CN103073290A - Piezoceramic material and preparation method thereof - Google Patents
Piezoceramic material and preparation method thereof Download PDFInfo
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- CN103073290A CN103073290A CN2013100308554A CN201310030855A CN103073290A CN 103073290 A CN103073290 A CN 103073290A CN 2013100308554 A CN2013100308554 A CN 2013100308554A CN 201310030855 A CN201310030855 A CN 201310030855A CN 103073290 A CN103073290 A CN 103073290A
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Abstract
The invention provides piezoelectric ceramic which comprises a main component and an auxiliary component, wherein an expression of the main component is shown as follows: Pba(Mn1/3Nb2/3)bZrxTiyO3; a is greater than or equal to 0.95 and less than or equal to 1.05; b is greater than or equal to 0.05 and less than or equal to 0.2; b plus x plus y is equal to 1; and the auxiliary component comprises at least one of oxide or salt of W, Cu, Ba, Si and Mn. The invention also discloses a preparation method of the piezoelectric ceramic. Compared with the prior art, the piezoelectric ceramic prepared by the preparation method has a high electromechanical coupling factor, and the temperature stability can be improved. In addition, as the auxiliary component containing a fluxing agent is added to the piezoelectric ceramic, on the premise that the performance and the temperature stability are guaranteed, a sintering temperature range is extended, and low temperature sintering and the practicability of a piezoelectric material are facilitated.
Description
Technical field
The present invention relates to a kind of piezoceramic material and preparation method thereof, relate in particular to a kind of piezoceramic material that has simultaneously high electromechanical coupling factor and high-temperature stability and preparation method thereof.
Background technology
Have important application aspect a lot of in people life of piezoelectric ceramics, but the whole world is still traditional lead piezoelectric ceramics that contains at a large amount of piezoceramic materials that use at present, wherein lead element content is up to more than 60%.
Plumbous oxide (PbO) is a kind of volatile toxic substance, in the treating processes after producing, prepare, use and discarding, cause damage all can for the mankind and ecotope.Day by day deep along with environmental consciousness just actively forbidden leaded electronic product by forms such as law, rules, government's instructions in the world.The volatilization of PbO during high temperature sintering in to environment, also can cause departing from of ceramic stoichiometric ratio, affects material property.Therefore, the sintering temperature of how improving in the piezoceramic material course of processing is the industry problem demanding prompt solution.
On the other hand, as the performance of the requirement on devices piezoceramic materials such as the piezoelectric ceramic filter of piezoelectric element, frequency discriminator particularly frequency constant good stability is arranged, but adopting high electromechanical coupling factor and the high frequency temperature stability of the piezoelectric ceramics that present preparation method obtains is conflict, is difficult to accomplish to satisfy simultaneously.And the Reflow Soldering in the encapsulation of modern integrated circuits (reflow) often needs higher temperature (220-270 ℃), and this has just proposed challenge to the thermal shock resistance of piezoelectric element itself, and present preparation method is difficult to be satisfied.
Summary of the invention
The technical problem that the present invention mainly solves is that existing piezoelectric ceramics can not have high electromechanical coupling factor and high frequency temperature stability simultaneously.
In order to solve the problems of the technologies described above, the embodiment of the invention discloses a kind of piezoceramic material, described piezoceramic material comprises main ingredient and auxiliary component, and the expression formula of described main ingredient is Pb
a(Mn
1/3Nb
2/3)
bZr
xTi
yO
3, wherein, 0.95≤a≤1.05,0.05≤b≤0.2, b+x+y=1, described auxiliary component are at least a oxide compound or the salt among W, Cu, Ba, Si, the Mn.
In a preferred embodiment of the present invention, the weight percentage of described auxiliary component in described piezoceramic material is less than 2%.
In order to solve the problems of the technologies described above, the embodiment of the invention also discloses a kind of preparation method of above-mentioned piezoceramic material, described preparation method comprises:
Batching is also mixed: mix each component to form the hopcalite that contains at least Pb, Zr, Ti, Nb and Mn;
Pre-burning: the raw material after the mixing and ball milling is carried out pre-burning;
Pulverize and the doping auxiliary component: with the reacted material disintegrating of pre-burning, at least a oxide compound among mix simultaneously W, Cu, Ba, Si and the Mn or salt form the mixture that contains auxiliary component as auxiliary component;
Moulding: in the mixture that contains auxiliary component, add formed material to form ceramic size, to ceramic size de-bubble aftershaping;
By electropolarization: ceramic green sheet and inner electrode layer is alternately laminated to obtain the lamination product;
Sintering: sintered layer is cut down output thing to produce sintered product under the sintering temperature;
Polarization: with the sintered product polarization, namely obtain required piezoceramic material.
In a preferred embodiment of the present invention, mix described starting material and realize by ball mill.
In a preferred embodiment of the present invention, during moulding, the formed material that adds in the mixture that contains auxiliary component is to comprise at least a in binding agent, softening agent, dispersion agent and the solvent, and mixes to form ceramic size.
In a preferred embodiment of the present invention, described forming method comprises it being to adopt the flow casting molding method to process the ceramic membrane band.
In a preferred embodiment of the present invention, in by the electrode step, described inner electrode layer is any one in silver, copper, gold, the platinum.
In a preferred embodiment of the present invention, the described default sintering temperature in the sintering step is 1050 ℃ to 1100 ℃.
In a preferred embodiment of the present invention, the described default sintering temperature in the burn in step is that the time of 380 ℃ and default sintering is 3 hours.
Compared to prior art, the piezoelectric ceramics that preparation method of the present invention makes has high electromechanical coupling factor, can also solve this problem of temperature stability.In addition, add the auxiliary component that contains fusing assistant in the described piezoelectric ceramics, under the prerequisite of guaranteed performance and temperature stability, enlarged the scope of sintering temperature, be conducive to the practical of low-temperature sintering and piezoelectric.
Embodiment
The below will be clearly and completely described the technical scheme in the embodiment of the invention, and obviously, described embodiment only is a part of embodiment of the present invention, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills belong to the scope of protection of the invention not making all other embodiment that obtain under the creative work prerequisite.
The disclosed piezoceramic material of the embodiment of the invention is for comprising at least lead, zirconium and titanium composite oxides, and the doping by niobium manganese phase and some oxide compounds, had simultaneously high electromechanical coupling factor and high-temperature stability, specifically describes as follows.
The embodiment of the invention discloses a kind of piezoceramic material, described piezoceramic material comprises main ingredient and auxiliary component, and the expression formula of described main ingredient is Pb
a(Mn
1/3Nb
2/3)
bZr
xTi
yO
3, wherein, 0.95≤a≤1.05,0.05≤b≤0.2, b+x+y=1, described auxiliary component are at least a oxide compound or the salt among W, Cu, Ba, Si, the Mn.By adjusting the proportioning of x and y, adjust the performance of described piezoceramic material, finally make the combination of its degree of reaching a high temperature stability and high coupling coefficient.
Wherein, the weight percentage of described auxiliary component in described piezoceramic material is less than 2%, and described auxiliary component is used for strengthening the piezoelectric property of piezoelectric, and the sintering temperature of piezoelectric is reduced to 1100 ℃ or lower.
In addition, the embodiment of the invention also discloses a kind of preparation method of piezoceramic material, described preparation method synthesizes required principal phase afterwards by the mixing of various oxide compounds, prepares required piezoceramic material by doctor-blade casting process again, and described preparation method specifically comprises the steps:
Step S1, batching is also mixed
Each starting material is provided, and correspondence is mixed each starting material component to form the hopcalite that contains at least Pb, Zr, Ti, Nb and Mn by ball mill.The raw material selection purity that provides is high, fineness is little and active large powder, and wherein a kind of prescription is to adopt to comprise that following component mixing forms, specifically as shown in Table 1.
Table one
Select raw materials usedly according to prescription or molecular formula, and carry out corrected Calculation by material purity, then carry out the weighing of raw material.Press after the stoicheiometry batching, use planetary ball mill that various batchings are mixed.What industry adopted usually is that horizontal direction is rotated ball milling method, can certainly select the blending meanss such as vibrations ball milling and comminution by gas stream.
Step S2, pre-burning
Raw material after the mixing and ball milling is carried out pre-burning.Pre-burning is to make stock yard generation solid state reaction to generate the process of required product, should maintain the temperature at the selection of 380 degrees centigrade and 3 hours pre-burning time in the pre-burning process.
Step S3 pulverizes and the doping auxiliary component
The reacted materials'use planetary ball mill of pre-burning is pulverized.Simultaneously, at least a oxide compound or the salt that mix in the material after pulverizing among W, Cu, Ba, Si and the Mn form the mixture that contains auxiliary component as auxiliary component.
In the present invention, the hotchpotch that adopts of a kind of preferred embodiment is: 1wt%BaW
0.5Cu
0.5O
3And 0.05wt%CuO.
Step S4, moulding
In the mixture that contains auxiliary component, add binding agent, softening agent, dispersion agent and solvent and mix to form ceramic size.To ceramic size de-bubble aftershaping, generate ceramic green sheet.The principal phase of described ceramic green sheet: Pb
0.998(Mn
1/3Nb
2/3)
0.1(Zr
0.51Ti
0.49)
0.9O
3
The method of forming ceramic base sheet mainly contains four kinds; Rolling formation, flow casting molding, dry-pressing formed and hydrostaticpressure moulding.Rolling formation is applicable to thin sheet element; Flow casting molding is suitable for thinner element, and thickness can be less than 10m; The dry-pressing formed block elements that is suitable for; The hydrostaticpressure moulding is suitable for abnormity or block elements.Except the hydrostaticpressure moulding, other forming methods all need to have tackiness agent, and tackiness agent generally accounts for about 3% of raw material weight.Moulding needs later on binder removal.The effect of tackiness agent just is beneficial to moulding, but it is the strong material of a kind of reductibility, should be with its discharge in order to avoid affect sintering quality after the moulding.Among the present invention, adopt the flow casting molding method to form the ceramic membrane band.
Step S5 is by electrode
Ceramic green sheet and inner electrode layer is alternately laminated to obtain the lamination product.Described ceramic green sheet form electrode layer with realize piezoelectric ceramics by electrode, wherein available electrode materials has silver, copper, gold, platinum etc.The method that forms described electrode layer has vacuum-evaporation, electroless plating etc. multiple.What adopt in the present embodiment is to coat the silver slurry, fired electrodes in air.
Step S6, sintering
Sintered layer is cut down output thing to produce sintered product under the sintering temperature that presets, and described setting sintering temperature is preferably 1050 ℃ to 1100 ℃.Sintering is that base substrate is heated to sufficiently high temperature, the process that ceramic green sheet generation volumetric shrinkage, density raising and intensity are increased.The mechanism of sintering process is the diffusion motion that forms the atom of this material.
Step S6, polarization
In order to prevent that air under high pressure ionizing, puncturing, the sintered product polarization is namely obtained required piezoelectric ceramics.Polarization generally is to carry out in silicone oil.In order to obtain good piezoelectric property, need to select suitable strength of electric field, suitable polarization temperature.Piezoelectric ceramics after polarization is processed was placed after 24 hours, measured d33 with the piezoelectric constant survey meter, with high-frequency resistance analyser (Agilent4294A etc.) Measuring Dielectric Constant, dielectric loss, resonant frequency etc.
Compared to prior art, the piezoceramic material that preparation method of the present invention makes has high electromechanical coupling factor, can also solve this problem of temperature stability.In addition, add the auxiliary component that contains fusing assistant in the described piezoceramic material, under the prerequisite of guaranteed performance and temperature stability, enlarged the scope of sintering temperature, be conducive to the practical of low-temperature sintering and piezoelectric.
The above only is embodiments of the invention; be not so limit claim of the present invention; every equivalent structure or equivalent flow process conversion that utilizes description of the present invention to do; or directly or indirectly be used in other relevant technical field, all in like manner be included in the scope of patent protection of the present invention.
Claims (9)
1. a piezoceramic material is characterized in that, comprises main ingredient and auxiliary component, and the expression formula of described main ingredient is Pb
a(Mn
1/3Nb
2/3)
bZr
xTi
yO
3, wherein, 0.95≤a≤1.05,0.05≤b≤0.2, b+x+y=1, described auxiliary component are at least a oxide compound or the salt among W, Cu, Ba, Si, the Mn.
2. piezoceramic material according to claim 1 is characterized in that, the weight percentage of described auxiliary component in described piezoelectric ceramics is less than 2%.
3. the preparation method of piezoceramic material according to claim 1 and 2 is characterized in that, comprises the steps:
Step S1, batching is also mixed: mix each component to form the hopcalite that contains at least Pb, Zr, Ti, Nb and Mn;
Step S2, pre-burning: the raw material after the mixing and ball milling is carried out pre-burning;
Step S3, pulverize and the doping auxiliary component: with the reacted material disintegrating of pre-burning, at least a oxide compound among mix simultaneously W, Cu, Ba, Si and the Mn or salt form the mixture that contains auxiliary component as auxiliary component;
Step S4, moulding: in the mixture that contains auxiliary component, add formed material to form ceramic size;
Step S5 is by electropolarization: ceramic green sheet and inner electrode layer is alternately laminated to obtain the lamination product;
Step S6, sintering: sintered layer is cut down output thing to produce sintered product under the sintering temperature;
Step S7, polarization: with the sintered product polarization, namely obtain required piezoceramic material.
4. preparation method according to claim 3 is characterized in that, mixes described starting material and realize by ball mill in step S1.
5. preparation method according to claim 3, it is characterized in that, in step S4 during moulding, the formed material that adds in the mixture that contains auxiliary component is to comprise at least a in binding agent, softening agent, dispersion agent and the solvent, and mixes to form ceramic size.
6. preparation method according to claim 5 is characterized in that, described forming method comprises it being to adopt the flow casting molding method to process the ceramic membrane band.
7. preparation method according to claim 3 is characterized in that, in by the electrode step, described inner electrode layer is any one in silver, copper, gold, the platinum.
8. preparation method according to claim 3 is characterized in that, the described default sintering temperature in the sintering step is 1050 ℃ to 1100 ℃.
9. preparation method according to claim 3 is characterized in that, the described default sintering temperature in the burn in step is that the time of 380 ℃ and default sintering is 3 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107263701A (en) * | 2017-07-25 | 2017-10-20 | 苏州雾联医疗科技有限公司 | A kind of preparation method of piezoelectric ceramics |
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| CN1340476A (en) * | 2000-08-25 | 2002-03-20 | 株式会社村田制作所 | Piezoelectric ceramic composition and piezoelectric element |
| CN101805183A (en) * | 2010-03-02 | 2010-08-18 | 中国科学院上海硅酸盐研究所 | A low-temperature sintered Pb (Ni1/3Nb2/3) O3-Pb (Zr, ti) O3ceramic powder and its prepn |
-
2013
- 2013-01-25 CN CN2013100308554A patent/CN103073290A/en active Pending
Patent Citations (3)
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| JP2000103674A (en) * | 1998-09-29 | 2000-04-11 | Matsushita Electric Ind Co Ltd | Piezoelectric ceramic composition and its production |
| CN1340476A (en) * | 2000-08-25 | 2002-03-20 | 株式会社村田制作所 | Piezoelectric ceramic composition and piezoelectric element |
| CN101805183A (en) * | 2010-03-02 | 2010-08-18 | 中国科学院上海硅酸盐研究所 | A low-temperature sintered Pb (Ni1/3Nb2/3) O3-Pb (Zr, ti) O3ceramic powder and its prepn |
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| XIAOLIAN CHAO ET AL.: "Effect of addition of Ba(W0.5Cu0.5)O3 in Pb(Mg1/3Nb2/3)O3-Pb(Zn1/3Nb2/3)O3-Pb(Zr0.52Ti0.48)O3 ceramics on the sintering temperature, electrical properties and phase transition", 《JOURNAL OF ALLOYS AND COMPOUNDS》, vol. 509, 24 September 2010 (2010-09-24), pages 512 - 517 * |
Cited By (1)
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| CN107263701A (en) * | 2017-07-25 | 2017-10-20 | 苏州雾联医疗科技有限公司 | A kind of preparation method of piezoelectric ceramics |
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Application publication date: 20130501 |