CN103467090A - Piezoelectric ceramic material, sintered body and preparation method thereof, and piezoelectric ceramic device - Google Patents
Piezoelectric ceramic material, sintered body and preparation method thereof, and piezoelectric ceramic device Download PDFInfo
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- CN103467090A CN103467090A CN2013103962333A CN201310396233A CN103467090A CN 103467090 A CN103467090 A CN 103467090A CN 2013103962333 A CN2013103962333 A CN 2013103962333A CN 201310396233 A CN201310396233 A CN 201310396233A CN 103467090 A CN103467090 A CN 103467090A
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Abstract
The invention provides a piezoelectric ceramic material of which the chemical general formula is PbxSr1-x(Mn1/3Sb2/3)yZrzTi1-y-zO3+m%CeO2+n%Cr2O3, wherein 0.9<=x<=1, 0<=y<=0.15, 0.4<=z<=0.62, 0<=m<=1, and 0<=n<=1. The running method is especially suitable for forming flaky ceramic products which are 20-300 mu m thick, has the advantages of high speed, high automation degree, high efficiency, uniform product structure, good quality and the like, and therefore, can satisfy the development requirements of miniaturation, integration, low noise and multifunction for modern electronic components; and by adjusting the formula, the piezoelectric ceramic has excellent piezoelectricity and temperature stability at the same time, thereby satisfying the operational requirements of the product.
Description
Technical field
The present invention relates to a kind of piezoceramic material, sintered compact, piezoelectric ceramic devices of high tension performance and adopt the preparation method of the sintered compact of described piezoceramic material.
Background technology
After within 1954, having it is found that the PZT lead titanate piezoelectric ceramics, 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 basis, also all arise at the historic moment with the improved three component system of multiple element, four-component-system piezoelectric ceramics.
In order to obtain as obtaining high performance piezoelectric ceramics, many employings are to Pb (Zr, Ti) O at present
3the part displacement is carried out in A position (Pb) or the B position (Zr, Ti) of modification, and changes zirconium titanium ratio to reach the purpose of adjusting performance.The preparation method adopts common solid sintering technology, by the powder after pre-burning and certain proportionings such as binding agent, the dry-pressing formed sintering that carried out afterwards.This sintering method not only can not meet piezo component diversification and complicated requirement day by day, need higher sintering temperature (1200 ℃-1300 ℃) simultaneously, also be unfavorable for the reduction of cost, and the PbO volatilization is serious in sintering process, not only can damage the mankind's health and contaminate environment, also can cause departing from of actual constituent, thereby make performance change, plumbous volatilization also can cause corrosion to the heating rod of agglomerating plant, has reduced the work-ing life of equipment.
Along with the development of surface mounting technology (SMT), multilayer piezoelectric ceramic is favored with its high-level efficiency, miniaturization, the integrated market that enjoys of function, and this just requires interior electrode and ceramic burnt together altogether to become.Silver point is 961 ℃, and on this temperature, the general palladium-silver alloy that adopts is as common burning electrode, and along with the rising of palladium content, its price will drive the significantly rising of product cost.
At present piezoelectric ceramics adopts traditional solid sintering technology, by the powder after pre-burning and certain proportionings such as binding agent, the dry-pressing formed sintering that carried out afterwards.That this traditional method has that structure is single, size is wayward, product composition rises and falls is large, production efficiency is low, be unsuitable for batch production, can not produce the shortcoming such as large-scale thin plate, can not meet the piezo component requirement of multiple stratification and structure complicated day by day, meanwhile, piezoelectric ceramics performance and the temperature stability of formula often can not be met simultaneously at present, are unfavorable for practical.
Summary of the invention
The casting method that the present invention adopts is particularly suitable for the flaky pottery goods of moulding 20-300 μ m thickness, produce this series products and there is the many advantages such as speed is fast, level of automation is high, efficiency is high, product is organized even structure, quality is good, thereby can meet the demand for development of the microminiaturization of hyundai electronics components and parts, integrated, lower noise and multifunction, and by the adjustment of formula, make piezoelectric ceramics there is excellent piezoelectric property and temperature stability simultaneously, met the service requirements of product.
The invention provides a kind of piezoceramic material, described piezoceramic material contains useful chemical general formula:
Pb
xsr
1-x(Mn
1/3sb
2/3)
yzr
zti
1-y-zo
3+ m%CeO
2+ n%Cr
2o
3mean and meet the main ingredient of following relation: 0.9≤x≤1,0≤y≤0.15,0.4≤z≤0.62,0≤m≤1,0≤n≤1.
A kind of piezoelectric ceramics sintered compact, described piezoelectric ceramics sintered compact is the sintered compact obtained as above-mentioned piezoceramic material by firing.
A kind of preparation method of piezoelectric ceramics sintered compact, described preparation method comprises the steps: batching: press Pb
xsr
1-x(Mn
1/3sb
2/3)
yzr
zti
1-y-zo
3+ m%CeO
2+ n%Cr
2o
3the chemical formula proportioning provides each component of piezoceramic material and described component is made to powder, and described component comprises Pb
3o
4, SrCO
3, MnCO
3, Sb
2o
3, ZrO
2, TiO
2, CeO
2, Cr
2o
3; Batch mixing: the distilled water that the above-mentioned powder configured is added to the 1:1 quality mixes 8 hours post-dryings; Calcining: the product after above-mentioned oven dry is calcined in the environment of 840-930 ℃ to 3h and obtained calcinate to synthesize; Pulverize: above-mentioned calcinate is ground into to powder and dries to form mixture; Slurrying: in said mixture, add binding agent, softening agent, dispersion agent, solvent and mix to form ceramic size; Moulding: curtain coating after described ceramic size de-bubble is formed to ceramic membrane; Stacked: by the stacked setting of above-mentioned ceramic membrane and etc. static pressure form the lamination product; Sintering: in the environment of 1050-1150 ℃, insulation 3h fires described lamination product and forms the piezoelectric ceramics sintered compact.
Preferably, in batching step, the mode that described component is mixed by material choice or ball milling is made powder.
Preferably, in batching step, the granularity median of described powder is controlled at below 2 μ m.
Preferably, in described batch mixing step, the powder configured is mixed in ball mill with distilled water.
Preferably, in pulverising step, adopt the microballon ball milling to shatter described calcinate.
Preferably, in pulverising step, the size-grade distribution of the mixture after shattering is below median 1 μ m.
A kind of piezoelectric ceramic devices, described piezoelectric ceramic devices form by the above-mentioned piezoelectric ceramics sintered compact of polarization of electrode.
Preferably, described piezoelectric ceramic devices are that in 120 ℃ of silicone oil under 7000-8000V/mm, polarization 20min obtains in the polarized electric field scope.
Compared to correlation technique, the casting method that the present invention adopts is particularly suitable for the flaky pottery goods of moulding 20-300 μ m thickness, produce this series products and there is the many advantages such as speed is fast, level of automation is high, efficiency is high, product is organized even structure, quality is good, thereby can meet the demand for development of the microminiaturization of hyundai electronics components and parts, integrated, lower noise and multifunction, and by the adjustment of formula, make piezoelectric ceramics there is excellent piezoelectric property and temperature stability simultaneously, met the service requirements of product.
The accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, in below describing embodiment, the accompanying drawing of required use is briefly described, 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 ceramic section microstructure of one embodiment of the invention piezoelectric ceramics;
Fig. 2 is the power spectrum of ceramic section shown in sintering Fig. 1;
Fig. 3 is the dielectric temperature spectrum of piezoelectric ceramics embodiment illustrated in fig. 1;
Fig. 4 is the ferroelectric hysteresis loop of piezoelectric ceramics embodiment illustrated in fig. 1.
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.Embodiment based in the present invention, those of ordinary skills, not making all other embodiment that obtain under the creative work prerequisite, belong to the scope of protection of the invention.
The invention provides and the invention provides a kind of piezoceramic material, described piezoceramic material contains useful chemical general formula:
Pb
xsr
1-x(Mn
1/3sb
2/3)
yzr
zti
1-y-zo
3+ m%CeO
2+ n%Cr
2o
3mean and meet the main ingredient of following relation: 0.9≤x≤1,0≤y≤0.15,0.4≤z≤0.62,0≤m≤1,0≤n≤1.Add Mn in the PZT lead titanate piezoelectric ceramics
2+can improve Qm, add Sb
5+rear Kp improves, and densified sintering product is good, reproducible.Doped Ce O
2can improve the volume specific resistance of material, the time is aging, temperature is aging, the high field aging resistance improves, and doping Cr
2o
3also can improve time stability and temperature stability.
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 controlling the granularity of powder after raw material and pre-burning, use doctor-blade casting process to prepare required low temperature piezoelectric ceramics sintered compact, then be that in 120 ℃ of silicone oil under 7000-8000V/mm, polarization 20min obtains needed piezoelectric ceramic devices by the polarized electric field scope, specifically comprise the steps:
Step S1, batching: press Pb
xsr
1-x(Mn
1/3sb
2/3)
yzr
zti
1-y-zo
3+ m%CeO
2+ n%Cr
2o
3the chemical formula proportioning provides each component of piezoceramic material and described component is made to powder, and described component comprises Pb
3o
4, SrCO
3, MnCO
3, Sb
2o
3, ZrO
2, TiO
2, CeO
2, Cr
2o
3.
Calculate the quality of each feed composition according to the proportioning of chemical formula, with the weighing of precise electronic balance, by methods such as material choice or ball millings, the granularity median of above-mentioned each component is controlled at below 2 μ m, to improve the reactive behavior of raw material.
Step S2, batch mixing: the distilled water that the above-mentioned powder configured is added to the 1:1 quality mixes 8 hours post-dryings.The powder configured is mixed in ball mill with distilled water and makes mixing more even.
Step S3, calcining: the product after above-mentioned oven dry is calcined in the environment of 840-930 ℃ to 3h and obtained calcinate to synthesize.
Step S4, pulverize: above-mentioned calcinate is ground into to powder and dries to form mixture.
Wherein, use microballon ball mill pulverizing said mixture, the size-grade distribution of described mixture is also dried below median 1 μ m.The microballon ball milling has improved the specific surface area of split, makes the increased activity of powder, has increased the motivating force of sintering, and then has reduced ceramic sintering temperature; Cryogenic booster forms liquid phase in earlier stage at sintering, has promoted sintering, and in the sintering later stage, the frit component portion enters the principal crystalline phase lattice, thereby has also played the effect of doping vario-property.
Step S5, slurrying: in said mixture, add binding agent, softening agent, dispersion agent, solvent and mix to form ceramic size.
Wherein, described slurrying adds binding agent, softening agent, dispersion agent, solvent are as shown in table 1 below.
Table 1
Step S6, moulding: curtain coating after described ceramic size de-bubble is formed to ceramic membrane.
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 binder removal later.The effect of tackiness agent just is beneficial to moulding, but it is the material that a kind of reductibility is strong, should be by its discharge in order to avoid affect sintering quality after moulding.
Step S7, stacked: by the stacked setting of above-mentioned ceramic membrane and etc. static pressure form the lamination product.
Step S8, sintering: in the environment of 1050-1150 ℃, insulation 3h fires described lamination product and forms the piezoelectric ceramics sintered compact.
As shown in Figure 1, the microstructure figure of the ceramic section of the piezoelectric ceramics of making by above-mentioned preparation method, can find out, ceramic sintered compact, and major part is fractured into transgranular fracture, grain-size 2-3 μ m left and right.In addition, as shown in Figure 2, be the power spectrum of this pottery section of sintering, can reflect that ceramic principal element is Pb, Zr, Ti, Sb.
As shown in Figure 3, be the dielectric thermogram of this piezoelectric ceramics, Curie temperature, 282 ℃ of left and right, at this Curie temperature place, increases with frequency, and specific inductivity and dielectric loss all descend.In addition, shown in Fig. 4, be the ferroelectric hysteresis loop figure of this piezoelectric ceramics, its test frequency is 0.5Hz, remnant polarization is 12.2 μ C/cm
2, coercive field is 12.7kV/cm.The dielectric temperature spectrum of above-mentioned piezoelectric ceramics and ferroelectric hysteresis loop are all the piezoelectric ceramics test gained to being polarized.The piezoelectric ceramics sintered compact that has formed electrode layer is placed in to air, and be that in 120 ℃ of silicone oil under 7000-8000V/mm, polarization 20min obtains in the polarized electric field scope, then remove electric field, so obtain the piezoelectric ceramic devices that above-mentioned piezoelectric ceramics sintered compact is implemented polarization of electrode.
Described piezoelectric ceramic devices are tested and calculated piezoelectric property and temperature stability according to GB, wherein test result refers to table 2.
Table 2
Wherein, calculate specific inductivity by measure sample size and LCR.
The casting method that the present invention adopts is particularly suitable for the flaky pottery goods of moulding 20-300 μ m thickness, produce this series products and there is the many advantages such as speed is fast, level of automation is high, efficiency is high, product is organized even structure, quality is good, thereby can meet the demand for development of the microminiaturization of hyundai electronics components and parts, integrated, lower noise and multifunction, and by the adjustment of formula, make piezoelectric ceramics there is excellent piezoelectric property and temperature stability simultaneously, met the service requirements of product.
The foregoing is only embodiments of the invention; not thereby limit the scope of the claims of the present invention; every equivalent structure or conversion of equivalent flow process 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. a piezoceramic material, is characterized in that, described piezoceramic material contains useful chemical general formula:
Pb
xsr
1-x(Mn
1/3sb
2/3)
yzr
zti
1-y-zo
3+ m%CeO
2+ n%Cr
2o
3mean and meet the main ingredient of following relation: 0.9≤x≤1,0≤y≤0.15,0.4≤z≤0.62,0≤m≤1,0≤n≤1.
2. a piezoelectric ceramics sintered compact, is characterized in that, described piezoelectric ceramics sintered compact is the sintered compact obtained by firing piezoceramic material as claimed in claim 1.
3. the preparation method of a piezoelectric ceramics sintered compact, is characterized in that, described preparation method comprises the steps:
Batching: press Pb
xsr
1-x(Mn
1/3sb
2/3)
yzr
zti
1-y-zo
3+ m%CeO
2+ n%Cr
2o
3the chemical formula proportioning provides each component of piezoceramic material and described component is made to powder, and described component comprises Pb
3o
4, SrCO
3, MnCO
3, Sb
2o
3, ZrO
2, TiO
2, CeO
2, Cr
2o
3;
Batch mixing: the distilled water that the above-mentioned powder configured is added to the 1:1 quality mixes 8 hours post-dryings;
Calcining: the product after above-mentioned oven dry is calcined in the environment of 840-930 ℃ to 3h and obtained calcinate to synthesize;
Pulverize: above-mentioned calcinate is ground into to powder and dries to form mixture;
Slurrying: in said mixture, add binding agent, softening agent, dispersion agent, solvent and mix to form ceramic size;
Moulding: curtain coating after described ceramic size de-bubble is formed to ceramic membrane;
Stacked: by the stacked setting of above-mentioned ceramic membrane and etc. static pressure form the lamination product;
Sintering: in the environment of 1050-1150 ℃, insulation 3h fires described lamination product and forms the piezoelectric ceramics sintered compact.
4. the preparation method of piezoelectric ceramics sintered compact according to claim 3, is characterized in that, in batching step, the mode that described component is mixed by material choice or ball milling is made powder.
5. the preparation method of piezoelectric ceramics sintered compact according to claim 3, is characterized in that, in batching step, the granularity median of described powder is controlled at below 2 μ m.
6. the preparation method of piezoelectric ceramics sintered compact according to claim 3, is characterized in that, in described batch mixing step, the powder configured is mixed in ball mill with distilled water.
7. the preparation method of piezoelectric ceramics sintered compact according to claim 3, is characterized in that, in pulverising step, adopts the microballon ball milling to shatter described calcinate.
8. the preparation method of piezoelectric ceramics sintered compact according to claim 3, is characterized in that, in pulverising step, the size-grade distribution of the mixture after shattering is below median 1 μ m.
9. piezoelectric ceramic devices, is characterized in that, described piezoelectric ceramic devices form by polarization of electrode piezoelectric ceramics sintered compact as described as claim 3 to 8 any one.
10. piezoelectric ceramic devices according to claim 9, is characterized in that, described piezoelectric ceramic devices are that in 120 ℃ of silicone oil under 7000-8000V/mm, polarization 20min obtains in the polarized electric field scope.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105924165A (en) * | 2016-05-01 | 2016-09-07 | 林尔福 | High-strength ceramic material used for frequency converter and preparation method thereof |
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| CN1546427A (en) * | 2003-12-05 | 2004-11-17 | 中国科学院上海硅酸盐研究所 | Doped lead antimony manganese zirconia titanate piezoelectric ceramic materials suitable for industrial production and method for preparing same |
| CN103214240A (en) * | 2013-03-20 | 2013-07-24 | 瑞声精密制造科技(常州)有限公司 | Piezoceramic material, sintered body, preparation method thereof, and piezoceramic device |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546427A (en) * | 2003-12-05 | 2004-11-17 | 中国科学院上海硅酸盐研究所 | Doped lead antimony manganese zirconia titanate piezoelectric ceramic materials suitable for industrial production and method for preparing same |
| CN103214240A (en) * | 2013-03-20 | 2013-07-24 | 瑞声精密制造科技(常州)有限公司 | Piezoceramic material, sintered body, preparation method thereof, and piezoceramic device |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105924165A (en) * | 2016-05-01 | 2016-09-07 | 林尔福 | High-strength ceramic material used for frequency converter and preparation method thereof |
| CN105924165B (en) * | 2016-05-01 | 2019-01-04 | 林尔福 | A kind of high strength ceramics material and preparation method thereof for frequency converter |
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Application publication date: 20131225 |