CN103159472A - Piezoelectric ceramic material, sintering body, manufacture method of piezoelectric ceramic and piezoelectric ceramic device - Google Patents
Piezoelectric ceramic material, sintering body, manufacture method of piezoelectric ceramic and piezoelectric ceramic device Download PDFInfo
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- CN103159472A CN103159472A CN2013100522825A CN201310052282A CN103159472A CN 103159472 A CN103159472 A CN 103159472A CN 2013100522825 A CN2013100522825 A CN 2013100522825A CN 201310052282 A CN201310052282 A CN 201310052282A CN 103159472 A CN103159472 A CN 103159472A
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Abstract
The invention provides a piezoelectric ceramic material which comprises composite oxide comprising lead and titanic. The piezoelectric ceramic material has main components showed by a chemical general formula (PbaAbLn2/3 (1-a-b)) (TicMn1-c) O3 and satisfies the following relations, namely, a is larger or equal to 0.8 and smaller or equal to 0.9, b is larger or equal to 0 and smaller or equal to 0.5 , and c is larger or equal to 0.9 and smaller or equal to 1.0, wherein A is at least one of Cd and Ca, and Ln is one of La, Ce, Nd, Sm and Eu. The piezoelectric ceramic material has good and high anisotropism electromechanical coupling performance, high Curie temperature and low dielectric constants. Compared with a PZT piezoelectric ceramic system, the piezoelectric ceramic material has obvious advantages in application of aspects of high-temperature and high-frequency (frequency is larger than 5MHz) devices (an infrared probe and a surface acoustic wave device) and the like. A manufacture method is simple in technology, a formula is adjustable, the piezoelectric ceramic material is not prone to break, capable of full polarization, and capable of being used for industrial production.
Description
Technical field
The present invention relates to a kind of piezoceramic material, sintered compact, piezoelectric ceramic devices of high anisotropy and adopt the preparation method of the sintered compact of described piezoceramic material.
Background technology
After it is found that the PZT lead titanate piezoelectric ceramics in 1954, many countries such as the U.S., Japan, Holland have carried out detailed research to the piezoelectric ceramics system, and along with the PZT piezoceramic material that has deeply derived a series of superior performances of development, the range of application of piezoceramic material is also expanded greatly.Wherein take Pb-based lanthanumdoped zirconate titanates as the basis, also all arise at the historic moment with the improved three component system of multiple element, four-component-system piezoelectric ceramics, nineteen sixty-five the PANASONIC electric corporation Pb (Mg
1/3Nb
2/3) O
3Join as the 3rd component and made the first ternary system ceramics in PZT, not only can improve electromechanical coupling factor KP and high mechanical quality factor Qm after finding after deliberation to add some oxide compounds in this ternary system piezoelectric ceramics, frequency constant and aging property are improved.Ternary system ceramics has more superior performance than binary system ceramics, can regulate significantly alternative composition and piezoelectricity, easily obtains the reception shaped material of high electromechanical coupling number.
Due to the expansion of piezoelectric ceramics range of application, the device of different purposes is more and more higher to the piezoceramic material performance requriements, and the quality of piezoceramic material even becomes the development bottleneck in some field.For example the change of ultrasonic cleaning transverter and medical supersonic wave transducer, piezoelectric ceramic transformer and piezoelectric ceramic loudspeaker all exists with piezoceramic material with development and directly contacts.Therefore, make the piezoelectric vibrator product have better quality and more superior performance, research and development piezoceramic material and device are the keys that guarantees that quality product improves.
Studies show that in a large number various relaxation ferroelectrics soluble solids and PZT ceramic combination and the piezoelectric ceramics of this system is carried out ion exchange and doping vario-property, can obtain high dielectric, high tension performance, and developed more complicated quaternary system, five yuan of series ceramic materials on the basis of three component system, make the Research Prospects of piezoelectric ceramics more wide.
Piezo component is diversification and complicated requirement day by day, can not satisfy it to high anisotropy, easy-sintering, the easily requirement of polarization.
Therefore, the purpose of this invention is to provide a kind of piezoceramic material with good high anisotropy electromechanical coupling performance, high-curie temperature and low-k, and sintered compact and the various piezoelectric ceramic devices of firing formation by these piezoceramic materials are provided.
Summary of the invention
The present invention mainly solve be very easy to when ceramic product that existing piezoceramic material causes due to the strong anisotropy of structure cell is difficult in sintering, process of cooling through Curie temperature broken, be difficult to the problem that polarizes simultaneously.
In order to address the above problem, the invention provides a kind of piezoceramic material, it contains lead and titanium composite oxides, and described piezoceramic material contains useful chemical general formula (Pb
aA
bLn
2/3 (1-a-b)) (Ti
cMn
1-c) O
3Represent and satisfy the main ingredient of following relation:
0.8≤a≤0.9,0≤b≤0.05,0.9≤c≤1.0, wherein, A is at least a in Cd, Ca, and Ln is at least a in La, Ce, Nd, Sm, Eu.
Preferably, described piezoceramic material forms by the doping of cadmium, rare-earth phase.
A kind of piezoelectric ceramics sintered compact, described piezoelectric ceramics sintered compact are a kind ofly to contain lead and titanium composite oxides by firing, and contain useful chemical general formula (Pb
aA
bLn
2/3 (1-a-b)) (Ti
cMn
1-c) O
3Represent and satisfy the main ingredient of following relation:
0.8≤a≤0.9,0≤b≤0.05,0.9≤c≤1.0, wherein, A is at least a in Cd, Ca, and Ln is the sintered compact that at least a piezoceramic material in La, Ce, Nd, Sm, Eu obtains.
A kind of preparation method of piezoelectric ceramics sintered compact, described preparation method comprises the steps:
Batching: each component that piezoceramic material is provided;
Batch mixing: mix to form hopcalite and the oven dry that contains at least Pb, Ti, Mn according to the chemical formula proportioning;
Calcining: the mixture after above-mentioned oven dry is calcined 3h with the synthetic calcinate that obtains in the environment of 850-950 ℃;
Pulverize: pulverize above-mentioned calcinate, to obtain powder and oven dry;
Slurrying: add binding agent, softening agent, dispersion agent, solvent and mix to form ceramic size in above-mentioned powder;
Moulding: after de-bubble, curtain coating forms ceramic membrane;
Stacked: with the stacked form layers thing of cutting down output that arranges of above-mentioned ceramic membrane;
Sintering: insulation 3h fires described lamination product and forms the piezoelectric ceramics sintered compact in the environment of 1150-1250 ℃.
Preferably, in batching and batch mixing step, described component also contains manganous carbonate.
Preferably, in batch mixing and pulverising step, mix by ball milling the mode that shatters with ball milling respectively and realize mixing and shattering.
Preferably, in described pulverising step, the median of the size-grade distribution of resulting powder is below 1 micron.
Preferably, described piezoelectric ceramic devices form by polarization of electrode piezoelectric ceramics sintered compact as described in claim 4 to 6 any one.
Preferably, described piezoelectric ceramic devices polarize at 150 ℃ of temperature, and 20min obtains.
Preferably, the electric field scope of described polarization is 5100V/mm-7600V/mm.
Compared to correlation technique, the thickness electromechanical coupling coefficient of modified lead titanate piezoelectric ceramic provided by the invention (Kt＞0.5) is much larger than planar electromechanical coupling factor (Kp＜0.04), Kt/Kp＞16, have good high anisotropy electromechanical coupling performance, the size of ceramic product needn't be subjected to width much larger than the restriction of thickness.Therefore meanwhile, this kind material has high-curie temperature and low-k, and (application of the aspects such as the device (infrared probe, surface acoustic wave device) of frequency＞5MHz) has obvious advantage with respect to PZT piezoelectric ceramics system at high-temperature high-frequency.Its preparation method technique is simple, formula is adjustable, it is broken to be difficult for, can fully polarize, can be used for suitability for industrialized production in batches.
Description of drawings
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, during the below will describe embodiment, the accompanying drawing of required use is done to introduce simply, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain other accompanying drawing according to these accompanying drawings, wherein:
Fig. 1 is the structural representation after piezoelectric ceramics sintered compact of the present invention forms electrode layer;
Fig. 2 is the microstructure of piezoelectric ceramics sintered compact section of the present invention;
Fig. 3 is the frequency-impedance oscillogram of piezoelectric ceramics sintered compact shown in Figure 1;
Fig. 4 is that the electromechanical coupling factor of piezoelectric ceramics sintered compact shown in Figure 1 is with the variation diagram of polarized electric field.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only a part of embodiment of the present invention, rather than whole embodiment.Based on the embodiment in 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 invention provides a kind of piezoceramic material, it comprises plumbous at least and titanium composite oxides also obtains by the doping of cadmium, rare-earth phase, and it possesses high anisotropy.Described piezoceramic material comprises the main ingredient that is expressed from the next:
(Pb
aA
bLn
2/3(1-a-b))(Ti
cMn
1-c)O
3，
Wherein satisfy 0.8≤a≤0.9,0≤b≤0.05,0.9≤c≤1.0, A is at least a in Cd, Ca, and Ln is at least a in La, Ce, Nd, Sm, Eu.By adjusting the proportioning of a, b, c, adjust its performance, finally make it reach high anisotropy and be easy to and make.
The present invention provides a kind of preparation method who adopts above-mentioned piezoceramic material to be processed to form the piezoelectric ceramics sintered compact simultaneously, it is by various hopcalites or carbonate and various hopcalite to the main ingredient that forms described piezoceramic material, process the synthetic piezoceramic material principal phase of obtaining the tool high anisotropy, prepare required piezoelectric ceramics sintered compact by doctor-blade casting process again, then obtain needed piezoelectric ceramic devices by the described piezoelectric ceramics sintered compact that polarizes under certain condition, specifically comprise the steps:
Step S1, batching: each component and the oven dry of piezoceramic material are provided.
Each component is provided, and the starting material component contains at least a at least a and La, Ce in the oxide compound, Cd, Ca of Pb, Ti, Mn, Nd, Sm, Eu at least.Preferably, can also add a certain amount of manganous carbonate in described component.The raw material selection purity that provides is high, fineness is little and active large powder, calculates the quality of each raw material according to the proportioning of chemical formula, with the weighing of precise electronic balance.
Step S2, batch mixing: mix to form the hopcalite that contains at least Pb, Ti, Mn according to the chemical formula proportioning, the distilled water that this mixture is added 1:1 ratio weight mixes and dries 8h.
Correspondence is mixed each starting material component to form the hopcalite that contains at least Pb, Ti, Mn by ball mill, and the oxide compound of described Pb, Ti, Mn refers to Pb3O4, TiO2, MnO2.After pressing the stoicheiometry batching, and press the raw material gross weight and add distilled water at 1: 1, then use ball mill with various batching ball milling mixing 8h.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 S3, synthetic: as the mixture after above-mentioned batch mixing to be calcined 3 hours to obtain calcinate with synthetic required composition in 850-950 ℃ of hot environment.
Step S4 pulverizes: pulverize above-mentioned calcinate, to obtain powder and oven dry.Wherein said pulverising step is to realize mixture after described calcining is pulverized by the ball mill pulverizing mode, and described pulverising step obtains the median of size-grade distribution at the powder below 1 micron.
Step S5, slurrying: add binding agent, softening agent, dispersion agent, solvent in the powder after the above-mentioned pulverizing and mix to form ceramic size.Wherein, the binding agent, softening agent, dispersion agent, the solvent that add of described slurrying is as shown in table 1 below.
Table 1
Step S6, moulding: form ceramic membrane after de-bubble.
The method of forming ceramic film 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 10 μ m; 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 3% left and right 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 moulding.In the present invention, adopt the flow casting molding method to form ceramic membrane.
Step S7, stacked: with the stacked setting of the ceramic membrane after moulding and the static pressure form layers thing of cutting down output.
Step S8, sintering: insulation was fired described lamination product in three hours and is formed the piezoelectric ceramics sintered compact in 1150-1250 ℃ of environment.
As shown in Figure 2, the microstructure figure of the section of the piezoelectric ceramics sintered compact that forms by above-mentioned preparation method, in addition, as shown in Figure 3, by observing the frequency that width and Thickness Ratio are the concrete sample piezoelectric ceramics sintered compact of 4:1-impedance oscillogram, can find out near (5M-5.25M) obviously not assorted peak tuning-points, tuning-points has good discrimination, can be used for the making of product, have an assorted peak and conventional situation is next.
Form on described piezoelectric ceramics sintered compact 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 layer in air.As shown in Figure 1, form the schematic diagram of the piezoelectric ceramics sintered compact after electrode layer, the upper and lower surface of pottery 1 is all by upper silver layer 2.
The piezoelectric ceramics sintered compact that has formed electrode layer is placed in the temperature of 150 ℃, and through-thickness applies the DC electric field of 5100-7600V/mm, then polarization 20min removes electric field, so obtains the piezoelectric ceramic devices that above-mentioned piezoelectric ceramics sintered compact is implemented polarization of electrode.Specifically as shown in Figure 4, can find out, increase with polarized electric field, thickness direction electromechanical coupling factor (Kt) first increases afterwards and reduces, planar electromechanical coupling factor (Kp) first reduces rear increase, both all reach extreme value when 6600V/mm, Kt/Kp also reaches maximum value 16 naturally when this electric field, and 6600V/mm is the optimum polarization electric field of piezoelectric ceramics sintered compact for this reason.
Described piezoelectric ceramic devices are tested and calculated piezoelectric property according to GB, the concrete sample test after employing 6600V/mm optimum polarization electric field polarization is the results detailed in Table 2.
Table 2
Thus, can find out that the thickness electromechanical coupling coefficient (Kt＞0.5) of modified lead titanate piezoelectric ceramic provided by the invention is much larger than planar electromechanical coupling factor (Kp＜0.04), Kt/Kp＞16, have good high anisotropy electromechanical coupling performance, the size of ceramic product needn't be subjected to width much larger than the restriction of thickness.Therefore meanwhile, this kind material has high-curie temperature and low-k, and (application of the aspects such as the device (infrared probe, surface acoustic wave device) of frequency＞5MHz) has obvious advantage with respect to PZT piezoelectric ceramics system at high-temperature high-frequency.Its preparation method technique is simple, formula is adjustable, it is broken to be difficult for, can fully polarize, can be used for suitability for industrialized production in batches.
In above-mentioned preparation method, preparation method's technique of described piezoceramic material is simple, formula is adjustable, be difficult for fragmentation, can fully polarize, can be used for the batch suitability for industrialized production and utilize inverse piezoelectric effect to produce the various piezoelectric ceramic devices of deformation.
The above is only embodiments of the invention; not thereby limit the scope of the claims of the present invention; every equivalent structure or equivalent flow process conversion that utilizes specification sheets of the present invention and accompanying drawing content to do; or directly or indirectly be used in other relevant technical field, all in like manner be included in scope of patent protection of the present invention.
Claims (10)
1. piezoceramic material, it contains lead and titanium composite oxides, it is characterized in that, and described piezoceramic material contains useful chemical general formula (Pb
aA
bLn
2/3 (1-a-b)) (Ti
cMn
1-c) O
3Represent and satisfy the main ingredient of following relation:
0.8≤a≤0.9,0≤b≤0.05,0.9≤c≤1.0, wherein, A is at least a in Cd, Ca, and Ln is at least a in La, Ce, Nd, Sm, Eu.
2. piezoceramic material according to claim 1, is characterized in that, described piezoceramic material forms by the doping of cadmium, rare-earth phase.
3. a piezoelectric ceramics sintered compact, is characterized in that, described piezoelectric ceramics sintered compact is the sintered compact that obtains by firing piezoceramic material as claimed in claim 1 or 2.
4. the preparation method of a piezoelectric ceramics sintered compact, is characterized in that, described preparation method comprises the steps:
Batching: each component that piezoceramic material is provided;
Batch mixing: mix to form hopcalite and the oven dry that contains at least Pb, Ti, Mn according to the chemical formula proportioning;
Calcining: the mixture after above-mentioned oven dry is calcined 3h with the synthetic calcinate that obtains in the environment of 850-950 ℃;
Pulverize: pulverize above-mentioned calcinate, to obtain powder and oven dry;
Slurrying: add binding agent, softening agent, dispersion agent, solvent and mix to form ceramic size in above-mentioned powder;
Moulding: after de-bubble, curtain coating forms ceramic membrane;
Stacked: with the stacked form layers thing of cutting down output that arranges of above-mentioned ceramic membrane;
Sintering: insulation 3h fires described lamination product and forms the piezoelectric ceramics sintered compact in the environment of 1150-1250 ℃.
5. the preparation method of piezoelectric ceramics sintered compact according to claim 4, is characterized in that, in batching and batch mixing step, described component also contains manganous carbonate.
6. the preparation method of piezoelectric ceramics sintered compact according to claim 4, is characterized in that, in batch mixing and pulverising step, mixes by ball milling the mode that shatters with ball milling respectively and realize mixing and shattering.
7. the preparation method of piezoelectric ceramics sintered compact according to claim 4, is characterized in that, in described pulverising step, the median of the size-grade distribution of resulting powder is below 1 micron.
8. piezoelectric ceramic devices, is characterized in that, described piezoelectric ceramic devices form by polarization of electrode piezoelectric ceramics sintered compact as described in claim 4 to 7 any one.
9. piezoelectric ceramic devices according to claim 8, is characterized in that, described piezoelectric ceramic devices polarize at 150 ℃ of temperature, and 20min obtains.
10. piezoelectric ceramic devices according to claim 9, is characterized in that, the electric field scope of described polarization is 5100V/mm-7600V/mm.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86106297A (en) * | 1985-09-20 | 1987-04-22 | 菲利浦(北美)有限公司 | Method of manufacturing piezoelectric ceramic elements |
| CN1413948A (en) * | 2002-10-21 | 2003-04-30 | 深圳富康精密电子陶瓷有限公司 | Low-temp. sintered high power piezoelectric ceramic transformer material and its manufacturing method |
| CN101412626A (en) * | 2007-10-18 | 2009-04-22 | Tdk株式会社 | Piezoelectric ceramic composition and oscillator |
-
2013
- 2013-02-18 CN CN2013100522825A patent/CN103159472A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86106297A (en) * | 1985-09-20 | 1987-04-22 | 菲利浦(北美)有限公司 | Method of manufacturing piezoelectric ceramic elements |
| CN1413948A (en) * | 2002-10-21 | 2003-04-30 | 深圳富康精密电子陶瓷有限公司 | Low-temp. sintered high power piezoelectric ceramic transformer material and its manufacturing method |
| CN101412626A (en) * | 2007-10-18 | 2009-04-22 | Tdk株式会社 | Piezoelectric ceramic composition and oscillator |
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Application publication date: 20130619 |