CN101429022A - Ferro-voltage ceramic component with low sintering temperature character, production and uses thereof - Google Patents
Ferro-voltage ceramic component with low sintering temperature character, production and uses thereof Download PDFInfo
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- CN101429022A CN101429022A CNA2008102044634A CN200810204463A CN101429022A CN 101429022 A CN101429022 A CN 101429022A CN A2008102044634 A CNA2008102044634 A CN A2008102044634A CN 200810204463 A CN200810204463 A CN 200810204463A CN 101429022 A CN101429022 A CN 101429022A
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Abstract
The invention relates to a ferroelectric piezoelectric ceramic with the characteristic of low sintering temperature. The compositions are (1-x-y)PbZrO3-xPbTiO3-yBi(Zn1/2Ti1/2)O3 and z weight percent of MnO2, wherein x is equal to between 0.30 and 0.50, y is equal to between 0.05 and 0.25, and z is equal to between 0.0 and 0.5. Oxide materials and the prior solid-state reaction electronic ceramic process are adopted to achieve the aim of sintering a compact piezoelectric ceramic chip at a low temperature between 900 and 1,000 DEG C. The PbZrO3-PbTiO3-Bi(Zn1/2Ti1/2)O3 ferroelectric piezoelectric ceramic is a single phase perovskite structure and has a 'hard' piezoelectric property. Presintering powder of the PbZrO3-PbTiO3-Bi(Zn1/2Ti1/2)O3 ferroelectric ceramic powder as a sintering auxiliary, and an electronic ceramic process of solid phase reaction are adopted so as to achieve the low temperature sintering of the strontium-doped lead zirconate titanate at a temperature of 1,050 DEG C as well as the modification of the piezoelectric property. The ferroelectric piezoelectric ceramic is particularly applicable to the manufactures of functional devices such as emission piezoelectric ceramic devices, low-temperature cofiring multi-layer ceramic piezoelectric drives, transformers, and transducers.
Description
Technical field
The invention belongs to material science, relate to PZT piezoceramic material and device technology of preparing.
Background technology
The PZT piezoelectric ceramics is a kind of important functional material and intelligent material, is widely used in fields such as electronic component, micrometric displacement control, miniature ultrasonic motor.PZT pottery is owing to have strong, the easy characteristics such as doping vario-property, good stability of Curie temperature height, piezoelectricity, at present at piezoceramic material and devices field dominate still.The PZT ceramic driver comprises one chip and multilayer driving mechanism, is used widely already in micrometric displacement control and ultrasound electric machine system.
The densification sintering technology of PZT ceramic powder is very big to the influence of PZT quality of item.Traditional PZT piezoelectric ceramics pressureless sintering is carried out at 1200-1400 ℃ of high temperature usually, owing to plumbous just begin volatilization being higher than 800 ℃, is difficult to obtain the uniform ceramic of compact sheet of component.Plumbous volatilization causes component deviation stoichiometry and product properties is reduced accurately, the stability of the Zr/Ti influence of fluctuations PZT product properties that causes thus simultaneously in the sintering process.In addition, higher sintering temperature causes alligatoring of PZT particle and reunion, reduces the microtexture and the character of pottery.If be lower than 1000 ℃ of temperature sintering PZT piezoelectric ceramics goods, because this moment, the saturated vapor pressure of PbO was lower, only less than 1% volatilization, can simplify agglomerating plant and technology greatly, needn't add sintering PbO atmospheric pellet and avoid using the double crucible technology, and adopt individual layer crucible covered and enclosed sintering can obtain high quality P ZT goods (reference 1,2).People have carried out multiple effort and have reduced the piezoelectric ceramics sintering temperature for this reason, as 1) adopt wet chemistry method or high-energy ball milling to prepare the nanoscale super-fine powder, improve powder active, thereby reduce sintering temperature, reduce plumbous volatilization, guarantee stoichiometry accurately; 2) sintering aids such as compound that add glass powder with low melting point or formation low melting point fused matter carry out liquid phase sintering.Adopt this kind method sintering temperature can be reduced to below 800 ℃, but range of application has great restriction,, reduce the piezoelectric property and the mechanical property of final ceramic component because additive forms second phase of non-piezoelectricity in last sintered compact; 3) solid solution reaction sintering is as 0.05mol% MnO
2(Nb
2O
5) doping 0.92Pb (ZrTi) O
3-0.05BiFeO
3-0.03Ba (Cu
0.5W
0.5) O
3+ 0.08wt%CuO, powder is synthetic to be finished with one step of dense sintering.In order to reach the sintering temperature that reduces the PZT material, balance between acceleration of sintering and raising electricity, the machine performance, people are still exploring and are adopting new sintering process, are optimized combination in conjunction with the advantage of several method, and all morning makes the piezoceramic material and the device direction effort of excellent property.
An important motivity that reduces the research work of PZT ceramic powder sintering temperature comes from the technology of preparing demand of multilayer piezoelectric ceramic driving mechanism, low temperature co-fired (LTCC, sintering temperature is lower than 1000 ℃) the development pole the earth of technology promoted driving mechanism and has been the device such as ultrasound electric machine of core drive device and the designs (reference 3,4) of system with it.Ultrasound electric machine is electrostrictive effect and the ultrasonic vibration that utilizes piezoelectric ceramics, the microscopic deformation of stator is converted to a kind of all solid state motor of the macroscopic motion of rotor (rotary-type motor) or mover (linear electric motor) by resonance amplification and friction coupling.Features such as that this motor has is fast such as response, control characteristic is good, low-speed big, simple and compact for structure, flexible design, lower noise, no electromagnetic interference can be used for systems such as spacecraft, flyer, automobile, robot and precision instrument.Good solid-state drive requires bigger mechanical shift (greater than 10 microns) and lower driving voltage (less than 100 volts).It is the normal a kind of important way that adopts of present Driven by Ultrasonic Motors device that thin driving mechanism is stacked to the multilayer driving mechanism.At present, at high temperature co-firing (HTCC, sintering temperature is higher than 1200 ℃) in the multilayered structure piezoelectric driving device making processes, because sintering temperature is higher, interaction between inner electrode Pd or Ag-Pd and PZT pottery causes less chemical uniformity and grain-size, reduce the stoicheiometry of PZT, thereby caused drive performance to worsen (reference 5).The rigid ferroelectric piezoelectric ceramics that employing has sintering temperature and low is that a kind of LTCC makes multilayer piezoelectric acutator spare efficient manner (reference 6,7); But also be a difficult point of current commercial technology exploitation, correlative study report less (reference 2,4).
Reference:
1, Y.Ponomarev, Y.M.Kim, Low temperature firable PZT compositions and piezoelectricceramic devices using the same, United States Patent (USP) 6878307.http://www.freepatentsonline.com/6878307.html
2、A.
，H.-J.Gesemann，L.Seffner，Low-Sintering?PZT-Ceramics?for?AdvancedActuators?In?ISAF’96.Proc.of?the?Tenth?IEEE?International?Symposium?on?Applicationsof?Ferroelectrics，eds.B.M.Kulwicki，A.A.Amin?and?A.Safari，Vol.1，263-266(1996)
3、K.Nakamura，M.Kurosawa，and?S.Ueha，Design?of?a?Hybrid?Transducer?Type?UltrasonicMotor，IEEE?Trans.Ultrason.，Ferroelect.，Freq.Contr.40(4)，395-401(1993)
4、K.Yao，B.Koc，and?K.Uchino，Longitudinal-Bending?Mode?Micromotor?UsingMultilayer?Piezoelectric?Actuator，IEEE?Trans.Ultrason.，Ferroelect.，Freq.Contr.，vol.48，no.4，pp.1066-107l，(2001)
5、K.Lubitz，H.Bodinger，And?C.Schuh，Interaction?Between?Electrodes?And?CeramicsIn?Multilayer?PZT，ISAF98
6、B.K.Gan，K.Yao，and?X.J.He，Complex?Oxide?Ferroelectric?CeramicsPb(Ni
1/3Nb
2/3)O
3-Pb(Zn
1/3Nb
2/3)O
3-Pb(Mg
1/3Nb
2/3)O
3-PbZrO
3-PbTiO
3?with?a?LowSinteringTemperature，J.Am.Ceram.Soc.，90，1186-1192(2007)
7、F.Bamiere，K.Benkert，M.Radanielina，C.Schuh，and?M.J.Hoffmann，Lowtemperature?sintering?and?high?piezoelectric?properties?of?strontiumdoped?PNZT-PNNceramics?processed?via?the?columbite?route，J.Europ.Ceram.Soc.27，3613-3617(2007)
Summary of the invention
The purpose of this invention is to provide a kind of ferroelectric piezoelectric ceramics with sintering temperature and low characteristic; The ferroelectric ceramic(s) powder that provides a kind of employing to have low-temperature sintering characteristic is done sintering agent, by sintering mechanism such as solid solution reactions, realizes the pressureless lower temperature sintering of PZT ceramics powder.Be different from the PZT piezoelectric ceramics low-temperature sintering technology of the non-ferroelectricity of traditional interpolation, low melting glass phase or formation low melting point fused matter compound, provide the new type low temperature of devices such as making high-performance " firmly " property PZT piezoceramic multilayer driving mechanism, transformer, transverter to burn material and device technology altogether.
For reaching above purpose, solution of the present invention is:
A kind of ferroelectric piezoelectric ceramics with sintering temperature and low characteristic is characterized in that: its component is (1-x-y) PbZrO
3-xPbTiO
3-yBi (Zn
1/2Ti
1/2) O
3+ zwt%MnO
2: x=0.30～0.50, y=0.05～0.25, z=0.0～0.5.PbZrO
3-PbTiO
3-Bi (Zn
1/2Ti
1/2) O
3Ferroelectric piezoelectric ceramics is single-phase perovskite structure.
A kind of method for preparing the ceramic of compact sheet is used (1-x-y) PbZrO
3-xPbTiO
3-yBi (Zn
1/2Ti
1/2) O
3+ zwt%MnO
2: x=0.30～0.50, y=0.05～0.25, the material component of z=0.0～0.5 comprises:
A, Bi
2O
3-PbO-ZnO-ZrO
2-TiO
2The powder wet-mixed;
B, 800 ℃ of pre-burnings 5 hours;
C, preburning powdered material wet grinding;
D, granulation, 200～250MPa pressure compressing tablet;
E, green sheet were 950～1050 ℃ of insulations 2～10 hours.
The piezoelectric ceramic actuator, the piezoelectric transformer that use described piezoelectric ceramics to make.
Use multilayer driving mechanism, transformer and the transverter of the low temperature co-fired making of electrode in described piezoelectric ceramics and the Ag-Pd.
A kind of pressureless lower temperature sintering method, the doped PZT PbZr that to adopt described ferroelectric ceramic(s) preburning powdered material be commercial applications
1-xTi
xO
3The low-temperature sintering auxiliary agent of piezoelectric ceramics powder, x=0.02～1.0 wherein, this ferroelectric ceramic(s) is 5.0～10.0wt% as the addition of sintering aid, the piezoelectric ceramics of pressureless lower temperature sintering commercial applications.
Use piezoelectric ceramics that described method makes and piezoelectric ceramic actuator, piezoelectric transformer.
Use the piezoelectric ceramics of described method making and multilayer driving mechanism, transformer and the transverter of the interior low temperature co-fired making of electrode of Ag-Pd.The preparation technology of above-mentioned ferroelectric piezoelectric ceramics is traditional solid state reaction electronic ceramic technology:
A, Bi
2O
3, PbO, ZnO, ZrO
2And TiO
2Powder is by (1-x-y) PbZrO
3-xPbTiO
3-yBi (Zn
1/2Ti
1/2) O
3Weighing, wet-mixed;
B, 800 ℃ of pre-burnings 5 hours;
C, preburning powdered material wet grinding;
D, Bi
2O
3-PbO-ZnO-ZrO
2-TiO
2Preburning powdered material mixes with the PZT powder, wet grinding;
E, granulation, binding agent is: 200ml deionized water-2gPVA-1ml glycerine-30ml ethanol, 200～250MPa pressure compressing tablet;
F, green sheet were 900～1050 ℃ of insulations 2～10 hours.
Owing to adopted such scheme, the present invention to have following characteristics:
(1) has the ferroelectric piezoelectric ceramics of sintering temperature and low characteristic, have " firmly " property piezoelectric property;
(2) the forming and sintering temperature of PZT ferroelectric piezoelectric ceramics can be lower than 950 ℃, can burn altogether with electrodes in base metal materials such as Ag, Ag-Pd alloys, is applicable to low temperature co-fired multilayer piezoelectric ceramic device;
(3) adopt the pressureless lower temperature sintering auxiliary agent of this low-temperature sintering characteristic ferroelectric ceramic(s) oxide raw material powder, PZT forming process of ceramics sintering temperature can be reduced to be lower than 1050 ℃ as commercial PZT piezoelectric ceramics powder;
(4) adopt traditional electronic ceramic technology, technology is simple, greatly reduced Pb volatilization, improve the quality of products, reduce environmental pollution, improve Working environment, significantly reduce PZT piezoelectric ceramics industrial energy consumption and cost;
(6) the present invention has special meaning to devices such as exploitation high-performance multilayer piezoelectric ceramic actuator, transformer, transverters.
Description of drawings
Fig. 1 is (1-x) of the present invention Pb (Zr
0.52Ti
0.48) O
3-xBi (Zn
1/2Ti
1/2) O
3The ferroelectric piezoelectric ceramics sheet shrinking percentage of different components, different sintering temperature and soaking time.
Fig. 2 is the X-ray diffraction spectrum of 5 hours sintered piezoelectric ceramics sheets of 1000 ℃ of insulations.
Fig. 3 is the X-ray diffraction spectrum of x=0.15 differing temps, different time sintered piezoelectric ceramics sheet.
Fig. 4 is x=0.10,5 hours sintered piezoelectric ceramics sheet dielectric propertiess of 0.15 and 0.20,1000 ℃ of insulation.
Fig. 5 is the room temperature P-E ferroelectric hysteresis loop of x=0.10,5 hours sintered piezoelectric ceramics sheets of 0.15 and 0.20,1000 ℃ of insulation.
Fig. 6 is the room temperature electric field induced strain loop line of x=0.10,5 hours sintered piezoelectric ceramics sheets of 0.15 and 0.20,1000 ℃ of insulation.The sample processing that do not polarize.
Embodiment
The present invention is further illustrated below in conjunction with the accompanying drawing illustrated embodiment.
1, (1-x) Pb (Zr
0.52Ti
0.48) O
3-xBi (Zn
1/2Ti
1/2) O
3Ferroelectric piezoelectric ceramics preparation: with Bi
2O
3, PbO, ZnO, ZrO
2And TiO
2Oxide powder is pressed the stoicheiometry weighing, adds dehydrated alcohol and grinds 2 hours at agate mortar, 800 ℃ of pre-burnings 5 hours; Add dehydrated alcohol and ground 2 hours granulation at agate mortar; The simple stress moulding, forming pressure 250MPa, green compact diameter 10mm; Green sheet is at 40 minutes-10 hours sintering of 900 ℃-1100 ℃ insulations.Sintered ceramic sheet shrinking percentage is seen Fig. 1, to the x=0.10-0.25 sample, at 950 ℃ of sintering shrinkages greater than 10%.X-ray diffraction measurement of x=0.10-0.20 sample is single-phase perovskite structure, and test result is seen Fig. 2 and Fig. 3.
To the sample of x=0.10,0.15 and 0.20 three component,, carried out dielectric properties, ferroelectric properties and electric field induced strain performance test behind silver, the silver ink firing with the ceramic plate polishing both surfaces that makes.Fig. 4-6 is given in high-temperature dielectric character, room temperature ferroelectric hysteresis loop and the electric field induced strain loop line of 5 hours sintered piezoelectric ceramics sheets of 1000 ℃ of insulations respectively.With Pb (Zr
0.52Ti
0.48) O
3Compare, along with x increases, Curie temperature T
CReduce, and phase change characteristics changes the second-order phase transition of x=0.15 and 0.20 into from the first-order phase transition of x=0.10.For the x=0.10 sample, 1kHz frequency room temperature relative permittivity ε
r=1152, dissipation factor tan δ=2.3%, residual polarization P
r=17.0 μ C/cm
2, the strong E of coercive field
c=1.9kV/mm; During x=0.15, ε
r=1399, tan δ=3.1%, P
r=33.2 μ C/cm
2, E
c=2.4kV/mm; During x=0.20, ε
r=1390, tan δ=4.1%, P
r=30.0 μ C/cm
2, E
c=3.1kV/mm.(1-x) Pb (Zr
0.52Ti
0.48) O
3-xBi (Zn
1/2Ti
1/2) O
3Ferroelectric ceramic(s) belongs to " rigid " piezoelectric ceramics.
2,0.85Pb (Zr
0.52Ti
0.48) O
3-0.15Bi (Zn
1/2Ti
1/2) O
3+ 0.5wt%MnO
2Ferroelectric piezoelectric ceramics preparation: with MnO
2, Bi
2O
3, PbO, ZnO, ZrO
2And TiO
2Oxide powder is pressed the stoicheiometry weighing, adds dehydrated alcohol and grinds 2 hours at agate mortar, 800 ℃ of pre-burnings 5 hours; Add dehydrated alcohol and ground 2 hours granulation at agate mortar; The simple stress moulding, forming pressure 250MPa, green compact diameter 10mm.Green sheet is at 5 hours sintering of 950 ℃ of insulations, and the ceramic plate shrinking percentage is 1 hour shrinking percentage 10.5% of 9.3%, 1000 ℃ of sintering, 10.0%, 1050 ℃ of sintering of 5 hours shrinking percentages.
3, (1-x) (0.6PbTiO
3-0.3Bi (Zn
1/2Ti
1/2) O
3-0.1BiFeO
3)-xPbZrO
3Ferroelectric piezoelectric ceramics preparation: with Bi
2O
3, PbO, ZnO, Fe
2O
3, ZrO
2And TiO
2Oxide powder is pressed the stoicheiometry weighing, adds dehydrated alcohol and grinds 2 hours at agate mortar, 800 ℃ of pre-burnings 5 hours; Add dehydrated alcohol and ground 2 hours granulation at agate mortar; The simple stress moulding, forming pressure 250MPa, green compact diameter 10mm; Green sheet is at 1-5 hour sintering of 950 ℃-1050 ℃ insulations.950 ℃ of insulations 5 hours, experiment recorded shrinking percentage and is respectively 11.09% (x=0.0); 9.50% (x=0.2); 8.81% (x=0.3); 10.50% (x=0.4).In 5 hours four component shrinking percentages of 1000 ℃ of sintering all greater than 11.2%.
4, PZT piezoelectric ceramics forming and sintering: the Pb of 800 ℃ of pre-burnings of employing
0.95Sr
0.05Zr
0.53Ti
0.48O
3+ 0.3wt%MnO
2(1-x) Pb (Zr of ceramic powder and embodiment 1 pre-burning
0.52Ti
0.48) O
3-xBi (Zn
1/2Ti
1/2) O
3(x=0.25,0.30) powder is sintering and modified additive, and sintering aid is by 3%, 6%, 9% weight proportion weighing; Add dehydrated alcohol and ground 2 hours granulation at agate mortar; The simple stress moulding, forming pressure 250MPa, green compact diameter 23mm; Green sheet was 1050 ℃ of insulations 10 hours, and experiment measuring sintered ceramic sheet shrinking percentage is respectively 6.0%, 8.8% and 9.5%.
Above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention for improvement and modification that the present invention makes according to announcement of the present invention.
Claims (9)
1, a kind of ferroelectric piezoelectric ceramics with sintering temperature and low characteristic is characterized in that: its component is (1-x-y) PbZrO
3-xPbTiO
3-yBi (Zn
1/2Ti
1/2) O
3+ zwt%MnO
2: x=0.30～0.50, y=0.05～0.25, z=0.0～0.5.
2, the ferroelectric piezoelectric ceramics with sintering temperature and low characteristic according to claim 1 is characterized in that: PbZrO
3-PbTiO
3-Bi (Zn
1/2Ti
1/2) o
3Ferroelectric piezoelectric ceramics is single-phase perovskite structure.
3, a kind of method for preparing the ceramic of compact sheet is characterized in that: use (1-x-y) PbZrO
3-xPbTiO
3-yBi (Zn
1/2Ti
1/2) O
3+ zwt%MnO
2: x=0.30～0.50, y=0.05～0.25, the material component of z=0.0～0.5 comprises:
A, Bi
2O
3-PbO-ZnO-ZrO
2-TiO
2The powder wet-mixed;
B, 800 ℃ of pre-burnings 5 hours;
C, preburning powdered material wet grinding;
D, granulation, 200～250MPa pressure compressing tablet;
E, green sheet were 950～1050 ℃ of insulations 2～10 hours.
4, piezoelectric ceramic actuator, the piezoelectric transformer that uses the described piezoelectric ceramics of claim 1 to make.
5, use multilayer driving mechanism, transformer and the transverter of the low temperature co-fired making of electrode in described piezoelectric ceramics of claim 1 and the Ag-Pd.
6, a kind of pressureless lower temperature sintering method is characterized in that: adopting the ferroelectric ceramic(s) preburning powdered material that obtains behind claim 3 step c is the low-temperature sintering auxiliary agent of the doped PZT piezoelectric ceramics powder of commercial applications.
7, method according to claim 6 is characterized in that: this ferroelectric piezoelectric ceramics is as pressureless lower temperature sintering PbZr
1-xTi
xO
3The sintering aid of commercial applications piezoelectric ceramics, x=0.02～1.0 wherein, this ferroelectric ceramic(s) is 5.0～10.0wt% as the addition of sintering aid.
8, the piezoelectric ceramics of the described method making of use claim 6 and piezoelectric ceramic actuator, piezoelectric transformer.
9, use the piezoelectric ceramics of the described method making of claim 6 and multilayer driving mechanism, transformer and the transverter of the interior low temperature co-fired making of electrode of Ag-Pd.
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| CN101857432A (en) * | 2010-06-11 | 2010-10-13 | 天津大学 | Magnesium titanate bismuth-lead titanate piezoelectric ceramics suitable for high-temperature field |
| CN102030529A (en) * | 2010-11-17 | 2011-04-27 | 合肥工业大学 | Bismuth-containing complex perovskite-lead zirconate titanate quasi-ternary system piezoelectric ceramic and preparation method thereof |
| CN102060528A (en) * | 2010-11-29 | 2011-05-18 | 法库县矿产资源研究发展中心 | High Curie point and low lead piezoelectric ceramic material and preparation method thereof |
| CN102320831A (en) * | 2011-05-27 | 2012-01-18 | 合肥工业大学 | Zinc-bismuth based perovskite-lead titanate-lead based relaxor ferroelectric ternary system piezoceramics and preparation method thereof |
| CN102320828A (en) * | 2011-06-16 | 2012-01-18 | 桂林电子科技大学 | Unleaded piezoelectric ceramic consisting of B-site composite Bi-based compound and preparation method thereof |
| CN102351529A (en) * | 2011-06-09 | 2012-02-15 | 西北工业大学 | Non-ferroelectric and ferroelectric composite titanate temperature stable high dielectric ceramic |
| CN102515756A (en) * | 2012-01-31 | 2012-06-27 | 佛山市亿强电子有限公司 | Low-temperature sintering and preparing method of high-performance PZT (lead zirconate titanate)-based piezoelectric ceramic discharge plasma |
| CN103159475A (en) * | 2011-06-16 | 2013-06-19 | 桂林电子科技大学 | Leadless piezoelectric ceramic composed of B-bit composite Bi-based compound and preparation method thereof |
| CN104129992A (en) * | 2014-07-17 | 2014-11-05 | 宁波凯普电子有限公司 | Modified PZT piezoelectric ceramic material and preparation method thereof |
| CN104291817A (en) * | 2013-07-17 | 2015-01-21 | 淄博宇海电子陶瓷有限公司 | High-Curie-temperature PZT piezoceramic material and preparation method thereof |
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| CN101857432A (en) * | 2010-06-11 | 2010-10-13 | 天津大学 | Magnesium titanate bismuth-lead titanate piezoelectric ceramics suitable for high-temperature field |
| CN102030529A (en) * | 2010-11-17 | 2011-04-27 | 合肥工业大学 | Bismuth-containing complex perovskite-lead zirconate titanate quasi-ternary system piezoelectric ceramic and preparation method thereof |
| CN102030529B (en) * | 2010-11-17 | 2013-06-12 | 合肥工业大学 | Bismuth-containing complex perovskite-lead zirconate titanate quasi-ternary system piezoelectric ceramic and preparation method thereof |
| CN102060528B (en) * | 2010-11-29 | 2013-02-27 | 辽宁省轻工科学研究院 | High Curie point and low lead piezoelectric ceramic material and preparation method thereof |
| CN102060528A (en) * | 2010-11-29 | 2011-05-18 | 法库县矿产资源研究发展中心 | High Curie point and low lead piezoelectric ceramic material and preparation method thereof |
| CN102320831A (en) * | 2011-05-27 | 2012-01-18 | 合肥工业大学 | Zinc-bismuth based perovskite-lead titanate-lead based relaxor ferroelectric ternary system piezoceramics and preparation method thereof |
| CN102320831B (en) * | 2011-05-27 | 2013-09-18 | 合肥工业大学 | Zinc-bismuth based perovskite-lead titanate-lead based relaxor ferroelectric ternary system piezoceramics and preparation method thereof |
| CN102351529A (en) * | 2011-06-09 | 2012-02-15 | 西北工业大学 | Non-ferroelectric and ferroelectric composite titanate temperature stable high dielectric ceramic |
| CN103159475A (en) * | 2011-06-16 | 2013-06-19 | 桂林电子科技大学 | Leadless piezoelectric ceramic composed of B-bit composite Bi-based compound and preparation method thereof |
| CN102320828A (en) * | 2011-06-16 | 2012-01-18 | 桂林电子科技大学 | Unleaded piezoelectric ceramic consisting of B-site composite Bi-based compound and preparation method thereof |
| CN103159475B (en) * | 2011-06-16 | 2014-09-10 | 桂林电子科技大学 | Leadless piezoelectric ceramic composed of B-bit composite Bi-based compound and preparation method thereof |
| CN102515756A (en) * | 2012-01-31 | 2012-06-27 | 佛山市亿强电子有限公司 | Low-temperature sintering and preparing method of high-performance PZT (lead zirconate titanate)-based piezoelectric ceramic discharge plasma |
| CN102515756B (en) * | 2012-01-31 | 2014-04-16 | 佛山市亿强电子有限公司 | Low-temperature sintering and preparing method of high-performance PZT (lead zirconate titanate)-based piezoelectric ceramic discharge plasma |
| CN104291817A (en) * | 2013-07-17 | 2015-01-21 | 淄博宇海电子陶瓷有限公司 | High-Curie-temperature PZT piezoceramic material and preparation method thereof |
| CN104291817B (en) * | 2013-07-17 | 2016-03-23 | 淄博宇海电子陶瓷有限公司 | PZT piezoceramic material of high-curie temperature and preparation method thereof |
| CN104129992A (en) * | 2014-07-17 | 2014-11-05 | 宁波凯普电子有限公司 | Modified PZT piezoelectric ceramic material and preparation method thereof |
| CN104129992B (en) * | 2014-07-17 | 2016-01-13 | 宁波凯普电子有限公司 | modified PZT piezoelectric ceramic material and preparation method thereof |
| CN109650888A (en) * | 2018-12-27 | 2019-04-19 | 哈尔滨工业大学 | A kind of high electric property ternary system lead titanate relaxor ferroelectric orientation ceramic of low temperature texture and its preparation method and application |
| CN112062551A (en) * | 2020-08-06 | 2020-12-11 | 同济大学 | Bismuth ferrite-based piezoelectric ceramic material with high depolarization temperature and high piezoelectric performance and preparation method thereof |
| CN113582689A (en) * | 2021-08-27 | 2021-11-02 | 成都汇通西电电子有限公司 | Low-temperature co-fired piezoelectric ceramic material for laminated actuator and preparation method thereof |
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