CN101935212A - Lead-free calcium barium zirconate titanate piezoelectric ceramics and preparation method thereof - Google Patents
Lead-free calcium barium zirconate titanate piezoelectric ceramics and preparation method thereof Download PDFInfo
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- CN101935212A CN101935212A CN 201010277864 CN201010277864A CN101935212A CN 101935212 A CN101935212 A CN 101935212A CN 201010277864 CN201010277864 CN 201010277864 CN 201010277864 A CN201010277864 A CN 201010277864A CN 101935212 A CN101935212 A CN 101935212A
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Abstract
The invention discloses lead-free calcium barium zirconate titanate piezoelectric ceramics and a preparation method thereof. The invention is characterized in that: the material composition is (1-x)Ba(Ti0.8Zr0.2)O3-x(Ba0.7Ca0.3)TiO3, wherein x=0.45 to 0.60; in the method, the (1-x)Ba(Ti0.8Zr0.2)O3-x(Ba0.7Ca0.3)TiO3 ceramics are prepared by a two-step presintering method. The lead-free calcium barium zirconate titanate piezoelectric ceramics have a main crystalline phase of a perovskite phase, have better piezoelectric property, the piezoelectric constants d33 of more than 240 pC/N, and the mechanical coupling factors kp of more than 0.40. The lead-free calcium barium zirconate titanate piezoelectric ceramics have higher piezoelectric constant, achieve the properties of the conventional lead-containing piezoelectric ceramics, have a stable and reliable preparation process, and have better application prospect.
Description
Technical field
The present invention relates to the piezoceramic material technical field, specifically is a kind of barium calcium zirconate titanate leadless piezoelectric ceramics and preparation method thereof.
Background technology
Piezoceramic material is meant that the ferroelectric ceramic material with piezoelectric effect is widely used in electronic devices and components such as piezoelectric ceramics resonator, piezoelectric filter, piezoelectric buzzer, ultrasonic transducer and piezoelectric ceramic transformer after the high direct voltage polarization.In traditional piezoceramic material most widely used general, the most sophisticated be plumbiferous Pb (Zr, Ti) O
3The brilliant material in (being abbreviated as PZT) Quito; but the main component of PZT pottery is PbO; and the fusing point of PbO is 889 ℃; it is a kind of volatile toxic substance; cause the severe problem of Lead contamination thus; along with the attention of countries in the world, certainly will adopt unleaded piezoelectric to substitute traditional lead base piezoceramic material, to reduce environmental pollution to environment protection.
Leadless piezoelectric ceramics is owing to its good prospects for application and have important meaning pollution-free, nuisanceless, that help environment protection, and developed countries such as the U.S., Japan pay close attention to the research of such material.Europe parliament in 2002 and EU Council have passed through the rules about " some objectionable impurities instruction is used in restriction in electrical equipment and the electronics ", comprising: the flint glass in dystectic leaded scolding tin, plumbiferous piezoelectric device, the electronic component etc., the enforcement time is 2006~2008 years; Japan has announced to realize the unleaded of piezoelectric ceramics in the period of 2006~2010; Recently, " the electronics and IT products production prevention and cure of pollution management method " that the Ministry of Information industry is working out will formally be put into effect at the end of this year, and then household appliances will be determined to use safely the time limit.From legislation, trade barrier (WTO) with strengthen the enterprise aspects such as core competitiveness in market at home and abroad, the research and development leadless piezoelectric ceramics has become a urgent strategic problem with alternative traditional PZT sill.
At present, the leadless piezoelectric ceramics system of people's research mainly contains: (1) perovskite structure leadless piezoelectric ceramics; (2) bismuth laminated leadless piezoelectric ceramic; (3) tungsten bronze structure leadless piezoelectric ceramics etc.In general, the bismuth laminated leadless piezoelectric ceramic Curie temperature is higher, and anisotropy is big and piezoelectric activity is lower, and Haixue Yan etc. has studied bismuth layer structured CaBi
2Nb
2O
9Pottery (being abbreviated as CBNO), its Curie temperature T
CBe 943 ℃, but its piezoelectric constant is very low, the piezoelectric constant d of OF CBNO
33Be about 7.5pC/N, the d of SPS (⊥) and SPS (//) CBNO
33Be respectively 19.5pC/N, 0.2pC/N (Haixue Yan, Hongtao Zhang, Rick Ubic, MichaelJ.Reece, Jing Liu, Zhijian Shen and Zhen Zhang.A Lead-Free High-Curie-PointFerroelectric Ceramic, CaBi
2Nb
2O
9[J] .Advanced Materials, 2005,17:1261-1265).The tungsten bronze structure pottery has characteristics such as spontaneous polarization strength is big, Curie temperature is higher, specific inductivity is lower, its composition has material impact with the ferroelectric properties of constructing it, studying more tungsten bronze structure leadless piezoelectric material material is strontium barium niobate, but the report to this system piezoelectric ceramics performance less (Peng Chun pretty young woman Li Jing cutting edge of a knife or a sword. the application of leadless piezoelectric ceramics and progress [J]. new material industry, 2005,3:45-51).Perovskite structure has relative higher piezoelectric constant, BaTiO
3Pottery has medium piezoelectric property, d
33Be 191pC/N.At publication number is in the patent of invention of CN 1715242A, and Li Long soil etc. has been studied (1-x) Bi
1/2(Na
1-zK
z)
1/2TiO
3-xBa (Zr
yTi
1-y) O
3The piezoelectric property of pottery, its piezoelectric constant d
33Reach 165pC/N.The publication number of honest announcement such as quick of renting is in the patent of invention of CN 101239824A, (1-z) (K
1-xNa
x) NbO
3-zBa (Ti
1-yZr
y) O
3The d of pottery
33Value reaches 234pC/N.No matter yet the leadless piezoelectric ceramics of above-mentioned which kind of structure, with Pb (Zr, Ti) O
3Base piezoelectric ceramic is compared the problem that exists piezoelectric activity low, particularly the piezoelectric constant d of the leadless piezoelectric ceramics prepared of conventional piezoelectric ceramic process
33Be difficult to be higher than 250pC/N, hinder its practical application, therefore improve performance, improve focus and difficult point that piezoelectric activity just becomes research.Particularly after the China joined WTO, successfully developing and have leadless piezoelectric ceramics system original creativity, that have independent intellectual property right, excellent property, concerning China's piezoelectric ceramics industry, is stern challenge, is again the opportunity of rapid development.
Summary of the invention
For solve existing piezoelectric ceramics because of leaded use and discarded last handling process in the problem that pollutes to environment, and the piezoelectric property that improves unleaded serial piezoelectric ceramics, the present invention proposes a kind of barium calcium zirconate titanate leadless piezoelectric ceramics and preparation method thereof.
Of the present invention consisting of (1-x) Ba (Ti
0.8Zr
0.2) O
3-x (Ba
0.7Ca
0.3) TiO
3, x=0.45~0.60 wherein.
Preparation process of the present invention comprises:
The first step, preparation BaTiO
3, BaZrO
3And CaTiO
3Powder; Preparation BaTiO
3Powder: establishing n is amount of substance, with analytically pure BaCO
3, TiO
2Be raw material, press n (BaCO
3): n (TiO
2)=1: 1 weigh batching, ball milling 12h in anhydrous ethanol medium after 50~60 ℃ insulation 8~20h is dried powder down, at 1000~1200 ℃ of pre-burning 2~6h, obtains BaTiO
3Powder; Preparation BaZrO
3Powder: with analytically pure BaCO
3, ZrO
2Be raw material, press n (BaCO
3): n (ZrO
2)=1: 1 weigh batching, ball milling 12h in anhydrous ethanol medium after 50~60 ℃ insulation 8~20h is dried powder down, at 1000~1200 ℃ of pre-burning 2~6h, obtains BaZrO
3Powder; Preparation CaTiO
3Powder: with analytically pure CaCO
3, TiO
2Be raw material, press n (CaCO
3): n (TiO
2)=1: 1 weigh batching, ball milling 12h in anhydrous ethanol medium after 50~60 ℃ insulation 8~20h is dried powder down, at 1000~1200 ℃ of pre-burning 2~6h, obtains CaTiO
3Powder;
Second step, preparation Ba (Ti
0.8Zr
0.2) O
3, (Ba
0.7Ca
0.3) TiO
3Powder; Preparation Ba (Ti
0.8Zr
0.2) O
3Powder: with the BaTiO of previous step acquisition
3, BaZrO
3Powder is a raw material, presses n (BaTiO
3): n (BaZrO
3)=4: 1 weigh batching, ball milling 12h in anhydrous ethanol medium after 50~60 ℃ insulation 8~20h is dried powder down, at 1200~1400 ℃ of pre-burning 2~6h, obtains Ba (Ti
0.8Zr
0.2) O
3Powder; Preparation (Ba
0.7Ca
0.3) TiO
3Powder: with the BaTiO of previous step acquisition
3, CaTiO
3Powder is a raw material, presses n (BaTiO
3): n (CaTiO
3)=7: 3 weigh batching, ball milling 12h in anhydrous ethanol medium after 50~60 ℃ insulation 8~20h is dried powder down, at 1200~1400 ℃ of pre-burning 2~6h, obtains (Ba
0.7Ca
0.3) TiO
3Powder;
The 3rd step, batch mixing and moulding; According to forming (1-x) Ba (Ti
0.8Zr
0.2) O
3-x (Ba
0.7Ca
0.3) TiO
3, with the Ba (Ti that is obtained
0.8Zr
0.2) O
3(Ba
0.7Ca
0.3) TiO
3Powder is a raw material, presses n (Ba (Ti
0.8Zr
0.2) O
3): n ((Ba
0.7Ca
0.3) TiO
3)=(1-x): the x weigh batching, x=0.45~0.60 wherein, and in anhydrous ethanol medium mixing and ball milling 12h, in 50~60 ℃ down behind insulation 8~20h oven dry powder, add the PVA granulation of 5wt%, compression moulding under the pressure of 100~200MPa;
The 4th step, sintering; Behind the abundant binder removal of ceramic green, sintering 2~6h in 1400~1500 ℃ prepares the barium calcium zirconate titanate pottery.
To the barium calcium zirconate titanate leadless piezoelectric ceramics fine grinding processing that obtains, by silver electrode, be used for the piezoelectric property test after the ultrasonic cleaning.
Barium calcium zirconate titanate pottery provided by the present invention is the piezoelectrics of perovskite structure, and at room temperature the four directions coexists mutually with water chestnut side mutually, according to accurate homotype phase boundary theory as can be known, this piezoelectric ceramics performance can be improved significantly.From the above, choose the method for two step pre-burnings, overcome the inherent defect of existing lead base material, and improved the performance of existing leadless piezoelectric ceramics.
(1-x) Ba (Ti of the present invention's preparation
0.8Zr
0.2) O
3-x (Ba
0.7Ca
0.3) TiO
3Stupalith has obtained higher density and high tension performance, piezoelectric constant d
33All greater than 240pC/N, electromechanical coupling factor k
pAll greater than 0.40.Compare with other leadless piezoelectric ceramics, its piezoelectric constant is higher, and has reached business-like conventional P ZT performance of piezoelectric ceramics.Stable preparation process of the present invention is reliable, obtains bigger piezoelectric constant with technology simple to operate, is hopeful very much to replace the PZT material, at industrial circle very big application potential is arranged.
Description of drawings
Fig. 1 is the schema of barium calcium zirconate titanate ceramic preparation.
Fig. 2 is the XRD figure spectrum of embodiment one to embodiment four sample, and wherein: a is the XRD figure spectrum of sample among the embodiment one; B is the XRD figure spectrum of sample among the embodiment two; C is the XRD figure spectrum of sample among the embodiment three; D represents the XRD figure spectrum of sample among the embodiment four.
Embodiment
Embodiment one
The component of present embodiment is (1-x) Ba (Ti
0.8Zr
0.2) O
3-x (Ba
0.7Ca
0.3) TiO
3, x=0.45 wherein.
The first step, preparation BaTiO
3, BaZrO
3And CaTiO
3Powder; Preparation BaTiO
3Powder: establish n and represent amount of substance, with analytically pure BaCO
3, TiO
2Be raw material, press n (BaCO
3): n (TiO
2)=1: 1 weigh batching, ball milling 12h in anhydrous ethanol medium after 50 ℃ insulation 14h is dried powder down, at 1100 ℃ of pre-burning 4h, obtains BaTiO
3Powder; Preparation BaZrO
3Powder: with analytically pure BaCO
3, ZrO
2Be raw material, press n (BaCO
3): n (ZrO
2)=1: 1 weigh batching, ball milling 12h in anhydrous ethanol medium after 50 ℃ insulation 14h is dried powder down, at 1100 ℃ of pre-burning 4h, obtains BaZrO
3Powder; Preparation CaTiO
3Powder: with analytically pure CaCO
3, TiO
2Be raw material, press n (CaCO
3): n (TiO
2)=1: 1 weigh batching, ball milling 12h in anhydrous ethanol medium after 50 ℃ insulation 14h is dried powder down, at 1100 ℃ of pre-burning 4h, obtains CaTiO
3Powder.BaCO wherein
3, TiO
2And ZrO
2Purity be 99%, CaCO
3Purity be 99.95%;
Second step, preparation Ba (Ti
0.8Zr
0.2) O
3, (Ba
0.7Ca
0.3) TiO
3Powder; Preparation Ba (Ti
0.8Zr
0.2) O
3Powder: with the BaTiO of previous step acquisition
3, BaZrO
3Powder is a raw material, presses n (BaTiO
3): n (BaZrO
3)=4: 1 weigh batching, ball milling 12h in anhydrous ethanol medium after 50 ℃ insulation 14h is dried powder down, at 1300 ℃ of pre-burning 4h, obtains Ba (Ti
0.8Zr
0.2) O
3Powder; Preparation (Ba
0.7Ca
0.3) TiO
3Powder: with the BaTiO of previous step acquisition
3, CaTiO
3Powder is a raw material, presses n (BaTiO
3): n (CaTiO
3)=7: 3 weigh batching, ball milling 12h in anhydrous ethanol medium after 50 ℃ insulation 14h is dried powder down, at 1300 ℃ of pre-burning 4h, obtains (Ba
0.7Ca
0.3) TiO
3Powder;
The 3rd step, batch mixing and moulding; According to forming (1-x) Ba (Ti
0.8Zr
0.2) O
3-x (Ba
0.7Ca
0.3) TiO
3Weigh batching, wherein x is 0.45, with Ba (Ti
0.8Zr
0.2) O
3(Ba
0.7Ca
0.3) TiO
3Powder is mixing and ball milling 12h in anhydrous ethanol medium, after 50 ℃ insulation 14h is dried powder down, adds the PVA granulation of 5wt%, compression moulding under the pressure of 100MPa;
The 4th step, sintering; Behind the abundant binder removal of ceramic green, sintering 4h in 1450 ℃ prepares the barium calcium zirconate titanate pottery.
Fig. 2 (a) has provided the XRD figure spectrum of sample, and the visible material principal crystalline phase is the uhligite phase structure.The electric property of sample sees Table 1, its piezoelectric constant d
33〉=290pC/N, electromechanical coupling factor k
pBe 0.42, mechanical quality factor Q
mBe 189.
Embodiment two
The component of present embodiment is (1-x) Ba (Ti
0.8Zr
0.2) O
3-x (Ba
0.7Ca
0.3) TiO
3, x=0.50 wherein.
The first step, preparation BaTiO
3, BaZrO
3And CaTiO
3Powder; Preparation BaTiO
3Powder: establish n and represent amount of substance, with analytically pure BaCO
3, TiO
2Be raw material, press n (BaCO
3): n (TiO
2)=1: 1 weigh batching, ball milling 12h in anhydrous ethanol medium after 60 ℃ insulation 8h is dried powder down, at 1200 ℃ of pre-burning 2h, obtains BaTiO
3Powder; Preparation BaZrO
3Powder: with analytically pure BaCO
3, ZrO
2Be raw material, press n (BaCO
3): n (ZrO
2)=1: 1 weigh batching, ball milling 12h in anhydrous ethanol medium after 60 ℃ insulation 8h is dried powder down, at 1200 ℃ of pre-burning 2h, obtains BaZrO
3Powder; Preparation CaTiO
3Powder: with analytically pure CaCO
3, TiO
2Be raw material, press n (CaCO
3): n (TiO
2)=1: 1 weigh batching, ball milling 12h in anhydrous ethanol medium after 60 ℃ insulation 8h is dried powder down, at 1200 ℃ of pre-burning 2h, obtains CaTiO
3Powder.BaCO wherein
3, TiO
2And ZrO
2Purity be 99%, CaCO
3Purity be 99.95%;
Second step, preparation Ba (Ti
0.8Zr
0.2) O
3, (Ba
0.7Ca
0.3) TiO
3Powder; Preparation Ba (Ti
0.8Zr
0.2) O
3Powder: with the BaTiO of previous step acquisition
3, BaZrO
3Powder is a raw material, presses n (BaTiO
3): n (BaZrO
3)=4: 1 weigh batching, ball milling 12h in anhydrous ethanol medium after 60 ℃ insulation 8h is dried powder down, at 1400 ℃ of pre-burning 2h, obtains Ba (Ti
0.8Zr
0.2) O
3Powder; Preparation (Ba
0.7Ca
0.3) TiO
3Powder: with the made BaTiO of previous step
3, CaTiO
3Powder is a raw material, presses n (BaTiO
3): n (CaTiO
3)=7: 3 weigh batching, ball milling 12h in anhydrous ethanol medium after 60 ℃ insulation 8h is dried powder down, at 1400 ℃ of pre-burning 2h, obtains (Ba
0.7Ca
0.3) TiO
3Powder;
The 3rd step, batch mixing and moulding; According to forming (1-x) Ba (Ti
0.8Zr
0.2) O
3-x (Ba
0.7Ca
0.3) TiO
3Weigh batching, wherein x is 0.50, with Ba (Ti
0.8Zr
0.2) O
3(Ba
0.7Ca
0.3) TiO
3Powder is mixing and ball milling 12h in anhydrous ethanol medium, after 60 ℃ insulation 8h is dried powder down, adds the PVA granulation of 5wt%, compression moulding under the pressure of 100MPa;
The 4th step, sintering; Behind the abundant binder removal of ceramic green, sintering 2h in 1500 ℃ prepares the barium calcium zirconate titanate pottery.
Fig. 2 (b) has provided the XRD figure spectrum of sample, and the visible material principal crystalline phase is the uhligite phase structure.The electric property of sample sees Table 1, its piezoelectric constant d
33〉=385pC/N, electromechanical coupling factor k
pBe 0.46, mechanical quality factor Q
mBe 124.
Embodiment three
The component of present embodiment is (1-x) Ba (Ti
0.8Zr
0.2) O
3-x (Ba
0.7Ca
0.3) TiO
3, x=0.55 wherein.
The first step, preparation BaTiO
3, BaZrO
3And CaTiO
3Powder; Preparation BaTiO
3Powder: establish n and represent amount of substance, with analytically pure BaCO
3, TiO
2Be raw material, press n (BaCO
3): n (TiO
2)=1: 1 weigh batching, ball milling 12h in anhydrous ethanol medium after 50 ℃ insulation 20h is dried powder down, at 1000 ℃ of pre-burning 6h, obtains BaTiO
3Powder; Preparation BaZrO
3Powder: with analytically pure BaCO
3, ZrO
2Be raw material, press n (BaCO
3): n (ZrO
2)=1: 1 weigh batching, ball milling 12h in anhydrous ethanol medium after 50 ℃ insulation 20h is dried powder down, at 1000 ℃ of pre-burning 6h, obtains BaZrO
3Powder; Preparation CaTiO
3Powder: with analytically pure CaCO
3, TiO
2Be raw material, press n (CaCO
3): n (TiO
2)=1: 1 weigh batching, ball milling 12h in anhydrous ethanol medium after 50 ℃ insulation 20h is dried powder down, at 1000 ℃ of pre-burning 6h, obtains CaTiO
3Powder.BaCO wherein
3, TiO
2And ZrO
2Purity be 99%, CaCO
3Purity be 99.95%;
Second step, preparation Ba (Ti
0.8Zr
0.2) O
3, (Ba
0.7Ca
0.3) TiO
3Powder; Preparation Ba (Ti
0.8Zr
0.2) O
3Powder: with the BaTiO of previous step acquisition
3, BaZrO
3Powder is a raw material, presses n (BaTiO
3): n (BaZrO
3)=4: 1 weigh batching, ball milling 12h in anhydrous ethanol medium after 50 ℃ insulation 20h is dried powder down, at 1200 ℃ of pre-burning 6h, obtains Ba (Ti
0.8Zr
0.2) O
3Powder; Preparation (Ba
0.7Ca
0.3) TiO
3Powder: with the made BaTiO of previous step
3, CaTiO
3Powder is a raw material, presses n (BaTiO
3): n (CaTiO
3)=7: 3 weigh batching, ball milling 12h in anhydrous ethanol medium after 50 ℃ insulation 20h is dried powder down, at 1200 ℃ of pre-burning 6h, obtains (Ba
0.7Ca
0.3) TiO
3Powder;
The 3rd step, batch mixing and moulding; According to forming (1-x) Ba (Ti
0.8Zr
0.2) O
3-x (Ba
0.7Ca
0.3) TiO
3Weigh batching, wherein x is 0.55, with Ba (Ti
0.8Zr
0.2) O
3(Ba
0.7Ca
0.3) TiO
3Powder is mixing and ball milling 12h in anhydrous ethanol medium, after 50 ℃ insulation 20h is dried powder down, adds the PVA granulation of 5wt%, compression moulding under the pressure of 200MPa;
The 4th step, sintering; Behind the abundant binder removal of ceramic green, sintering 6h in 1400 ℃ prepares the barium calcium zirconate titanate pottery.
Fig. 2 (c) has provided the XRD figure spectrum of sample, and the visible material principal crystalline phase is the uhligite phase structure.The electric property of sample sees Table 1, its piezoelectric constant d
33〉=304pC/N, electromechanical coupling factor k
pBe 0.41, mechanical quality factor Q
mBe 174.
Embodiment four
The component of present embodiment is (1-x) Ba (Ti
0.8Zr
0.2) O
3-x (Ba
0.7Ca
0.3) TiO
3, x=0.60 wherein.
The first step, preparation BaTiO
3, BaZrO
3And CaTiO
3Powder; Preparation BaTiO
3Powder: establish n and represent amount of substance, with analytically pure BaCO
3, TiO
2Be raw material, press n (BaCO
3): n (TiO
2)=1: 1 weigh batching, ball milling 12h in anhydrous ethanol medium after 50 ℃ insulation 8h is dried powder down, at 1100 ℃ of pre-burning 4h, obtains BaTiO
3Powder; Preparation BaZrO
3Powder: with analytically pure BaCO
3, ZrO
2Be raw material, press n (BaCO
3): n (ZrO
2)=1: 1 weigh batching, ball milling 12h in anhydrous ethanol medium after 50 ℃ insulation 8h is dried powder down, at 1100 ℃ of pre-burning 4h, obtains BaZrO
3Powder; Preparation CaTiO
3Powder: with analytically pure CaCO
3, TiO
2Be raw material, press n (CaCO
3): n (TiO
2)=1: 1 weigh batching, ball milling 12h in anhydrous ethanol medium after 50 ℃ insulation 8h is dried powder down, at 1100 ℃ of pre-burning 4h, obtains CaTiO
3Powder.BaCO wherein
3, TiO
2And ZrO
2Purity be 99%, CaCO
3Purity be 99.95%;
Second step, preparation Ba (Ti
0.8Zr
0.2) O
3, (Ba
0.7Ca
0.3) TiO
3Powder; Preparation Ba (Ti
0.8Zr
0.2) O
3Powder: with the BaTiO of previous step acquisition
3, BaZrO
3Powder is a raw material, presses n (BaTiO
3): n (BaZrO
3)=4: 1 weigh batching, ball milling 12h in anhydrous ethanol medium after 50 ℃ insulation 8h is dried powder down, at 1300 ℃ of pre-burning 4h, obtains Ba (Ti
0.8Zr
0.2) O
3Powder; Preparation (Ba
0.7Ca
0.3) TiO
3Powder: with the BaTiO of previous step acquisition
3, CaTiO
3Powder is a raw material, presses n (BaTiO
3): n (CaTiO
3)=7: 3 weigh batching, ball milling 12h in anhydrous ethanol medium after 50 ℃ insulation 8h is dried powder down, at 1300 ℃ of pre-burning 4h, obtains (Ba
0.7Ca
0.3) TiO
3Powder;
The 3rd step, batch mixing and moulding; According to forming (1-x) Ba (Ti
0.8Zr
0.2) O
3-x (Ba
0.7Ca
0.3) TiO
3Weigh batching, wherein x is 0.60, with Ba (Ti
0.8Zr
0.2) O
3(Ba
0.7Ca
0.3) TiO
3Powder is mixing and ball milling 12h in anhydrous ethanol medium, after 50 ℃ insulation 8h is dried powder down, adds the PVA granulation of 5wt%, compression moulding under the pressure of 150MPa;
The 4th step, sintering; Behind the abundant binder removal of ceramic green, sintering 4h in 1450 ℃ prepares the barium calcium zirconate titanate pottery.
Fig. 2 (d) has provided the XRD figure spectrum of sample, and the visible material principal crystalline phase is the uhligite phase structure.The electric property of sample sees Table 1, its piezoelectric constant d
33〉=240pC/N, electromechanical coupling factor k
pBe 0.40, mechanical quality factor Q
mBe 184.
The electrical property of table 1 embodiment one to embodiment four sample
Claims (2)
1. a barium calcium zirconate titanate leadless piezoelectric ceramics is characterized in that the component of described barium calcium zirconate titanate leadless piezoelectric ceramics is (1-x) Ba (Ti
0.8Zr
0.2) O
3-x (Ba
0.7Ca
0.3) TiO
3, x=0.45~0.60 wherein.
2. one kind prepares the method for barium calcium zirconate titanate leadless piezoelectric ceramics according to claim 1, it is characterized in that the preparation process of described barium calcium zirconate titanate leadless piezoelectric ceramics may further comprise the steps:
The first step, preparation BaTiO
3, BaZrO
3And CaTiO
3Powder; Preparation BaTiO
3Powder: establishing n is amount of substance, with analytically pure BaCO
3, TiO
2Be raw material, press n (BaCO
3): n (TiO
2)=1: 1 weigh batching, ball milling 12h in anhydrous ethanol medium after 50~60 ℃ insulation 8~20h is dried powder down, at 1000~1200 ℃ of pre-burning 2~6h, obtains BaTiO
3Powder; Preparation BaZrO
3Powder: with analytically pure BaCO
3, ZrO
2Be raw material, press n (BaCO
3): n (ZrO
2)=1: 1 weigh batching, ball milling 12h in anhydrous ethanol medium after 50~60 ℃ insulation 8~20h is dried powder down, at 1000~1200 ℃ of pre-burning 2~6h, obtains BaZrO
3Powder; Preparation CaTiO
3Powder: with analytically pure CaCO
3, TiO
2Be raw material, press n (CaCO
3): n (TiO
2)=1: 1 weigh batching, ball milling 12h in anhydrous ethanol medium after 50~60 ℃ insulation 8~20h is dried powder down, at 1000~1200 ℃ of pre-burning 2~6h, obtains CaTiO
3Powder;
Second step, preparation Ba (Ti
0.8Zr
0.2) O
3, (Ba
0.7Ca
0.3) TiO
3Powder; Preparation Ba (Ti
0.8Zr
0.2) O
3Powder: with the BaTiO of previous step acquisition
3, BaZrO
3Powder is a raw material, presses n (BaTiO
3): n (BaZrO
3)=4: 1 weigh batching, ball milling 12h in anhydrous ethanol medium after 50~60 ℃ insulation 8~20h is dried powder down, at 1200~1400 ℃ of pre-burning 2~6h, obtains Ba (Ti
0.8Zr
0.2) O
3Powder; Preparation (Ba
0.7Ca
0.3) TiO
3Powder: with the BaTiO of previous step acquisition
3, CaTiO
3Powder is a raw material, presses n (BaTiO
3): n (CaTiO
3)=7: 3 weigh batching, ball milling 12h in anhydrous ethanol medium after 50~60 ℃ insulation 8~20h is dried powder down, at 1200~1400 ℃ of pre-burning 2~6h, obtains (Ba
0.7Ca
0.3) TiO
3Powder;
The 3rd step, batch mixing and moulding; According to forming (1-x) Ba (Ti
0.8Zr
0.2) O
3-x (Ba
0.7Ca
0.3) TiO
3, with the Ba (Ti that obtains
0.8Zr
0.2) O
3(Ba
0.7Ca
0.3) TiO
3Powder is a raw material, presses n (Ba (Ti
0.8Zr
0.2) O
3): n ((Ba
0.7Ca
0.3) TiO
3)=(1-x): the x weigh batching, x=0.45~0.60 wherein, and in anhydrous ethanol medium mixing and ball milling 12h, in 50~60 ℃ down behind insulation 8~20h oven dry powder, add the PVA granulation of 5wt%, compression moulding under the pressure of 100~200MPa;
The 4th step, sintering; Behind the abundant binder removal of ceramic green, sintering 2~6h in 1400~1500 ℃ prepares the barium calcium zirconate titanate pottery.
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