CN102584230A - Piezoceramic material with high piezoelectric modulus and high electrostriction under low temperature sintering and preparation method thereof - Google Patents
Piezoceramic material with high piezoelectric modulus and high electrostriction under low temperature sintering and preparation method thereof Download PDFInfo
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- CN102584230A CN102584230A CN2012100520327A CN201210052032A CN102584230A CN 102584230 A CN102584230 A CN 102584230A CN 2012100520327 A CN2012100520327 A CN 2012100520327A CN 201210052032 A CN201210052032 A CN 201210052032A CN 102584230 A CN102584230 A CN 102584230A
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Abstract
The invention relates to a piezoceramic material with high piezoelectric modulus and high electrostriction under low temperature sintering. In the components of the piezoceramic material provided by the invention, lead magnesium niobate-lead zirconate titanate compositely doped and modified by strontium and barium is adopted as a matrix, and CuO also exists. By selecting an appropriate preparation process, an appropriate ratio of Zr to Ti, an appropriate doping amount of the strontium and the barium and an appropriate sintering assistant, the densified piezoceramic material with high piezoelectric modulus and high electrostriction properties and piezoelectric elements are prepared under the condition of lowering the sintering temperature. The piezoceramic material has a promising application prospect in stacked piezoelectric filters, stacked piezoelectric micro-displacement machines, stacked piezoelectric transformers and the like.
Description
Technical field
The present invention relates to technical field of piezoelectric materials, be specifically related to a kind of high tension electricity coefficient, the low sintering piezoceramic material of high electric field induced strain and preparation method thereof.
Background technology
Piezoelectric has through applying electric field generation strain effects (electric energy is changed to mechanical energy) from the outside and through receive stress produces the effect (mechanical energy is changed to electric energy) of electric charge on the surface material from the outside; Can be used for detection and storage of various information etc., be widely used in technical fields such as military affairs, automobile, commerce and medical treatment.Like lead zirconate titanate salt (Pb (Zr, Ti)) O
3PZT) etc. piezoelectric can be 1 * 10 for the voltage that applies
-10The strain of ratio takes place roughly to be in the instruction of m/V, therefore can adjust small position.Opposite with it in addition, piezoelectric can generation and stress application or with the proportional electric charge of self-deformation amount, therefore can be applicable to transmitter.
Piezoelectric ceramics is a kind of polycrystal piezoelectric with piezoelectric effect, and piezoelectric ceramics commonly used has barium titanate series, lead titanate-lead zirconates two component system and in two component system, adds the third ABO
3(A representes divalent-metal ion, and B representes that quadrivalent metallic ion or several kinds of ion summations are positive tetravalence) type compound if on three-part system, add the 4th kind or more compound again, can be formed quaternary system or polynary system piezoelectric ceramics.
Along with the raising of modern integrated circuits scale and speed, piezoelectric ceramic devices are just integrated towards complete machine, the direction of miniaturized, slimming, lightness, high performance develops.Under demand pull and technology promoted, the stacked piezoelectric electronic component arose at the historic moment.The stacked piezoelectric electronic component is to be superimposed together a ceramic membrane biscuit that applies internal and external electrode in some way, through once sintered make it to become one process.The electronic devices and components of processing through this technology have advantages such as volume is little, internal inductance is little, moisture-proof, life-span length, good reliability; Become one of element that adapts to the electronic technology development most; At home and abroad paid attention to fully at present; Corresponding product has appearred in the Japan and the U.S., and is domestic, and the research of stacked piezoelectric electronic component is also carried out.Because electrode and biscuit of ceramics burnt altogether in the stacked piezoelectric electronic component adopted; In order to guarantee ceramic sintered compact; Must use high-temperature electrode materials such as Pd, Pt; Thereby having improved cost, so manage to reduce sintering temperature of piezoelectric ceramics so that adopt Ag, Ag/Ni, Ag/Pd electrode to realize burning altogether, is an important research direction all the time.
Study more Pb (Zr, Ti) O at present
3The sintering temperature of (brief PZT) pottery can be reduced to about about 1050 ℃, but in order really to realize low temperature co-fired (~950 ℃), also needs further to reduce sintering temperature of piezoelectric ceramics, and make the piezoelectric property that keeps good.On the other hand, the research to the electric field induced strain performance in the present report is very few, can not satisfy the application demand of stacked piezoelectric wave filter, stacked piezoelectric micro positioner and stacked piezoelectric X-former etc.
Summary of the invention
Problem in the face of the prior art existence; The inventor recognizes provides a kind of have high tension electricity coefficient, high electric field induced strain characteristic; Can realize the strontium of dense sintering, the lead magnoniobate-lead lanthanum zirconate titanate (PLZT) electrooptical ceramics material of barium composite doping modification at low temperature again, to satisfy the application demand of stacked piezoelectric wave filter, stacked piezoelectric micro positioner and stacked piezoelectric X-former etc.The preparation method preparation technology of piezoceramic material provided by the invention is simple simultaneously, prescription is adjustable, applicable to scale prodn.
For this reason, the present invention provides a kind of high tension electricity coefficient, the low sintering piezoceramic material of high electric field induced strain, and wherein, the composition of said material is a matrix with the lead magnoniobate-Pb-based lanthanumdoped zirconate titanates of strontium, barium composite doping modification, and contains CuO.
Among the present invention, said piezoceramic material can be represented with following general formula:
Pb
1-x-ySr
xBa
y(Mg
1/3Nb
2/3)
0.25Ti
0.40Zr
0.35O
3+ awt.%CuO, wherein, 0.02≤x≤0.06,0.02≤y≤0.06,0.2≤a≤0.5.Preferably, the content of CuO is 0.2~0.5wt.%.
The present invention also provides a kind of preparation method of above-mentioned piezoceramic material, wherein, comprising:
With pulverous Pb
3O
4, ZrO
2, TiO
2, MgCO
35H
2O, Nb
2O
5, SrCO
3And BaCO
3Raw material is by the operation A of stoichiometric ratio proportioning wet ball grinding to desired particle size;
Will be after the said raw material stoving behind the operation A briquetting, divide two sections synthetic process B that obtain the lead magnoniobate-Pb-based lanthanumdoped zirconate titanates of strontium, barium composite doping modification in differing temps;
With the operation C that the lead magnoniobate-Pb-based lanthanumdoped zirconate titanates block lapping powder of strontium, barium composite doping modification is broken into powder, mixes 0.2~0.5wt.%CuO, compression moulding obtains biscuit after the fine grinding;
Said biscuit is got rid of organic step D;
To under 930~980 ℃ of temperature, be incubated the operation E of 2~5 hours sintering acquisition piezoceramic materials through the said biscuit of step D.
Preferably, in said operation A, adopt deionized water and agate ball as medium, with raw material, agate ball and deionized water according to 1: 1.2: 0.8 mixed wet ball grinding to desired particle size.Be preferably 6-10 hour in this ball milling time.
In said process B, preferably, first section synthetic is insulation 1~4h under 600~700 ℃ of temperature condition, and second section synthetic is insulation 1~4h under 800~900 ℃ of temperature condition.
In said operation C; With the lead magnoniobate-Pb-based lanthanumdoped zirconate titanates block lapping powder of strontium, barium composite doping modification be broken into powder, mix 0.2~0.5wt.%CuO, behind wet method fine grinding 20~50h; The discharging oven dry; Add 5~10wt%PVA granulating and forming, under the pressure of 100~200MPa, the pressed by powder moulding is obtained biscuit.Preferably, fine grinding adopts deionized water and agate ball as medium, with compound, agate ball and the deionized water of said powder and CuO according to 1: 1.5: 0.6 mixed wet ball grinding to desired particle size.
In said step D, preferably, make biscuit in 600~700 ℃ of TRs, be incubated 1~2 hour to get rid of the organism in the biscuit.Binder removal speed is no more than 3 ℃/min.
In said operation E, the sample that preferably will get rid of behind the organism is put into airtight sintering in the alumina crucible, and finally sintering in 930~980 ℃ of TRs is incubated 2~5 hours.
The present invention also provides a kind of piezoelectric element that utilizes above-mentioned piezoceramic material preparation, it is characterized in that the piezo-electric modulus of said piezoelectric element is d
33>500pC/N, the electric field induced strain amount under the 1.5kV/mm strength of electric field is S
11>=1.5 ‰.
The present invention; Through selecting suitable preparation technology, suitable Zr/Ti ratio, an amount of strontium and barium doping; And select suitable sintering aid for use; Under the situation that reduces sintering temperature, prepare fine and close piezoceramic material and piezoelectric element with high tension electricity coefficient and high electric field induced strain characteristic, this piezoceramic material has a good application prospect at aspects such as stacked piezoelectric wave filter, stacked piezoelectric micro positioner and stacked piezoelectric X-formers.
Description of drawings
Fig. 1 is the dielectric thermogram of the piezoceramic material of the embodiment of the invention 1;
Fig. 2 is the dielectric thermogram of the piezoceramic material of the embodiment of the invention 2;
Fig. 3 is the one pole electric field induced strain curve of the piezoceramic material of the embodiment of the invention 1;
Fig. 4 is the one pole electric field induced strain curve of the piezoceramic material of the embodiment of the invention 2;
Fig. 5 is the microstructure of the piezoceramic material of the embodiment of the invention 1;
Fig. 6 is the microstructure of the piezoceramic material of the embodiment of the invention 2;
Fig. 7 is the XRD diffracting spectrum of the piezoceramic material of the embodiment of the invention 1 and 2.
Embodiment
With reference to Figure of description, and combine following embodiment to further specify the present invention, should be understood that Figure of description and following embodiment only are used to explain the present invention, and unrestricted the present invention.
The composition of piezoceramic material of the present invention is a matrix with the lead magnoniobate-Pb-based lanthanumdoped zirconate titanates of strontium, barium composite doping modification, and contains CuO, can represent with following general formula: Pb
1-x-ySr
xBa
y(Mg
1/3Nb
2/3)
0.25Ti
0.40Zr
0.35O
3+ awt.%CuO, wherein, 0.02≤x≤0.06,0.02≤y≤0.06,0.2≤a≤0.5.
About the preparation of above-mentioned piezoceramic material of the present invention, at first, with Pb
3O
4(technical pure), ZrO
2(technical pure), TiO
2(technical pure), Nb
2O
5(CP), MgCO
35H
2O (technical pure), SrCO
3(analytical pure) and BaCO
3(analytical pure) by the stoichiometry weighing, concrete proportioning is according to general formula Pb
1-x-ySr
xBa
y(Mg
1/3Nb
2/3)
0.25Ti
0.40Zr
0.35O
3Calculate (0.02≤x≤0.06,0.02≤y≤0.06).Above raw material adopts the commercially available prod or according to the compound of ordinary method prepared in laboratory.
Can make raw materials mix evenly and reach needed fineness through wet-milling.In the present invention, ball-milling medium preferably adopts agate ball, but is not limited thereto, and also can use other like media such as natural cobblestones.Adopting material, agate ball, deionized water in one embodiment is 1: 1.2: 0.8 ratio.Ball milling is 6~10 hours in ball mill.
Ball milling reaches the raw material of certain fineness through oven dry, briquetting; Synthetic down in high temperature then; In order to improve synthetic effect, can divide two sections synthetic, preferably first section is synthesized under 650 ℃ condition and is incubated 1h; Second section is synthesized under 850 ℃ condition and is incubated 2h, obtains the lead magnoniobate-Pb-based lanthanumdoped zirconate titanates block of strontium, barium composite doping modification.
With the lead magnoniobate-Pb-based lanthanumdoped zirconate titanates block of the above-mentioned synthetic strontium that obtains, barium composite doping modification be ground into that powder mixes with CuO as sintering aid, fine grinding, oven dry, compression moulding.Preferably be ground into and mix 0.2~0.5wt.%CuO in the powder as sintering aid at lead magnoniobate-Pb-based lanthanumdoped zirconate titanates block.Ball-milling medium preferably adopts agate ball, but is not limited thereto, and also can use other like media such as natural cobblestones.Compound, agate ball and the deionized water that makes said powder and CuO in one embodiment was according to 1: 1.5: 0.6 mixed.Ball milling 20~50h.To reach the compound oven dry of certain fineness through ball milling, and in compound, add a certain amount of like stickers such as PVA, granulating and forming, under the pressure of 100~200MPa with the pressed by powder moulding.
Before sintering, also need under suitable temperature, carry out plastic removal usually to the biscuit of compression moulding.Sintering under high temperature at last.Can the sample of forming be placed on as carrying out plastic removal in the heating units such as van-type electric furnace, the plastic removal temperature is preferably 600~700 ℃, and the time is preferably 1~2 hour, and binder removal speed preferably is no more than 3 ℃/min.Sintering temperature is preferably 930~980 ℃, and sintering time is preferably 2~5h.
In order to test the performance of the piezoelectric that the present invention makes, the sample that sinters is carried out mechanical workout according to specification requirement; The sample that processes is carried out ultrasonic cleaning, and silver electrode is gone up in the oven dry back, puts into van-type electric furnace silver ink firing; To have the sample of electrode to be placed in the silicone oil then, at a certain temperature, the electric field that adds high pressure polarizes.Through test, the piezo-electric modulus of the standard of materials sheet of method preparation of the present invention is d
33>500pC/N, the electric field induced strain amount under the 1.5kV/mm strength of electric field is S
11>=1.5 ‰.
The present invention adopts ZJ-3A type quasistatic d
33The piezo-electric modulus of survey meter test piezoelectric element.AixACCT TFanalyzer 2000 is adopted in the test of electric field induced strain amount.
The preparation of piezoceramic material of the present invention more specifically is described below.Other alternative steps that can reach equal effect can omitted or use to certain that should understand in the following steps also, and each characteristic in each step neither be necessary or replaceable regularly and not, and just example ground explanation.
The preparation method of piezoceramic material of the present invention can comprise:
(1) mixing raw material: with pulverous Pb
3O
4, ZrO
2, TiO
2, MgCO
35H
2O, Nb
2O
5And SrCO
3, BaCO
3Be raw material, by the stoichiometric ratio proportioning, adopt deionized water, agate ball is done medium, according to mixing raw material: agate ball: the mixed of deionized water=1: 1.2: 0.8, wet ball grinding 6~10h;
(2) lead magnoniobate-Pb-based lanthanumdoped zirconate titanates of synthetic strontium, barium composite doping modification: the raw material that step (1) is obtained is poured container into and is put briquetting after the oven for drying into; And synthesize, synthesize and be divided into two sections: first section of 600~700 ℃ of following insulation of temperature condition 1~4h is synthetic; Second section of 800~900 ℃ of following insulation of temperature condition 1~4h is synthetic.And will synthesize good block and grind the lead magnoniobate-PZT powder that obtains strontium, barium composite doping modification;
(3) compression moulding of powder: with sintering aid raw material CuO according to the stoichiometric ratio proportioning; Be added into and synthesize in the step (2) in the good powder, adopt deionized water, agate ball is done medium; According to material: agate ball: behind the ratio wet method fine grinding 20~50h of deionized water=1: 1.5: 0.6; 5~10wt%PVA granulating and forming is added in discharging oven dry, under the pressure of 100~200MPa with the pressed by powder moulding;
(4) biscuit plastic removal: in 600~700 ℃ of TRs, be incubated 1~2 hour, get rid of the organic substance in the biscuit, binder removal speed is no more than 3 ℃/min;
(5) sample sintering: the sample behind the plastic removal is put into airtight sintering in the alumina crucible, and finally sintering in 930~980 ℃ of TRs is incubated 2~5h.
The sample that sinters is carried out mechanical workout according to specification requirement; The sample that processes is carried out ultrasonic cleaning, and silver electrode is gone up in the oven dry back, puts into van-type electric furnace silver ink firing; The silver ink firing condition is 450~500 ℃, insulation 30min.The sample that will be covered with electrode is then put into the silicone oil high voltage polarization, and polarization condition is: temperature is 30 ℃, and electric field is 3~5kV/mm, and the time is 15~20min.
Further enumerate embodiment below to specify example preparation technology of the present invention.Should be understood that following embodiment is for the present invention is described better, and unrestricted the present invention.
With Pb
3O
4(technical pure), ZrO
2(technical pure), TiO
2(technical pure), Nb
2O
5(CP), MgCO
35H
2O (technical pure), SrCO
3(analytical pure), BaCO
3(analytical pure) is raw material, presses Pb
0.92Sr
0.06Ba
0.02(Mg
1/3Nb
2/3)
0.25Ti
0.40Zr
0.35O
3The stoichiometry weighing, adopt deionized water and agate ball to make medium, according to mixing raw material: agate ball: the mixed of deionized water=1: 1.2: 0.8, through drum ball mill mixing 8h; Mixed raw material poured into carries out briquetting after container is put oven for drying into, divide two sections synthetic: insulation 1h under 650 ℃ temperature condition earlier is incubated 2h then under 850 ℃ temperature condition; Obtain the lead magnoniobate-Pb-based lanthanumdoped zirconate titanates of strontium, barium composite doping modification, and will synthesize good block lapping powder and be broken into powder; With sintering aid raw material CuO according to Pb
0.92Sr
0.06Ba
0.02(Mg
1/3Nb
2/3)
0.25Ti
0.40Zr
0.35O
3+ 0.25wt.%CuO proportioning, fine grinding adopt deionized water and agate ball to make medium, according to material: agate ball: and the mixed of deionized water=1: 1.5: 0.6, through drum ball milling 48h; PVA sticker, granulation, dry-pressing formed (forming pressure is 150MPa) are dried, are added in discharging then; The sample of forming is put into the van-type electric furnace carry out plastic removal, the plastic removal operation is 650 ℃/1h; Sample is put into airtight sintering in the alumina crucible, and the agglomerating system is insulation 4h under 950 ℃ of temperature condition;
The sample that sinters is carried out mechanical workout according to specification requirement; The sample that processes is carried out ultrasonic cleaning, and silver electrode is gone up in the oven dry back, puts into van-type electric furnace silver ink firing, and the silver ink firing condition is 450~500 ℃, insulation 30min; The sample that will be covered with electrode is then put into the silicone oil high voltage polarization, and polarization condition is that temperature is 30 ℃, and electric field is 4kV/mm, and the time is 20min.The salient features of standard of materials sheet is: S
11=1.6 ‰ (1.5kV/mm) d
33=525pC/N, ε
33 T/ ε
o=2567.Fig. 1 has provided the dielectric temperature spectrum of the said material of present embodiment, and Fig. 3 has provided the one pole electric field induced strain curve of the said material of present embodiment, and Fig. 5 has provided the microstructure of the said material of present embodiment.
According to Pb
0.92Sr
0.06Ba
0.02(Mg
1/3Nb
2/3)
0.25Ti
0.40Zr
0.35O
3+ 0.5wt.%CuO proportioning, concrete preparation technology such as embodiment 1, the salient features of gained standard film is: S
11=1.5 ‰ (1.5kV/mm) d
33=519pC/N, ε
33 T/ ε
o=2463.Fig. 2 has provided the dielectric temperature spectrum of the said component of present embodiment, and Fig. 4 has provided the one pole electric field induced strain curve of the said component of present embodiment, and Fig. 6 has provided the microstructure of the said component of present embodiment.
With Pb
3O
4(technical pure), ZrO
2(technical pure), TiO
2(technical pure), Nb
2O
5(CP), MgCO
35H
2O (technical pure), SrCO
3(analytical pure), BaCO
3(analytical pure) is raw material, presses Pb
0.92Sr
0.02Ba
0.06(Mg
1/3Nb
2/3)
0.25Ti
0.40Zr
0.35O
3The stoichiometry weighing, adopt deionized water and agate ball as medium, according to mixing raw material: agate ball: the mixed of deionized water=1: 1.2: 0.8, through drum ball mill mixing 10h; Mixed raw material poured into carries out briquetting after container is put oven for drying into, divide two sections synthetic: insulation 1h under 650 ℃ temperature condition earlier is incubated 2h then under 800 ℃ temperature condition; Obtain the lead magnoniobate-Pb-based lanthanumdoped zirconate titanates of strontium, barium composite doping modification, and will synthesize good block lapping powder and be broken into powder; With sintering aid raw material CuO according to Pb
0.92Sr
0.02Ba
0.06(Mg
1/3Nb
2/3)
0.25Ti
0.40Zr
0.35O
3+ 0.3wt.%CuO proportioning, fine grinding adopt deionized water and agate ball as medium, according to material: agate ball: and the mixed of deionized water=1: 1.5: 0.8, through drum ball milling 24h; PVA sticker, granulation, dry-pressing formed (forming pressure is 150MPa) are dried, are added in discharging then; The sample of forming is placed on the van-type electric furnace carries out plastic removal, the plastic removal operation is 600 ℃/2h; Sample is put into airtight sintering in the alumina crucible, and the agglomerating system is sintering 2h under 980 ℃ the temperature condition;
The sample that sinters is carried out mechanical workout according to specification requirement; The sample that processes is carried out ultrasonic cleaning, and silver electrode is gone up in the oven dry back, puts into van-type electric furnace silver ink firing, and the silver ink firing condition is 450~500 ℃, insulation 30min; The sample that will be covered with electrode is then put into the silicone oil high voltage polarization, and polarization condition is that temperature is 30 ℃, and electric field is 4kV/mm, and the time is 20min.The salient features of standard of materials sheet is: S
11=1.65 ‰ (1.5kV/mm) d
33=535pC/N, ε
33 T/ ε
o=2514.
With Pb
3O
4(technical pure), ZrO
2(technical pure), TiO
2(technical pure), Nb
2O
5(CP), MgCO
35H
2O (technical pure), SrCO
3(analytical pure), BaCO
3(analytical pure) is raw material, presses Pb
0.92Sr
0.02Ba
0.06(Mg
1/3Nb
2/3)
0.25Ti
0.40Zr
0.35O
3The stoichiometry weighing, adopt deionized water and agate ball as medium, according to mixing raw material: agate ball: the mixed of deionized water=1: 1.2: 0.8, through drum ball mill mixing 6h; Mixed raw material poured into carries out briquetting after container is put oven for drying into, divide two sections synthetic: insulation 1.5h under 700 ℃ temperature condition earlier is incubated 1.5h then under 900 ℃ temperature condition; Obtain the lead magnoniobate-Pb-based lanthanumdoped zirconate titanates of strontium, barium composite doping modification, and will synthesize good block lapping powder and be broken into powder; With sintering aid raw material CuO according to Pb
0.92Sr
0.02Ba
0.06(Mg
1/3Nb
2/3)
0.25Ti
0.40Zr
0.35O
3+ 0.4wt.%CuO proportioning, fine grinding adopt deionized water and agate ball as medium, according to material: agate ball: and the mixed of deionized water=1: 1.5: 0.8, through drum ball milling 36h; PVA sticker, granulation, dry-pressing formed (forming pressure is 140MPa) are dried, are added in discharging then; The sample of forming is placed on the van-type electric furnace carries out plastic removal, the plastic removal operation is 680 ℃/1.2h; Sample is put into airtight sintering in the alumina crucible, and the agglomerating system is sintering 4h under 930 ℃ the temperature condition;
The sample that sinters is carried out mechanical workout according to specification requirement; The sample that processes is carried out ultrasonic cleaning, and silver electrode is gone up in the oven dry back, puts into van-type electric furnace silver ink firing, and the silver ink firing condition is 450~500 ℃, insulation 30min; The sample that will be covered with electrode is then put into the silicone oil high voltage polarization, and polarization condition is that temperature is 30 ℃, and voltage is 4kv/mm, and the time is 20min.The salient features of standard of materials sheet is: S
11=1.7 ‰ (1.5kV/mm) d
33=540pC/N, ε
33 T/ ε
o=2485.
Industrial applicability: the present invention is mainly through selecting suitable preparation technology; Suitable Zr/Ti ratio; An amount of Strontium carbonate powder and barium carbonate doping; And select for use suitable sintering aid to realize both having high tension electricity coefficient, and having high electric field induced strain characteristic again and can realize the preparation of dense sintering material at low temperature, this material demonstrates good prospects for application at aspects such as stacked piezoelectric wave filter, stacked piezoelectric micro positioner and stacked piezoelectric X-formers.
Claims (8)
1. a high tension electricity coefficient, the low sintering piezoceramic material of high electric field induced strain is characterized in that the composition of said piezoceramic material is a matrix with the lead magnoniobate-Pb-based lanthanumdoped zirconate titanates of strontium, barium composite doping modification, and contains CuO.
2. piezoceramic material according to claim 1 is characterized in that, said material is represented with following general formula:
Pb
1-x-ySr
xBa
y(Mg
1/3Nb
2/3)
0.25Ti
0.40Zr
0.35O
3+ awt.%CuO, wherein, 0.02≤x≤0.06,0.02≤y≤0.06,0.2≤a≤0.5.
3. the preparation method of claim 1 or 2 described piezoceramic materials is characterized in that, comprising:
With pulverous Pb
3O
4, ZrO
2, TiO
2, MgCO
35H
2O, Nb
2O
5, SrCO
3And BaCO
3Raw material by the operation A of stoichiometric ratio proportioning wet ball grinding to desired particle size;
Will be after the said raw material stoving behind the operation A briquetting, divide two sections synthetic process B that obtain the lead magnoniobate-Pb-based lanthanumdoped zirconate titanates of strontium, barium composite doping modification in differing temps;
Lead magnoniobate-Pb-based lanthanumdoped zirconate titanates block the lapping powder of strontium, barium composite doping modification is broken into powder, mixes the operation C that compression moulding after the CuO of 0.2~0.5wt.%, the fine grinding obtains biscuit;
Said biscuit is got rid of organic step D;
To under 930~980 ℃ of temperature, be incubated the operation E of 2~5 hours sintering acquisition piezoceramic materials through the said biscuit of step D.
4. preparation method according to claim 3 is characterized in that, in said process B, first section synthetic is insulation 1~4h under 600~700 ℃ of temperature condition, and second section synthetic is insulation 1~4h under 800~900 ℃ of temperature condition.
5. according to claim 3 or 4 described preparing methods, it is characterized in that, in said operation A, adopt deionized water and agate ball as medium, with raw material, agate ball and deionized water according to 1: 1.2: 0.8 mixed wet ball grinding to desired particle size.
6. according to claim 3 or 4 described preparing methods; It is characterized in that; In said operation C, fine grinding adopts deionized water and agate ball as medium, with compound, agate ball and the deionized water of said powder and CuO according to 1: 1.5: 0.6 mixed wet ball grinding to desired particle size.
7. according to claim 3 or 4 described preparing methods, it is characterized in that, in said step D, make biscuit in 600 ℃~700 ℃ TRs, be incubated 1~2 hour to get rid of said organism.
8. piezoelectric element by claim 1 or the preparation of 2 described piezoceramic materials; Or the prepared piezoelectric element of piezoceramic material that obtains by each described preparation method in the claim 3 to 7; It is characterized in that the piezo-electric modulus of said piezoelectric element is d
33>500pC/N, the electric field induced strain amount under the 1.5kV/mm strength of electric field is S
11>=1.5 ‰.
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CN113185286A (en) * | 2021-04-22 | 2021-07-30 | 宁波凯普电子有限公司 | Piezoelectric buzzer and manufacturing method thereof |
CN114075073A (en) * | 2020-08-17 | 2022-02-22 | 中国科学院上海硅酸盐研究所 | PZT-Pb (Sb)1/2Nb1/2) Ternary system piezoelectric ceramic material and preparation method and application thereof |
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CN1475457A (en) * | 2002-05-30 | 2004-02-18 | Tdk��ʽ���� | Method for mfg. piezoelectric ceramics and piezodlectric elements |
CN1986486A (en) * | 2006-12-25 | 2007-06-27 | 中国科学院上海硅酸盐研究所 | Piezoelectric ceramic material for high performance type-B ultrasonic diagnosis apparatus transducer and its preparing method |
CN101475373A (en) * | 2009-01-22 | 2009-07-08 | 中国科学院上海硅酸盐研究所 | High piezoelectric strain constant d31, low piezoelectric strain constant g31 piezoelectric ceramic material and preparation thereof |
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CN1475457A (en) * | 2002-05-30 | 2004-02-18 | Tdk��ʽ���� | Method for mfg. piezoelectric ceramics and piezodlectric elements |
CN1986486A (en) * | 2006-12-25 | 2007-06-27 | 中国科学院上海硅酸盐研究所 | Piezoelectric ceramic material for high performance type-B ultrasonic diagnosis apparatus transducer and its preparing method |
CN101475373A (en) * | 2009-01-22 | 2009-07-08 | 中国科学院上海硅酸盐研究所 | High piezoelectric strain constant d31, low piezoelectric strain constant g31 piezoelectric ceramic material and preparation thereof |
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CN114075073A (en) * | 2020-08-17 | 2022-02-22 | 中国科学院上海硅酸盐研究所 | PZT-Pb (Sb)1/2Nb1/2) Ternary system piezoelectric ceramic material and preparation method and application thereof |
CN113185286A (en) * | 2021-04-22 | 2021-07-30 | 宁波凯普电子有限公司 | Piezoelectric buzzer and manufacturing method thereof |
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