤0.08,0.47≤y≤0.51.Preparation method is: mixed by raw material, with deionized water as ball-milling medium, and batch mixing; After batch mixing drainage, dry, add deionized water and cross after 30-50 mesh sieve after briquetting, pre-burning; After pre-burning again with deionized water as ball-milling medium, add tackiness agent, glycerine, dispersion agent, carry out pulverizing grinding, release after slip, utilize mist projection granulating tower to carry out granulation.Dry-pressing formed under powder condition after granulation, sintered by tunnel furnace; The standard film that work in-process after sintering are processed into, after silver electrode is coated on two sides, roasting silver, is then placed in silicone oil and polarizes.Piezoelectric property of the present invention is high, higher than conventional material Curie temperature, and preparation method is simple, and easy handling, pollution-free, cost is low.

Description

PZT piezoceramic material of high-curie temperature and preparation method thereof
Technical field
The invention belongs to piezoceramic material field, PZT piezoceramic material being specifically related to a kind of high-curie temperature and preparation method thereof.
Background technology
Piezoelectric ceramics, is a kind of ceramic material mechanical energy and electric energy can changed mutually, belongs to ceramic.This is a kind of material with piezoelectric effect.So-called piezoelectric effect refers to some medium under force, and produce deformation, cause dielectric surface charged, this is direct piezoelectric effect.Otherwise apply excitation electrical field, medium will produce mechanical deformation, claim inverse piezoelectric effect.This marvellous effect is applied in closely-related many fields of living with people, to realize energy transformation, sensing, driving, frequency control function by scientist.In energy transformation, utilize piezoelectric ceramics mechanical energy to be converted to the characteristic of electric energy, piezolighter, mobile X-ray power supply, shell igniter can be produced.Just have the flint that piezoelectric ceramics makes in electronic lighter, sparking number of times can more than 1,000,000 times.With piezoelectric ceramics, electric energy is converted to ultrasonic vibration, can be used for seeking position and the shape of the shoal of fish under water, non-destructive test(ing)(NDT) is carried out to metal, and ultrasonic cleaning, ultrasonic medical, various ultrasonic slitter, welding plant and flatiron can also be made, to plastics even metal process.
Since Curie brother in 1880 finds piezoelectric effect, this effect is widely used in all respects of all trades and professions and social life, and therefore piezoelectric ceramics also becomes the electron ceramic material that output is larger except dielectric ceramic.The piezoceramic material be found the earliest is barium titanate, but since the fifties, PZT pottery was found, PZT is just because its electromechanical coupling factor is high, temperature stability is good, Curie temperature is higher, and reach different purposes superiority by suitable replacement interpolation modification, occupy piezoelectric ceramics market in a large number.Research about PZT material also replaces from exploration is various the impact added material property, widens the relation of micro-structure and property and all respects of technological process gradually.The raising of PZT material Curie temperature is wherein one of direction.
Piezoelectric ceramics only just has piezoelectricity in a certain temperature range, and it has a critical temperature Tc.When temperature is higher than Tc, piezoelectric ceramics recurring structure phase in version, changes paraelectric phase into by ferroelectric phase, and spontaneous polarization disappears.This critical temperature Tc is just called the Curie temperature of piezoelectric ceramics.As can be seen here, the Curie temperature of piezoelectric ceramics plays a very important role for the scope of application of piezoelectric ceramics, uses, just necessarily require the Curie temperature of piezoceramic material higher in the environment that temperature is high.So the expansion of use range along with piezoelectric ceramics, hot environment also can get more and more, and just has higher requirement to the Curie temperature of piezoceramic material.
Summary of the invention
PZT piezoceramic material that the object of this invention is to provide a kind of high-curie temperature and preparation method thereof, piezoelectric property is high, higher than conventional material Curie temperature, and preparation method is simple, and easy handling, pollution-free, cost is low.
The PZT piezoceramic material of high-curie temperature of the present invention, the composition formula of material is Pb [(Sn 1/3nb 2/3) xzr yti 1-x-y] O 3, 1.02 ~ 1.75%MnO of additional mass percent 2, wherein 0.04≤x≤0.08,0.47≤y≤0.51.
Preparation method is as follows:
(1) by Pb 3o 4, ZrO 2, TiO 2, Nb 2o 5, SnO 2and MnO 2mixing, with deionized water as ball-milling medium, batch mixing;
(2) after batch mixing drainage, dry, add deionized water and cross after 30-50 mesh sieve after briquetting, pre-burning;
(3) after pre-burning again with deionized water as ball-milling medium, add tackiness agent, glycerine, dispersion agent, carry out pulverizing grinding, release after slip, utilize mist projection granulating tower to carry out granulation.Dry-pressing formed under powder condition after granulation, sintered by tunnel furnace;
(4) work in-process after sintering are processed into the standard film of Ф 20 × 2mm, at 700 ~ 820 DEG C of roasting silver after silver electrode is coated on two sides, are then placed in silicone oil and polarize.
Mixing time is 3 ~ 5 hours.
In step (2), the addition of deionized water is 5% ~ 9%.
The temperature of pre-burning is 790 ~ 825 DEG C, and the time of pre-burning is 2 ~ 3 hours.
The time of pulverizing grinding is 5 ~ 7 hours.
Dry-pressing formed pressure is the pressure of 10 ~ 20Mpa
Sintering temperature is 1240 ~ 1290 DEG C; Sinter 2 ~ 4 hours.
Poling temperature is 130 ~ 150 DEG C, and polarizing voltage is 2500 ~ 3000V/mm, and the polarization time is 15 ~ 30 minutes.
Tackiness agent is polyvinyl alcohol and distilled water 90-110 DEG C of heating.
Dispersion agent is defloculating agent.
Dispersion agent is the 0.5%-0.8% of raw material weight; Glycerine is the 0.02%-0.05% of raw material weight; Tackiness agent is the 8%-12% of raw material weight.
Obtain a kind of PZT piezoelectric ceramics novel material-PSnN-52 adding the high-curie temperature of manganese element.
Compared with prior art, the present invention has following beneficial effect:
Carry out doping vario-property by adjusting the ratio of the zirconium (Zr) in the formula of Pb-based lanthanumdoped zirconate titanates and titanium (Ti) and adding a small amount of manganese (Mn) element, piezoelectric property is high, higher than conventional material Curie temperature, preparation method is simple, easy handling, pollution-free, cost is low.
Embodiment
Below in conjunction with example, feature of the present invention is further described, but is not limited to following embodiment.
The following example Raw: Pb 3o 4for chemical pure, ZrO 2for electronic-grade, TiO 2for analytical pure, Nb 2o 5for analytical pure, SnO 2for analytical pure and MnO 2for analytical pure.
Embodiment 1
Preparation process is as follows:
With Pb 3o 4, ZrO 2, TiO 2, Nb 2o 5, SnO 2and MnO 2for raw material, according to composition formula Pb [(Sn 1/3nb 2/3) xzr yti 1-x-y] O 3, wherein x=0.04, y=0.49, calculates the quality of various raw material, takes Pb 3o 4, ZrO 2, TiO 2, Nb 2o 5, SnO 2preparation bulk composition, then add the MnO accounting for bulk composition mass percent 1.02% wherein 2as supplementary component.With deionized water as ball-milling medium, utilize agitating ball mill batch mixing 4 hours, discharging is with after pressure-filtering tank drainage, utilize oven for drying, add 7% deionized water and cross briquetting after 40 mesh sieves, at 790 DEG C, utilize tunnel furnace to carry out pre-burning, add tackiness agent, glycerine, dispersion agent with deionized water in agitating ball mill, carry out pulverizing grinding 6 hours as ball-milling medium again after pre-burning, after releasing slip, mist projection granulating tower is utilized to carry out granulation.Powder after granulation is dry-pressing formed under the pressure condition of 15Mpa, is then sintered by tunnel furnace under the condition of 1260 DEG C.Work in-process after sintering are processed into the standard film of Ф 20 × 2mm, and at 750 DEG C of roasting silver after silver electrode is coated on two sides, then polarize in transformer oil, poling temperature is 140 DEG C, and polarizing voltage is 3000V/mm, and the polarization time is 20 minutes.Place and test its piezoelectric property parameters and Curie temperature after 24 hours.
Wherein, tackiness agent is polyvinyl alcohol and distilled water 90 DEG C of heating.
Dispersion agent is defloculating agent.
Dispersion agent is 0.5% of raw material weight; Glycerine is 0.05% of raw material weight; Tackiness agent is 8% of raw material weight.
Measured by this sample, piezoelectric property parameters and Curie temperature are respectively:
Electromechanical coupling factor Kp=0.621, piezoelectric constant d 33=389pC/N, DIELECTRIC CONSTANT ε=1998, Curie temperature Tc=370 DEG C
Embodiment 2
Preparation process is as follows:
With Pb 3o 4, ZrO 2, TiO 2, Nb 2o 5, SnO 2and MnO 2for raw material, according to composition formula Pb [(Sn 1/3nb 2/3) xzr yti 1-x-y] O 3, wherein x=0.05, y=0.48, calculates the quality of various raw material, takes Pb 3o 4, ZrO 2, TiO 2, Nb 2o 5, SnO 2preparation bulk composition, then add the MnO accounting for bulk composition mass percent 1.23% wherein 2as supplementary component.With deionized water as ball-milling medium, utilize agitating ball mill batch mixing 4 hours, discharging is with after pressure-filtering tank drainage, utilize oven for drying, add 7% deionized water and cross briquetting after 40 mesh sieves, at 800 DEG C, utilize tunnel furnace to carry out pre-burning, add suitable amount of adhesive, glycerine, dispersion agent with deionized water in agitating ball mill, carry out pulverizing grinding 6 hours as ball-milling medium again after pre-burning, after releasing slip, mist projection granulating tower is utilized to carry out granulation.Powder after granulation is dry-pressing formed under the pressure condition of 15Mpa, is then sintered by tunnel furnace under the condition of 1270 DEG C.Work in-process after sintering are processed into the standard film of Ф 20 × 2mm, and at 750 DEG C of roasting silver after silver electrode is coated on two sides, then polarize in transformer oil, poling temperature is 150 DEG C, and polarizing voltage is 3000V/mm, and the polarization time is 25 minutes.Place and test its piezoelectric property parameters and Curie temperature after 24 hours.
Wherein, tackiness agent is polyvinyl alcohol and distilled water 110 DEG C of heating.
Dispersion agent is defloculating agent.
Dispersion agent is 0.8% of raw material weight; Glycerine is 0.04% of raw material weight; Tackiness agent is 10% of raw material weight.
Measured by this sample, piezoelectric property parameters and Curie temperature are respectively:
Electromechanical coupling factor Kp=0.625, piezoelectric constant d 33=394pC/N, DIELECTRIC CONSTANT ε=1945, Curie temperature Tc=365 DEG C.
Embodiment 3
Preparation process is as follows:
With Pb 3o 4, ZrO 2, TiO 2, Nb 2o 5, SnO 2and MnO 2for raw material, according to composition formula Pb [(Sn 1/3nb 2/3) xzr yti 1-x-y] O 3, wherein x=0.07, y=0.50, calculates the quality of various raw material, takes Pb 3o 4, ZrO 2, TiO 2, Nb 2o 5, SnO 2preparation bulk composition, then add the MnO accounting for bulk composition mass percent 1.35% wherein 2as supplementary component.With deionized water as ball-milling medium, utilize agitating ball mill batch mixing 5 hours, discharging is with after pressure-filtering tank drainage, utilize oven for drying, add 8% deionized water and cross briquetting after 40 mesh sieves, at 810 DEG C, utilize tunnel furnace to carry out pre-burning, add suitable amount of adhesive, glycerine, dispersion agent with deionized water in agitating ball mill, carry out pulverizing grinding 5 hours as ball-milling medium again after pre-burning, after releasing slip, mist projection granulating tower is utilized to carry out granulation.Powder after granulation is dry-pressing formed under the pressure condition of 15Mpa, is then sintered by tunnel furnace under the condition of 1290 DEG C.Work in-process after sintering are processed into the standard film of Ф 20 × 2mm, and at 760 DEG C of roasting silver after silver electrode is coated on two sides, then polarize in transformer oil, poling temperature is 140 DEG C, and polarizing voltage is 2500V/mm, and the polarization time is 20 minutes.Place and test its piezoelectric property parameters and Curie temperature after 24 hours.
Wherein, tackiness agent is polyvinyl alcohol and distilled water 100 DEG C of heating.
Dispersion agent is defloculating agent.
Dispersion agent is 0.7% of raw material weight; Glycerine is 0.02% of raw material weight; Tackiness agent is 12% of raw material weight.
Measured by this sample, piezoelectric property parameters and Curie temperature are respectively:
Electromechanical coupling factor Kp=0.631, piezoelectric constant d 33=403pC/N, DIELECTRIC CONSTANT ε=2014, Curie temperature Tc=375 DEG C.
Embodiment 4
Preparation process is as follows:
With Pb 3o 4, ZrO 2, TiO 2, Nb 2o 5, SnO 2and MnO 2for raw material, according to composition formula Pb [(Sn 1/3nb 2/3) xzr yti 1-x-y] O 3, wherein x=0.06, y=0.51, calculates the quality of various raw material, takes Pb 3o 4, ZrO 2, TiO 2, Nb 2o 5, SnO 2preparation bulk composition, then add the MnO accounting for bulk composition mass percent 1.45% wherein 2as supplementary component.With deionized water as ball-milling medium, utilize agitating ball mill batch mixing 4 hours, discharging is with after pressure-filtering tank drainage, utilize oven for drying, add 8% deionized water and cross briquetting after 40 mesh sieves, at 820 DEG C, utilize tunnel furnace to carry out pre-burning, add suitable amount of adhesive, glycerine, dispersion agent with deionized water in agitating ball mill, carry out pulverizing grinding 6 hours as ball-milling medium again after pre-burning, after releasing slip, mist projection granulating tower is utilized to carry out granulation.Powder after granulation is dry-pressing formed under the pressure condition of 15Mpa, is then sintered by tunnel furnace under the condition of 1100 DEG C.Work in-process after sintering are processed into the standard film of Ф 20 × 2mm, and at 780 DEG C of roasting silver after silver electrode is coated on two sides, then polarize in transformer oil, poling temperature is 140 DEG C, and polarizing voltage is 3000V/mm, and the polarization time is 15 minutes.Place and test its piezoelectric property parameters and Curie temperature after 24 hours.
Wherein, tackiness agent is polyvinyl alcohol and distilled water 100 DEG C of heating.
Dispersion agent is defloculating agent.
Dispersion agent is 0.8% of raw material weight; Glycerine is 0.03% of raw material weight; Tackiness agent is 11% of raw material weight.
Measured by this sample, piezoelectric property parameters and Curie temperature are respectively:
Electromechanical coupling factor Kp=0.627, piezoelectric constant d 33=412pC/N, DIELECTRIC CONSTANT ε=2020, Curie temperature Tc=365 DEG C.
Embodiment 5
Preparation process is as follows:
With Pb 3o 4, ZrO 2, TiO 2, Nb 2o 5, SnO 2and MnO 2for raw material, according to composition formula Pb [(Sn 1/3nb 2/3) xzr yti 1-x-y] O 3, wherein x=0.05, y=0.50, calculates the quality of various raw material, takes Pb 3o 4, ZrO 2, TiO 2, Nb 2o 5, SnO 2preparation bulk composition, then add the MnO accounting for bulk composition mass percent 1.55% wherein 2as supplementary component.With deionized water as ball-milling medium, utilize agitating ball mill batch mixing 3 hours, discharging is with after pressure-filtering tank drainage, utilize oven for drying, add 9% deionized water and cross briquetting after 40 mesh sieves, at 820 DEG C, utilize tunnel furnace to carry out pre-burning, add suitable amount of adhesive, glycerine, dispersion agent with deionized water in agitating ball mill, carry out pulverizing grinding 6 hours as ball-milling medium again after pre-burning, after releasing slip, mist projection granulating tower is utilized to carry out granulation.Powder after granulation is dry-pressing formed under the pressure condition of 15Mpa, is then sintered by tunnel furnace under the condition of 1250 DEG C.Work in-process after sintering are processed into the standard film of Ф 20 × 2mm, and at 800 DEG C of roasting silver after silver electrode is coated on two sides, then polarize in transformer oil, poling temperature is 140 DEG C, and polarizing voltage is 3000V/mm, and the polarization time is 20 minutes.Place and test its piezoelectric property parameters and Curie temperature after 24 hours.
Wherein, tackiness agent is polyvinyl alcohol and distilled water 105 DEG C of heating.
Dispersion agent is defloculating agent.
Dispersion agent is 0.7% of raw material weight; Glycerine is 0.04% of raw material weight; Tackiness agent is 10% of raw material weight.
Measured by this sample, piezoelectric property parameters and Curie temperature are respectively:
Electromechanical coupling factor Kp=0.620, piezoelectric constant d 33=408pC/N, DIELECTRIC CONSTANT ε=1995, Curie temperature Tc=375 DEG C.
Embodiment 6
Preparation process is as follows:
With Pb 3o 4, ZrO 2, TiO 2, Nb 2o 5, SnO 2and MnO 2for raw material, according to composition formula Pb [(Sn 1/3nb 2/3) xzr yti 1-x-y] O 3, wherein x=0.08, y=0.47, calculates the quality of various raw material, takes Pb 3o 4, ZrO 2, TiO 2, Nb 2o 5, SnO 2preparation bulk composition, then add the MnO accounting for bulk composition mass percent 1.65% wherein 2as supplementary component.With deionized water as ball-milling medium, utilize agitating ball mill batch mixing 4 hours, discharging is with after pressure-filtering tank drainage, utilize oven for drying, add 7% deionized water and cross briquetting after 40 mesh sieves, at 825 DEG C, utilize tunnel furnace to carry out pre-burning, add suitable amount of adhesive, glycerine, dispersion agent with deionized water in agitating ball mill, carry out pulverizing grinding 6 hours as ball-milling medium again after pre-burning, after releasing slip, mist projection granulating tower is utilized to carry out granulation.Powder after granulation is dry-pressing formed under the pressure condition of 15Mpa, is then sintered by tunnel furnace under the condition of 1270 DEG C.Work in-process after sintering are processed into the standard film of Ф 20 × 2mm, and at 820 DEG C of roasting silver after silver electrode is coated on two sides, then polarize in transformer oil, poling temperature is 150 DEG C, and polarizing voltage is 2500V/mm, and the polarization time is 25 minutes.Place and test its piezoelectric property parameters and Curie temperature after 24 hours.
Wherein, tackiness agent is polyvinyl alcohol and distilled water 105 DEG C of heating.
Dispersion agent is defloculating agent.
Dispersion agent is 0.7% of raw material weight; Glycerine is 0.04% of raw material weight; Tackiness agent is 10% of raw material weight.
Measured by this sample, piezoelectric property parameters and Curie temperature are respectively:
Electromechanical coupling factor Kp=0.626, piezoelectric constant d 33=397pC/N, DIELECTRIC CONSTANT ε=1956, Curie temperature Tc=370 DEG C.
Embodiment 7
Preparation process is as follows:
With Pb 3o 4, ZrO 2, TiO 2, Nb 2o 5, SnO 2and MnO 2for raw material, according to composition formula Pb [(Sn 1/3nb 2/3) xzr yti 1-x-y] O 3, wherein x=0.05, y=0.48, calculates the quality of various raw material, takes Pb 3o 4, ZrO 2, TiO 2, Nb 2o 5, SnO 2preparation bulk composition, then add the MnO accounting for bulk composition mass percent 1.75% wherein 2as supplementary component.With deionized water as ball-milling medium, utilize agitating ball mill batch mixing 5 hours, discharging is with after pressure-filtering tank drainage, utilize oven for drying, add 8% deionized water and cross briquetting after 40 mesh sieves, at 825 DEG C, utilize tunnel furnace to carry out pre-burning, add suitable amount of adhesive, glycerine, dispersion agent with deionized water in agitating ball mill, carry out pulverizing grinding 6 hours as ball-milling medium again after pre-burning, after releasing slip, mist projection granulating tower is utilized to carry out granulation.Powder after granulation is dry-pressing formed under the pressure condition of 20Mpa, is then sintered by tunnel furnace under the condition of 1280 DEG C.Work in-process after sintering are processed into the standard film of Ф 20 × 2mm, and at 740 DEG C of roasting silver after silver electrode is coated on two sides, then polarize in transformer oil, poling temperature is 130 DEG C, and polarizing voltage is 3000V/mm, and the polarization time is 30 minutes.Place and test its piezoelectric property parameters and Curie temperature after 24 hours.
Wherein, tackiness agent is polyvinyl alcohol and distilled water 105 DEG C of heating.
Dispersion agent is defloculating agent.
Dispersion agent is 0.6% of raw material weight; Glycerine is 0.04% of raw material weight; Tackiness agent is 9% of raw material weight.
Measured by this sample, piezoelectric property parameters and Curie temperature are respectively:
Electromechanical coupling factor Kp=0.623, piezoelectric constant d 33=388pC/N, DIELECTRIC CONSTANT ε=1963, Curie temperature Tc=375 DEG C.

Claims (9)

1. a PZT piezoceramic material for high-curie temperature, is characterized in that, the composition formula of material is Pb [(Sn 1/3nb 2/3) xzr yti 1-x-y] O 3, 1.02 ~ 1.75%MnO of additional mass percent 2, wherein 0.04≤x≤0.08,0.47≤y≤0.51.
2. a preparation method for the PZT piezoceramic material of high-curie temperature according to claim 1, it is characterized in that, preparation method is as follows:
(1) by Pb 3o 4, ZrO 2, TiO 2, Nb 2o 5, SnO 2and MnO 2mixing, with deionized water as ball-milling medium, batch mixing;
(2) after batch mixing drainage, dry, add deionized water and cross after 30-50 mesh sieve after briquetting, pre-burning;
(3) use deionized water as ball-milling medium after pre-burning again, add tackiness agent, glycerine, dispersion agent, carry out pulverizing grinding, after releasing slip, utilize mist projection granulating tower to carry out granulation, dry-pressing formed under the powder condition after granulation, sintered by tunnel furnace;
(4) work in-process after sintering are processed into the standard film of Ф 20 × 2mm, at 700 ~ 820 DEG C of roasting silver after silver electrode is coated on two sides, are then placed in silicone oil and polarize;
Wherein, in step (2), the addition of deionized water is 5%-9%.
3. the preparation method of the PZT piezoceramic material of high-curie temperature according to claim 2, is characterized in that, mixing time is 3 ~ 5 hours.
4. the preparation method of the PZT piezoceramic material of high-curie temperature according to claim 2, is characterized in that, the temperature of pre-burning is 790 ~ 825 DEG C, and the time of pre-burning is 2 ~ 3 hours.
5. the preparation method of the PZT piezoceramic material of high-curie temperature according to claim 2, is characterized in that, tackiness agent is polyvinyl alcohol and distilled water 90-110 DEG C of heating; Dispersion agent is defloculating agent.
6. the preparation method of the PZT piezoceramic material of high-curie temperature according to claim 2, is characterized in that, dispersion agent is the 0.5%-0.8% of raw material weight; Glycerine is the 0.02%-0.05% of raw material weight; Tackiness agent is the 8%-12% of raw material weight.
7. the preparation method of the PZT piezoceramic material of high-curie temperature according to claim 2, is characterized in that, the time of pulverizing grinding is 5 ~ 7 hours; Dry-pressing formed pressure is the pressure of 10 ~ 20Mpa.
8. the preparation method of the PZT piezoceramic material of high-curie temperature according to claim 2, is characterized in that, sintering temperature is 1240 ~ 1290 DEG C; Sinter 2 ~ 4 hours.
9. the preparation method of the PZT piezoceramic material of high-curie temperature according to claim 2, is characterized in that, poling temperature is 130 ~ 150 DEG C, and polarizing voltage is 2500 ~ 3000V/mm, and the polarization time is 15 ~ 30 minutes.
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CN1428791A (en) * 2001-12-27 2003-07-09 三星电机株式会社 Piezoelectric ceramic composition and piezoelectric device using the same
CN101429022A (en) * 2008-12-12 2009-05-13 同济大学 Ferro-voltage ceramic component with low sintering temperature character, production and uses thereof

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