CN102010195B - Zirconium and molybdenum-doped bismuth layer-shaped leadless piezoelectric ceramic material and preparation method thereof - Google Patents

Zirconium and molybdenum-doped bismuth layer-shaped leadless piezoelectric ceramic material and preparation method thereof Download PDF

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CN102010195B
CN102010195B CN 201010271191 CN201010271191A CN102010195B CN 102010195 B CN102010195 B CN 102010195B CN 201010271191 CN201010271191 CN 201010271191 CN 201010271191 A CN201010271191 A CN 201010271191A CN 102010195 B CN102010195 B CN 102010195B
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srbi
molybdenum
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piezoelectric ceramic
lead
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CN102010195A (en
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闵鑫
钱小龙
房明浩
黄朝晖
刘艳改
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China University of Geosciences
China University of Geosciences Beijing
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Abstract

The invention relates to a zirconium and molybdenum-doped bismuth layer-shaped leadless piezoelectric ceramic material and a preparation method thereof, belonging to the field of piezoelectric ceramic materials. The novel piezoelectric ceramic material can be prepared by doping Zr and Mo at Ta position in a certain mol ratio according to a preparation method of a solid-phase process, with a SrBi2Ta2O9 system leadless piezoelectric ceramic material as a matrix. The formula of the leadless piezoelectric ceramic material is SrBi2(Zr0.5Mo0.5)xTa2-xO9, wherein x is not less than 0 and not more than 2. On the basis of SrBi2Ta2O9, the material improves the piezoelectric constant and reduces the dielectric constant. Meanwhile, the layer-shaped leadless piezoelectric ceramic material has the advantages of low electromechanical coupling coefficient, high mechanical quality factor and the like, can be used for preparing various piezoelectric ceramic elements, can be assembled into various piezoelectric sensors and has excellent performance.

Description

A kind of bismuth stratiform lead-free piezoceramic material of mixing zirconium and molybdenum and preparation method thereof
Technical field
The present invention relates to bismuth stratiform lead-free piezoceramic material of a kind of mix zirconium and molybdenum and preparation method thereof, belong to the piezoelectric ceramic preparing technical field.
Background technology
In the piezoelectric ceramic field, occupied an leading position by lead zirconate titanate (PZT) for a long time.Yet lead zirconate titanate ceramic is leaded pottery, and wherein lead oxide (or lead orthoplumbate) accounts for about 70% of raw material gross mass.Leaded piezoelectricity ferro pottery brings harm all can for environment and the mankind in processing, sintering process and use procedure.Therefore, exploitation without the environment compatibility piezoceramic material of lead base be one urgent and have a problem of important scientific meaning.
At present, both at home and abroad the leadless piezoelectric ceramics system of research mainly contains: barium phthalate base, bismuth laminated, bismuth sodium titanate based, base metal niobate system and tungsten bronze structure leadless piezoelectric ceramics.Wherein, the bismuth laminated leadless piezoelectric ceramic material has the characteristics such as photoelectric effect, nonlinear optical effect, unusual photovoltaic effect, photorefractive effect as a kind of ferroelectric material; Also has simultaneously high Curie temperature, the advantage such as good fatigue resistance and leakage current are little and be subject to researcher's attention.But the piezoelectric property of bismuth laminated leadless piezoelectric ceramic is also not ideal, and polarization intensity is higher, and existing angle from process modification and prescription improvement is studied it, greatly improves the piezoelectric property of bismuth laminated leadless piezoelectric ceramic material.
In the bismuth oxide-based layered perovskite lead-free piezoceramic material, SrBi 2Ta 2O 9Be one of material of most study, its dielectric and piezoelectric properties is more stable, but also has the shortcomings such as polarization intensity is higher, sintering temperature is higher.In practice, Zr 4+And Mo 6+With Ta 5+Ionic radius is close, also so that its electricity price is consistent, therefore when composite permutation Ta, can make SrBi by compound 2Ta 2O 9The slippage of dislocation motion and crystal boundary appears in crystal grain inside, realizes that it is to SrBi 2Ta 2O 9The complex phase substitution of piezoceramic material when reducing polarization intensity, improves its piezoelectric property and dielectric property as much as possible.
Up to now, yet there are no with zirconium and molybdenum atom replacement SrBi 2Ta 2O 9Leadless piezoelectric ceramics and the report that its piezoelectric property is affected.
Summary of the invention
The object of the invention is to utilize metallic element zirconium and molybdenum to SrBi 2(Zr 0.5Mo 0.5) xTa 2-xO 9In the Ta ion carry out substituting modification, reduce its polarization intensity, improve its piezoelectric property, prepare a kind of novel, environmentally friendly bismuth laminated piezoelectric ceramic material.
The composition formula of material of the present invention is SrBi 2(Zr 0.5Mo 0.5) xTa 2-xO 9, wherein in 0≤x≤2.
Material preparation method of the present invention is as follows:
(1) be to prepare burden by above-mentioned stoicheiometry, raw material choose strontium carbonate (SrCO 3), bismuth oxide (Bi 2O 3), tantalum pentoxide (Ta 2O 5), zirconia (ZrO 2) and molybdenum oxide (MoO 3), its final structure is SrBi 2(Zr 0.5Mo 0.5) xTa 2-xO 9Solid solution structure.
(2) take by weighing an amount of SrCO according to above-mentioned chemical formula proportioning 3, Bi 2O 3, ZrO 2, MoO 3, Ta 2O 5Deng raw material, with alcohol as dispersant, utilize the planetary ball mill ball mill mixing after 12～24 hours, the discharging oven dry, mixed material is ground, the dry-pressing under the pressure condition of 20～30MPa of gained powder is in blocks, then open wide sintering 800 ℃-1300 ℃ lower insulations, temperature retention time is 0.1-6 hour, and heating rate is 1～20 ℃/min.
Effect of the present invention is: pass through Zr 4+And Mo 6+To SrBi 2(Zr 0.5Mo 0.5) xTa 2-xO 9In Ta 5+Carry out substituting modification, by analyzing the different doping proportionings of contrast and firing temperature to the impact of its piezoelectric property, obtain a kind of low relative dielectric constant ε, low-dielectric loss value tan δ, high piezoelectric constant d 33Novel dominance can lead-free piezoceramic material, to satisfy the needs of productive life.
The implementation step
Below in conjunction with example characteristics of the present invention are described further book, but are not only to be confined to following embodiment.
Embodiment 1:
The present invention is with SrCO 3(analyzing pure), Bi 2O 3(analyzing pure), ZrO 2(analyzing pure), MoO 3(analyzing pure) and Ta 2O 5(analyzing pure) is raw material, gets x=0.1 according to stoichiometric equation, a=0.05.Then calculate the quality of each raw material and prepare burden, with alcohol as ball-milling medium, utilized the planetary ball mill ball mill mixing 12 hours, the discharging oven dry, mixed material is ground, the dry-pressing under the pressure condition of 30MPa of gained powder is in blocks, then at 1000 ℃ of lower unlimited sintering, be incubated 3 hours and become porcelain, heating rate is 5 ℃/min.Be about 0.5mm with the two-sided parallel polished of the ceramic disks of burning till to thickness, clean with ultrasonic cleaning after, the two-sided silver electrode that is coated with, making alive polarizes in silicone oil.Polarization condition is in 40 ℃ of silicone oil, adds 4kV/mm voltage and keeps 5 minutes.
SrBi 2(Zr 0.5Mo 0.5) 0.1Ta 1.9O 9The measured performance of leadless piezoelectric ceramics sample is: piezoelectric constant d 33=20pC/N, DIELECTRIC CONSTANT ε=185, electromechanical coupling factor K p=5.2%, mechanical quality factor Q m=2960.
Embodiment 2:
The present invention is with SrCO 3(analyzing pure), Bi 2O 3(analyzing pure), ZrO 2(analyzing pure), MoO 3(analyzing pure) and Ta 2O 5(analyzing pure) is raw material, gets x=0.1 according to stoichiometric equation, a=0.05.Then calculate the quality of each raw material and prepare burden, with alcohol as ball-milling medium, utilized the planetary ball mill ball mill mixing 12 hours, the discharging oven dry, mixed material is ground, the dry-pressing under the pressure condition of 30MPa of gained powder is in blocks, then at 1050 ℃ of lower unlimited sintering, be incubated 3 hours and become porcelain, heating rate is 5 ℃/min.Be about 0.5mm with the two-sided parallel polished of the ceramic disks of burning till to thickness, clean with ultrasonic cleaning after, the two-sided silver electrode that is coated with, making alive polarizes in silicone oil.Polarization condition is in 40 ℃ of silicone oil, adds 4kV/mm voltage and keeps 5 minutes.
Under this condition, SrBi 2(Zr 0.5Mo 0.5) 0.1Ta 1.9O 9The measured performance of leadless piezoelectric ceramics sample is: piezoelectric constant d 33=17pC/N, DIELECTRIC CONSTANT ε=180, electromechanical coupling factor K p=5.4%, mechanical quality factor Q m=2610.
Embodiment 3:
The present invention is with SrCO 3(analyzing pure), Bi 2O 3(analyzing pure), ZrO 2(analyzing pure), MoO 3(analyzing pure) and Ta 2O 5(analyzing pure) is raw material, gets x=0.1 according to stoichiometric equation, a=0.05.Then calculate the quality of each raw material and prepare burden, with alcohol as ball-milling medium, utilized the planetary ball mill ball mill mixing 12 hours, the discharging oven dry, mixed material is ground, the dry-pressing under the pressure condition of 30MPa of gained powder is in blocks, then at 1100 ℃ of lower unlimited sintering, be incubated 3 hours and become porcelain, heating rate is 5 ℃/min.Be about 0.5mm with the two-sided parallel polished of the ceramic disks of burning till to thickness, clean with ultrasonic cleaning after, the two-sided silver electrode that is coated with, making alive polarizes in silicone oil.Polarization condition is in 40 ℃ of silicone oil, adds 4kV/mm voltage and keeps 5 minutes.
Under this condition, SrBi 2(Zr 0.5Mo 0.5) 0.1Ta 1.9O 9The measured performance of leadless piezoelectric ceramics sample is: piezoelectric constant d 33=18pC/N, DIELECTRIC CONSTANT ε=183, electromechanical coupling factor K p=6.0%, mechanical quality factor Q m=2390.

Claims (7)

1. the SrBi of doping zirconium and molybdenum 2(Zr 0.5Mo 0.5) xTa 2-xO 9System bismuth stratiform leadless piezoelectric ceramics is characterized in that:
Chemical formula is: SrBi 2(Zr 0.5Mo 0.5) xTa 2-xO 9, 0＜x≤2 wherein.
2. SrBi by doping zirconium claimed in claim 1 and molybdenum 2(Zr 0.5Mo 0.5) xTa 2-xO 9The preparation method of (wherein 0＜x≤2) system bismuth stratiform lead-free piezoceramic material, key step comprise that batching, batch mixing, drying, grinding, dry-pressing formed, sintering, polishing, electric polarization process, and it is characterized in that:
(1) according to chemical formula SrBi 2(Zr 0.5Mo 0.5) xTa 2-xO 9Join and get raw material;
(2) sintering temperature is 800 ℃-1300 ℃, and temperature retention time is 0.1-6 hour.
3. according to the SrBi of doping zirconium claimed in claim 2 and molybdenum 2(Zr 0.5Mo 0.5) xTa 2-xO 9The preparation method of (wherein 0＜x≤2) system bismuth stratiform lead-free piezoceramic material is characterized in that adopting SrCO 3, Bi 2O 3, ZrO 2, MoO 3, Ta 2O 5Be raw material.
4. according to the SrBi of doping zirconium claimed in claim 2 and molybdenum 2(Zr 0.5Mo 0.5) xTa 2-xO 9The preparation method of (wherein 0＜x≤2) system bismuth stratiform lead-free piezoceramic material is characterized in that batch mixing adopts planetary ball mill technique, take alcohol as ball-milling medium.
5. according to the SrBi of doping zirconium claimed in claim 2 and molybdenum 2(Zr 0.5Mo 0.5) xTa 2-xO 9The preparation method of (wherein 0＜x≤2) system bismuth stratiform lead-free piezoceramic material is characterized in that dry-pressing formed pressure is 0.1～100MPa.
6. according to the SrBi of doping zirconium claimed in claim 2 and molybdenum 2(Zr 0.5Mo 0.5) xTa 2-xO 9The preparation method of (wherein 0＜x≤2) system bismuth stratiform lead-free piezoceramic material is characterized in that adopting and opens wide the synthetic method of calcining, and its sintering temperature is 800 ℃-1300 ℃, and temperature retention time is 0.1-6 hour.
7. according to the SrBi of doping zirconium claimed in claim 1 and molybdenum 2(Zr 0.5Mo 0.5) xTa 2-xO 9(wherein 0＜x≤2) system bismuth stratiform lead-free piezoceramic material, it is mainly used in the piezo ceramic element of the various shapes of preparation or is assembled into all kinds of piezoelectric transducers.
CN 201010271191 2010-09-03 2010-09-03 Zirconium and molybdenum-doped bismuth layer-shaped leadless piezoelectric ceramic material and preparation method thereof Active CN102010195B (en)

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