CN102584230B - 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 PDF

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CN102584230B
CN102584230B CN201210052032.7A CN201210052032A CN102584230B CN 102584230 B CN102584230 B CN 102584230B CN 201210052032 A CN201210052032 A CN 201210052032A CN 102584230 B CN102584230 B CN 102584230B
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preparation
piezoceramic material
sintering
cuo
deionized water
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CN102584230A (en
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董显林
王丽
梁瑞虹
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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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

A kind of high tension electricity coefficient, the low sintering piezoceramic material of high electric field induced strain and preparation method thereof
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 by applying electric field generation strain effects (electric energy is changed to mechanical energy) from outside and producing the material of effect (mechanical energy is changed to electric energy) of electric charge by be subject to stress from outside on surface, can be used for detection and the storage etc. of various information, be widely used in the technical fields such as military affairs, automobile, business and medical treatment.As lead zirconate titanate salt (Pb (Zr, Ti)) O 3; Etc. PZT) piezoelectric, can be 1 × 10 for the voltage applying -10in the instruction of m/V, there is to be roughly the strain of ratio, therefore can adjust small position.Contrary with it in addition, piezoelectric can generation to stress application or with self-deformation amount proportional electric charge, therefore can be applicable to sensor.
Piezoelectric ceramics is a kind of polycrystal piezoelectric with piezoelectric effect, and conventional piezoelectric ceramics has barium titanate series, lead titanate-lead zirconates two component system and in two component system, adds the third ABO 3(A represents divalent-metal ion, and B represents that quadrivalent metallic ion or several ion summation are positive tetravalence) type compound, if add the 4th kind or more compound on three-part system, can form quaternary system or polynary system piezoelectric ceramics again.
Along with the raising of modern integrated circuits scale and speed, piezoelectric ceramic devices are just integrated towards complete machine, the future development of miniaturization, slimming, lightness, high performance.Under demand pull and promoting technology, stacked piezoelectric electronic component arises at the historic moment.Stacked piezoelectric electronic component is to be superimposed together in some way applying the ceramic membrane biscuit of internal and external electrode, through once sintered make it to become one make.The electronic devices and components of making through this technique have the advantages such as volume is little, internal inductance is little, moisture-proof, life-span length, good reliability, become one of element adapting to most electronic technology development, at home and abroad paid attention to fully at present, there is corresponding product in Japan and the U.S., domestic, the research of stacked piezoelectric electronic component is also carried out.Because adopting interior electrode and biscuit of ceramics, burns altogether by stacked piezoelectric electronic component, in order to ensure ceramic sintered compact, must use the high-temperature electrode materials such as Pd, Pt, thereby improve cost, so manage to reduce the sintering temperature of piezoelectric ceramics so that adopting Ag, Ag/Ni, Ag/Pd electrode to realize altogether burns, be an important research direction all the time.
More Pb (Zr, the Ti) O of research at present 3the sintering temperature of (brief PZT) pottery can be reduced to about 1050 DEG C of left and right, but in order really to realize low temperature co-fired (～950 DEG C), also needs further to reduce the sintering temperature of piezoelectric ceramics, and make the piezoelectric property that keeps good.On the other hand, very few to the research of electric field induced strain performance in current report, can not meet the application demand of stacked piezoelectric wave filter, stacked piezoelectric micro positioner and stacked piezoelectric transformer etc.
Summary of the invention
In the face of the problem of prior art existence, the inventor recognizes provides one to 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 meet the application demand of stacked piezoelectric wave filter, stacked piezoelectric micro positioner and stacked piezoelectric transformer etc.Simultaneously the preparation method preparation technology of piezoceramic material provided by the invention simple, fill a prescription adjustable, applicable to scale production.
For this reason, the invention provides a kind of high tension electricity coefficient, the low sintering piezoceramic material of high electric field induced strain, wherein, the composition of described material is taking the lead magnoniobate-Pb-based lanthanumdoped zirconate titanates of strontium, barium composite doping modification as matrix, and contains CuO.
In the present invention, described piezoceramic material 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.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:
By pulverous Pb 3o 4, ZrO 2, TiO 2, MgCO 35H 2o, Nb 2o 5, SrCO 3and BaCO 3raw material is the operation A to desired particle size by stoichiometric ratio proportioning wet ball grinding;
By briquetting after the described raw material stoving after operation A, the process B of dividing two sections of synthetic lead magnoniobate-Pb-based lanthanumdoped zirconate titanatess that obtain strontium, barium composite doping modification in differing temps;
By the operation C that 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 fine grinding;
Described biscuit is got rid of to organic step D;
Described biscuit through step D is incubated at 930～980 DEG C of temperature to the operation E of 2～5 hours sintering acquisition piezoceramic materials.
Preferably, in described operation A, adopt deionized water and agate ball as medium, raw material, agate ball and deionized water are mixed to wet ball grinding to desired particle size according to the ratio of 1: 1.2: 0.8.Be preferably 6-10 hour at this Ball-milling Time.
In described process B, preferably, first paragraph is synthetic is to be incubated 1～4h under 600～700 DEG C of temperature condition, and second segment is synthetic is to be incubated 1～4h under 800～900 DEG C of temperature condition.
In described operation C, by 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, after wet method fine grinding 20～50h, discharging is dried, add 5～10wt%PVA granulating and forming, under the pressure of 100～200MPa, pressed by powder moulding is obtained to biscuit.Preferably, fine grinding adopts deionized water and agate ball as medium, and the compound of described powder and CuO, agate ball and deionized water are mixed to wet ball grinding to desired particle size according to the ratio of 1: 1.5: 0.6.
In described step D, preferably, make biscuit in 600～700 DEG C of temperature ranges, be incubated 1～2 hour to get rid of the organism in biscuit.Binder removal speed is no more than 3 DEG C/min.
In described operation E, preferably the sample of getting rid of after organism is put into airtight sintering in alumina crucible, finally sintering in 930～980 DEG C of temperature ranges, is incubated 2～5 hours.
The present invention also provides a kind of piezoelectric element that utilizes above-mentioned piezoceramic material to prepare, and it is characterized in that, the piezo-electric modulus of described piezoelectric element is d 33> 500pC/N, the electric field induced strain amount under 1.5kV/mm strength of electric field is S 11>=1.5 ‰.
The present invention, by selecting suitable preparation technology, suitable Zr/Ti ratio, appropriate strontium and barium doping, and select suitable sintering aid, in the situation that reducing sintering temperature, prepare fine and close piezoceramic material and the 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 transformers.
Brief description of the drawings
Fig. 1 is the dielectric thermogram of the piezoceramic material of the embodiment of the present invention 1;
Fig. 2 is the dielectric thermogram of the piezoceramic material of the embodiment of the present invention 2;
Fig. 3 is the one pole electric field induced strain curve of the piezoceramic material of the embodiment of the present invention 1;
Fig. 4 is the one pole electric field induced strain curve of the piezoceramic material of the embodiment of the present invention 2;
Fig. 5 is the microstructure of the piezoceramic material of the embodiment of the present invention 1;
Fig. 6 is the microstructure of the piezoceramic material of the embodiment of the present invention 2;
Fig. 7 is the XRD diffracting spectrum of the piezoceramic material of the embodiment of the present invention 1 and 2.
Embodiment
With reference to Figure of description, and further illustrate with the following embodiments the present invention, should be understood that Figure of description and following embodiment are only for the present invention is described, and unrestricted the present invention.
The composition of piezoceramic material of the present invention is taking the lead magnoniobate-Pb-based lanthanumdoped zirconate titanates of strontium, barium composite doping modification as matrix, 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, first, by Pb 3o 4(technical pure), ZrO 2(technical pure), TiO 2(technical pure), Nb 2o 5(chemical pure), MgCO 35H 2o (technical pure), SrCO 3(analytical pure) and BaCO 3(analytical pure) weighs by stoichiometry, and 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).The compound that above raw material adopts commercially available prod or prepares according to ordinary method laboratory.
Can raw material be mixed and reach needed fineness by wet-milling.In the present invention, ball-milling medium preferably adopts agate ball, but is not limited thereto, and also can use other as media such as natural cobblestones.Adopt in one embodiment the ratio that material, agate ball, deionized water are 1: 1.2: 0.8.Ball milling 6～10 hours in ball mill.
Ball milling reaches raw material drying, the briquetting of certain fineness, then synthetic under high temperature, in order to improve synthetic effect, can divide two sections to synthesize, preferably first paragraph synthesizes under the condition of 650 DEG C and is incubated 1h, second segment synthesizes under the condition of 850 DEG C and is incubated 2h, obtains lead magnoniobate-Pb-based lanthanumdoped zirconate titanates block of strontium, barium composite doping modification.
Using lead magnoniobate-Pb-based lanthanumdoped zirconate titanates block of the above-mentioned synthetic strontium obtaining, barium composite doping modification be ground into that powder mixes with the CuO as sintering aid, fine grinding, oven dry, compression moulding.Preferably in being ground into powder, lead magnoniobate-Pb-based lanthanumdoped zirconate titanates block mixes 0.2～0.5wt.%CuO as sintering aid.Ball-milling medium preferably adopts agate ball, but is not limited thereto, and also can use other as media such as natural cobblestones.Make in one embodiment compound, agate ball and the deionized water of described powder and CuO mix according to the ratio of 1: 1.5: 0.6.Ball milling 20～50h.Will reach through ball milling the compound of certain fineness dry, and in compound, add a certain amount of as binding agents such as PVA, granulating and forming, under the pressure of 100～200MPa by pressed by powder moulding.
Before sintering, conventionally also need the biscuit of compression moulding to carry out plastic removal at suitable temperature.Finally sintering under high temperature.The sample of forming can be placed on as carried out plastic removal in the heating units such as van-type electric furnace, plastic removal temperature is preferably 600～700 DEG C, and the time is preferably 1～2 hour, and binder removal speed is preferably no more than 3 DEG C/min.Sintering temperature is preferably 930～980 DEG C, and sintering time is preferably 2～5h.
In order to test the performance of the piezoelectric that the present invention makes, the sample sintering is carried out to mechanical workout according to specification requirement; The sample processing is carried out to ultrasonic cleaning, and after drying, upper silver electrode, puts into van-type electric furnace silver ink firing; Then the sample that has electrode is placed in silicone oil, at a certain temperature, the electric field that adds high pressure, polarizes.The piezo-electric modulus of the standard of materials sheet that after tested, prepared by method of the present invention is d 33> 500pC/N, the electric field induced strain amount under 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.The test of electric field induced strain amount adopts aixACCT TFanalyzer 2000.
Be described more specifically the preparation of piezoceramic material of the present invention below.Other alternative steps that can reach same texts also can be omitted or use to certain that should understand in following steps, and each feature in each step neither or replaceable regularly and not, and just illustratively 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 3for raw material, by stoichiometric ratio proportioning, adopt deionized water, agate ball does medium, according to mixing raw material: agate ball: deionized water=1: the ratio of 1.2: 0.8 is mixed, 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 put briquetting after oven for drying into, and synthesize, synthesize and be divided into two sections: the first paragraph that is incubated 1～4h under 600～700 DEG C of temperature condition is synthetic; The second segment that is incubated 1～4h under 800～900 DEG C of temperature condition is synthetic.And synthetic block is ground to the lead magnoniobate-PZT powder that obtains strontium, barium composite doping modification;
(3) compression moulding of powder: by sintering aid raw material CuO according to stoichiometric ratio proportioning, be added in powder synthetic in step (2), adopt deionized water, agate ball does medium, according to material: agate ball: deionized water=1: after the ratio wet method fine grinding 20～50h of 1.5: 0.6, discharging is dried, and adds 5～10wt%PVA granulating and forming, under the pressure of 100～200MPa by pressed by powder moulding;
(4) biscuit plastic removal: in 600～700 DEG C of temperature ranges, be incubated 1～2 hour, get rid of the organic substance in biscuit, binder removal speed is no more than 3 DEG C/min;
(5) sample sintering: the sample after plastic removal is put into airtight sintering in alumina crucible, finally sintering in 930～980 DEG C of temperature ranges, insulation 2～5h.
The sample sintering is carried out to mechanical workout according to specification requirement; The sample processing is carried out to ultrasonic cleaning, and after drying, upper silver electrode, puts into van-type electric furnace silver ink firing; Silver ink firing condition is 450～500 DEG C, insulation 30min.Then the sample that is covered with electrode is put into silicone oil high voltage polarization, polarization condition is: temperature is 30 DEG C, and electric field is 3～5kV/mm, and the time is 15～20min.
Further enumerate embodiment below to describe example preparation technology of the present invention in detail.Should be understood that following embodiment is for the present invention is described better, and unrestricted the present invention.
Embodiment 1
With Pb 3o 4(technical pure), ZrO 2(technical pure), TiO 2(technical pure), Nb 2o 5(chemical pure), MgCO 35H 2o (technical pure), SrCO 3(analytical pure), BaCO 3(analytical pure) is raw material, by Pb 0.92sr 0.06ba 0.02(Mg 1/3nb 2/3) 0.25ti 0.40zr 0.35o 3stoichiometry weigh, adopt deionized water and agate ball to make medium, according to mixing raw material: agate ball: deionized water=1: the ratio of 1.2: 0.8 is mixed, through drum ball mill mixing 8h; Mixed raw material is poured into after container is put oven for drying into and carried out briquetting, divide two sections to synthesize: first under the temperature condition of 650 DEG C, to be incubated 1h, then under the temperature condition of 850 DEG C, to be incubated 2h; Obtain the lead magnoniobate-Pb-based lanthanumdoped zirconate titanates of strontium, barium composite doping modification, and synthetic block lapping powder is broken into powder; By 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 adopts deionized water and agate ball to make medium, according to material: agate ball: deionized water=1: the ratio of 1.5: 0.6 is mixed, through drum ball milling 48h; Then PVA binding agent, granulation, dry-pressing formed (forming pressure is 150MPa) are dried, are added in discharging; The sample of forming is put into van-type electric furnace and carry out plastic removal, plastic removal operation is 650 DEG C/1h; Sample is put into airtight sintering in alumina crucible, and the system of sintering is to be incubated 4h under 950 DEG C of temperature condition;
The sample sintering is carried out to mechanical workout according to specification requirement; The sample processing is carried out to ultrasonic cleaning, and after drying, upper silver electrode, puts into van-type electric furnace silver ink firing, and silver ink firing condition is 450～500 DEG C, insulation 30min; Then the sample that is covered with electrode is put into silicone oil high voltage polarization, polarization condition is that temperature is 30 DEG C, 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 material described in the present embodiment, and Fig. 3 has provided the one pole electric field induced strain curve of material described in the present embodiment, and Fig. 5 has provided the microstructure of material described in the present embodiment.
Embodiment 2
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 is as embodiment 1, and 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 component described in the present embodiment, and Fig. 4 has provided the one pole electric field induced strain curve of component described in the present embodiment, and Fig. 6 has provided the microstructure of component described in the present embodiment.
Embodiment 3
With Pb 3o 4(technical pure), ZrO 2(technical pure), TiO 2(technical pure), Nb 2o 5(chemical pure), MgCO 35H 2o (technical pure), SrCO 3(analytical pure), BaCO 3(analytical pure) is raw material, by Pb 0.92sr 0.02ba 0.06(Mg 1/3nb 2/3) 0.25ti 0.40zr 0.35o 3stoichiometry weigh, adopt deionized water and agate ball as medium, according to mixing raw material: agate ball: deionized water=1: the ratio of 1.2: 0.8 is mixed, through drum ball mill mixing 10h; Mixed raw material is poured into after container is put oven for drying into and carried out briquetting, divide two sections to synthesize: first under the temperature condition of 650 DEG C, to be incubated 1h, then under the temperature condition of 800 DEG C, to be incubated 2h; Obtain the lead magnoniobate-Pb-based lanthanumdoped zirconate titanates of strontium, barium composite doping modification, and synthetic block lapping powder is broken into powder; By 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 adopts deionized water and agate ball as medium, according to material: agate ball: deionized water=1: the ratio of 1.5: 0.8 is mixed, through drum ball milling 24h; Then PVA binding agent, granulation, dry-pressing formed (forming pressure is 150MPa) are dried, are added in discharging; The sample of forming is placed on to van-type electric furnace and carries out plastic removal, plastic removal operation is 600 DEG C/2h; Sample is put into airtight sintering in alumina crucible, and the system of sintering is sintering 2h under the temperature condition of 980 DEG C;
The sample sintering is carried out to mechanical workout according to specification requirement; The sample processing is carried out to ultrasonic cleaning, and after drying, upper silver electrode, puts into van-type electric furnace silver ink firing, and silver ink firing condition is 450～500 DEG C, insulation 30min; Then the sample that is covered with electrode is put into silicone oil high voltage polarization, polarization condition is that temperature is 30 DEG C, 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.
Embodiment 4
With Pb 3o 4(technical pure), ZrO 2(technical pure), TiO 2(technical pure), Nb 2o 5(chemical pure), MgCO 35H 2o (technical pure), SrCO 3(analytical pure), BaCO 3(analytical pure) is raw material, by Pb 0.92sr 0.02ba 0.06(Mg 1/3nb 2/3) 0.25ti 0.40zr 0.35o 3stoichiometry weigh, adopt deionized water and agate ball as medium, according to mixing raw material: agate ball: deionized water=1: the ratio of 1.2: 0.8 is mixed, through drum ball mill mixing 6h; Mixed raw material is poured into after container is put oven for drying into and carried out briquetting, divide two sections to synthesize: first under the temperature condition of 700 DEG C, to be incubated 1.5h, then under the temperature condition of 900 DEG C, to be incubated 1.5h; Obtain the lead magnoniobate-Pb-based lanthanumdoped zirconate titanates of strontium, barium composite doping modification, and synthetic block lapping powder is broken into powder; By 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 adopts deionized water and agate ball as medium, according to material: agate ball: deionized water=1: the ratio of 1.5: 0.8 is mixed, through drum ball milling 36h; Then PVA binding agent, granulation, dry-pressing formed (forming pressure is 140MPa) are dried, are added in discharging; The sample of forming is placed on to van-type electric furnace and carries out plastic removal, plastic removal operation is 680 DEG C/1.2h; Sample is put into airtight sintering in alumina crucible, and the system of sintering is sintering 4h under the temperature condition of 930 DEG C;
The sample sintering is carried out to mechanical workout according to specification requirement; The sample processing is carried out to ultrasonic cleaning, and after drying, upper silver electrode, puts into van-type electric furnace silver ink firing, and silver ink firing condition is 450～500 DEG C, insulation 30min; Then the sample that is covered with electrode is put into silicone oil high voltage polarization, polarization condition is that temperature is 30 DEG C, 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 by selecting suitable preparation technology, suitable Zr/Ti ratio, appropriate Strontium carbonate powder and barium carbonate doping, and select suitable sintering aid to realize both to there is high tension electricity coefficient, have again high electric field induced strain characteristic and can realize at low temperature the preparation of dense sintering material, this material demonstrates good application prospect at aspects such as stacked piezoelectric wave filter, stacked piezoelectric micro positioner and stacked piezoelectric transformers.

Claims (7)

1. a preparation method for high tension electricity coefficient, the low sintering piezoceramic material of high electric field induced strain, is characterized in that, the composition of described piezoceramic material is taking the lead magnoniobate-Pb-based lanthanumdoped zirconate titanates of strontium, barium composite doping modification as matrix, and contains CuO; And comprise pulverous Pb in the preparation process of described material 3o 4, ZrO 2, TiO 2, MgCO 35H 2o, Nb 2o 5, SrCO 3and BaCO 3the raw material operations of dividing two sections of synthetic lead magnoniobate-Pb-based lanthanumdoped zirconate titanates blocks that obtain strontium, barium composite doping modification by stoichiometric ratio proportioning wet ball grinding to desired particle size post-drying briquetting in differing temps, wherein first paragraph is synthetic is to be incubated 1～4h under 600～700 DEG C of temperature condition, and second segment is synthetic is to be incubated 1～4h under 800～900 DEG C of temperature condition; Also comprise synthetic described block lapping powder is broken into powder, the operation of carrying out fine grinding in the strontium preparing described in the described CuO of 0.2～0.5wt.% is added, the lead magnoniobate-PZT powder of barium composite doping modification.
2. the preparation method of piezoceramic material according to claim 1, is characterized in that, described material represents 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 piezoceramic material according to claim 1 and 2, is characterized in that the biscuit that compression moulding after fine grinding is obtained is incubated 2～5 hours sintering and obtains piezoceramic material at 930～980 DEG C of temperature.
4. preparation method according to claim 1, is characterized in that, described ball milling is to adopt deionized water and agate ball as medium, and raw material, agate ball and deionized water are mixed to wet ball grinding to desired particle size according to the ratio of 1:1.2:0.8.
5. preparation method according to claim 1, it is characterized in that, described fine grinding adopts deionized water and agate ball as medium, and the compound of described powder and CuO, agate ball and deionized water are mixed to wet ball grinding to desired particle size according to the ratio of 1:1.5:0.6.
6. preparation method according to claim 3, is characterized in that, makes described biscuit before described sintering, in 600 DEG C～700 DEG C temperature ranges, be incubated 1～2 hour to get rid of organism.
7. the prepared piezoelectric element of piezoceramic material being obtained by the preparation method described in any one in claim 1 to 6, is characterized in that, the piezo-electric modulus of described piezoelectric element is d 33﹥ 500 pC/N, the electric field induced strain amount under 1.5kV/mm strength of electric field is S 11>=1.5 ‰.
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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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