CN103360069A - Lead zirconate titanate B-site niobium-antimony composite substitution modified piezoelectric ceramic and preparation method thereof - Google Patents
Lead zirconate titanate B-site niobium-antimony composite substitution modified piezoelectric ceramic and preparation method thereof Download PDFInfo
- Publication number
- CN103360069A CN103360069A CN2013103016488A CN201310301648A CN103360069A CN 103360069 A CN103360069 A CN 103360069A CN 2013103016488 A CN2013103016488 A CN 2013103016488A CN 201310301648 A CN201310301648 A CN 201310301648A CN 103360069 A CN103360069 A CN 103360069A
- Authority
- CN
- China
- Prior art keywords
- piezoelectric ceramics
- piezoelectric
- base substrate
- piezoelectric ceramic
- ball
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 74
- CYVNAGQFZFNZEZ-UHFFFAOYSA-N [Nb].[Sb] Chemical compound [Nb].[Sb] CYVNAGQFZFNZEZ-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000002131 composite material Substances 0.000 title abstract 5
- 238000006467 substitution reaction Methods 0.000 title abstract 4
- 229910052451 lead zirconate titanate Inorganic materials 0.000 title abstract 3
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 title abstract 2
- 238000012986 modification Methods 0.000 claims abstract description 21
- 230000004048 modification Effects 0.000 claims abstract description 21
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052709 silver Inorganic materials 0.000 claims abstract description 19
- 239000004332 silver Substances 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 230000010287 polarization Effects 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000010955 niobium Substances 0.000 claims description 37
- 239000000758 substrate Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 22
- 238000010792 warming Methods 0.000 claims description 17
- 150000001875 compounds Chemical group 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 13
- 238000000498 ball milling Methods 0.000 claims description 9
- 238000010304 firing Methods 0.000 claims description 9
- 238000009413 insulation Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 230000005684 electric field Effects 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 238000004080 punching Methods 0.000 claims description 3
- 238000007650 screen-printing Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 229920002994 synthetic fiber Polymers 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 229910010293 ceramic material Inorganic materials 0.000 abstract 1
- 238000009740 moulding (composite fabrication) Methods 0.000 abstract 1
- 230000008878 coupling Effects 0.000 description 13
- 238000010168 coupling process Methods 0.000 description 13
- 238000005859 coupling reaction Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 230000008859 change Effects 0.000 description 8
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000004891 communication Methods 0.000 description 3
- 238000007766 curtain coating Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses lead zirconate titanate B-site niobium-antimony composite substitution modified piezoelectric ceramic and a preparation method thereof. The invention belongs to the field of piezoelectric ceramic materials. A niobium-antimony composite substituent of the ceramic is (Sb1/2Nb1/2). The piezoelectric ceramic comprises the components of, by stoichiometric ratio: Pb0.9Sr0.1(Sb1/2Nb1/2)x(Zr0.47Ti0.53)1-xO3, wherein x is larger than 0 and no larger than 0.06. The piezoelectric ceramic is prepared through the steps of blending, synthesis, forming, plastic removing, sintering, silver burning, polarization, and the like. According to the invention, pure PZT piezoelectric ceramic is subjected to B-site composite substitution modification by using (Sb1/2Nb1/2), such that niobium-antimony composite substitution modified piezoelectric ceramic is obtained. Piezoelectricity is substantially improved, such that high requirements of electronic devices such as ultrasonic sensors, piezoelectric broadband filters, piezoelectric surface-mount buzzer and piezoelectric actuators on piezoelectric ceramic piezoelectricity can be satisfied.
Description
Technical field
The present invention relates to a kind of piezoceramic material and preparation method thereof, particularly piezoelectric ceramics of the compound substituting modification of a kind of Pb-based lanthanumdoped zirconate titanates B position niobium antimony and preparation method thereof.
Background technology
Piezoelectric ceramics is made by high temperature sintering, has a kind of emerging stupalith of the electromechanical coupling performance of high-k, piezoelectricity and excellence.Wherein the most representative is Pb-based lanthanumdoped zirconate titanates (PZT) piezoelectric ceramics.The PZT piezoelectric ceramics is owing to its piezoelectric property and the multiple dielectric properties that caused by piezoelectricity, all is widely used in fields such as aerospace, electronics, computer, laser, the ultrasonic and energy.
Continuous development along with every profession and trade, piezoelectric property to the PZT piezoelectric ceramics requires also to improve constantly, therefore, pure PZT piezoelectric ceramics is carried out the PZT piezoceramic material that modification obtains modification, to improve its piezoelectric property, can satisfy the demand of the piezoelectric property that day by day improves, become the inexorable trend of PZT piezoelectric ceramics development.
Summary of the invention
In order to improve the piezoelectric property of pure PZT binary system piezoelectric ceramics, the embodiment of the invention provides piezoelectric ceramics of the compound substituting modification of a kind of Pb-based lanthanumdoped zirconate titanates B position niobium antimony and preparation method thereof.Described technical scheme is as follows:
On the one hand, the invention provides the piezoelectric ceramics of the compound substituting modification of a kind of Pb-based lanthanumdoped zirconate titanates B position niobium antimony, the compound substituent of niobium antimony wherein is: (Sb
1/2Nb
1/2), the composition of the piezoelectric ceramics of described modification and stoichiometric ratio thereof are: Pb
0.9Sr
0.1(Sb
1/2Nb
1/2) x(Zr
0.47Ti
0.53)
1-xO
3, 0＜X≤0.06 wherein.
Preferably, the composition of described piezoelectric ceramics and stoichiometric ratio thereof are: Pb
0.9Sr
0.1(Sb
1/2Nb
1/2) x(Zr
0.47Ti
0.53)
1-xO
3, X=0.04～0.055 wherein.
More preferably, the composition of described piezoelectric ceramics and stoichiometric ratio thereof are: Pb
0.9Sr
0.1(Sb
1/2Nb
1/2) x(Zr
0.47Ti
0.53)
1-xO
3, X=0.05 wherein.
On the other hand, the invention provides the method for the piezoelectric ceramics of the compound substituting modification of preparation described Pb-based lanthanumdoped zirconate titanates B position niobium antimony, described method operates in accordance with the following steps:
1) batching: at first calculate according to the composition of described piezoelectric ceramics and stoichiometric ratio thereof and take by weighing raw material, then described raw material is mixed the powder that obtains mixing in ball grinder;
2) synthetic: as after the powder oven dry of the mixing that step 1) is obtained, in alumina crucible, under the air-proof condition, 900 ℃～980 ℃ building-up reactions 2.5h, to obtain Pb
0.9Sr
0.1(Sb
1/2Nb
1/2) x(Zr
0.47Ti
0.53)
1-xO
3Powder;
3) moulding and plastic removal: at first with step 2) Pb that obtains
0.9Sr
0.1(Sb
1/2Nb
1/2) x(Zr
0.47Ti
0.53)
1-xO
3Casting film-forming, punching become base substrate after powder ball milling, the oven dry, then described base substrate are warming up to 400 ℃ through two sections, behind the insulation 30min, with the speed of 5 ℃/min described base substrate are warming up to 650 ℃ of insulation 15min, in order to discharge organism;
4) sintering: the base substrate behind the discharge organism that step 3) is obtained is with step 2) Pb that obtains
0.9Sr
0.1(Sb
1/2Nb
1/2) x(Zr
0.47Ti
0.53)
1-xO
3Powder buries burning: be warming up to 1250 ℃ with 5 ℃/min speed, be incubated 2 hours, furnace cooling obtains the base substrate of sintering;
5) coating silver electrode, silver ink firing: by silver, place again process furnace after the ultrasonic washing oven dry of the base substrate of the sintering that step 4) is obtained, naturally cool to room temperature after being warming up to 800 ℃ of insulation 10min, obtain the silver ink firing goods;
6) polarization: the silver ink firing goods with step 5) obtains, in 100 ℃ air, apply the DC electric field of 1500V/mm, polarization 10min obtains piezoelectric ceramics.
Particularly, the described raw material of step 1) comprises: Pb
3O
4, SrCO
3, ZrO
2, TiO
2, Sb
2O
5, and Nb
2O
5The condition that the described raw material of step 1) mixes in ball grinder is: ball-milling medium is deionized water and ZrO
2Ball, raw material, ZrO
2The weight ratio of ball, deionized water is 1:2.5:1, and the rotating speed of ball grinder is 750r/min, and Ball-milling Time is 2.5h.
Preferably, step 2) temperature of described building-up reactions is 950 ℃.
Particularly, step 2) described oven dry is for to dry in 60～100 ℃ of loft drier.
Particularly, the diameter of the described base substrate of step 3) is 17.20mm, and thickness is 12.5 ± 0.5um.
Particularly, the described two sections intensifications of step 3) are: the speed with 3 ℃/min is warming up to 200 ℃ with base substrate first, with 2 ℃/min speed base substrate is warming up to 400 ℃ from 200 ℃ again.
Particularly, the described of step 5) adopted silk-screen printing technique by silver.
The beneficial effect that the technical scheme that the embodiment of the invention provides is brought is:
The present invention is by adopting (Sb
1/2Nb
1/2) pure PZT piezoelectric ceramics is carried out the compound substituting modification in B position, obtain the piezoelectric ceramics of the compound substituting modification of niobium antimony.As (Sb
1/2Nb
1/2) replacement amount X=0.05, when synthesis reaction temperature was 950 ℃, the comprehensive piezoelectric property of the piezoelectric ceramics of the modification of acquisition was best, wherein, DIELECTRIC CONSTANT ε
T 33/ ε
0, piezoelectric coefficient d
33, electromechanical coupling factor K
pValue and loss value tan δ are respectively 1900,360pC/N, 73%, 2.3%, with respect to pure PZT piezoelectric ceramics, its above-mentioned piezoelectric property all is significantly improved, and can be used in the electron devices such as ultrasonic transducer, piezoelectricity wide band filter, piezoelectricity Surface Mount hummer and piezoelectric ceramic actuator, can satisfy above-mentioned electron device to the high requirement of the piezoelectric property of piezoelectric ceramics.
Description of drawings
In order to be illustrated more clearly in the technical scheme in the embodiment of the invention, the accompanying drawing of required use was done simple the introduction during the below will describe embodiment, obviously, accompanying drawing in the following describes only is some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the DIELECTRIC CONSTANT ε of the piezoelectric ceramics that provides of the embodiment of the invention
T 33/ ε
0The change curve that replacement amount X is done;
Fig. 2 is the piezoelectric coefficient d of the piezoelectric ceramics that provides of the embodiment of the invention
33The change curve that replacement amount X is done;
Fig. 3 is the electromechanical coupling factor K of the piezoelectric ceramics that provides of the embodiment of the invention
pThe change curve that replacement amount X is done;
Fig. 4 is the change curve that the dielectric loss tan δ of the piezoelectric ceramics that provides of the embodiment of the invention does replacement amount X.
The implication of each symbol is as follows among the figure:
1 change curve when being 900 ℃, 2 change curves when being 950 ℃, 3 change curves when being 980 ℃.
Embodiment
For making the purpose, technical solutions and advantages of the present invention clearer, embodiment of the present invention is described further in detail below in conjunction with accompanying drawing.
Piezoelectric ceramics is mainly used in following field at present:
1. piezoelectric high voltage generator: piezoelectric high voltage generator is the high pressure generating device that utilizes the data-collection characteristic of piezoceramic material to make.Wherein piezoelectric ceramic ignitor and piezoelectric ceramic transformer are two kinds commonly used in the piezoelectric high voltage generator.
2. piezoelectric ceramic transducer: PZT (piezoelectric transducer) is to utilize the piezoelectric effect of piezoelectrics, a kind of energy of form is changed into the device of another kind of form energy.Mainly comprise the application of two aspects: electroacoustic equipment and underwater sound.
3. the application on the metrology and measurement instrument: need to become electrical quantities to the non-electrical quantities information that detects in all respects such as science and industrial and agricultural productions, so that amplification, computing, transmission record and demonstration, the main devices that can finish this conversion is as main electronic sensor take solid component.The measurement made from piezoelectric ceramics and the sensor of the various physical quantitys of perception and variation thereof then are best selections, and piezoelectric transducer has also become the key part of various detecting instruments and Controlling System.Mainly contain that piezolectric gyroscope, piezoelectric accelerometer, piezoelectric ceramics under meter, piezoelectron claim, piezoelectricity counter, frost sensor, surfagauge, pendulum clock comprehensive tester and Grinding Contact detector etc.
4. piezoelectric filter: piezoelectric filter is the large field that the piezoelectricity ferro material is used.It is to utilize piezoelectric resonator or piezoelectric resonator and LRC circuit to make up a kind of device of realizing that frequency is selected.Piezoelectric filter is compared with the LC wave filter, and number of elements reduces, reliability increases, temperature stability is good, quality factor are high.At present, the adaptation frequency band of piezoelectric filter is from 1kHz～200MHz, relative bandwidth from 100,000/several to 20%.Piezoelectric filter is usually used in the filtering in channel bandpass filter, satellite communications and other range radio communications and the surveying instrument in the multiplex communication.
The present invention adopts (Sb
1/2Nb
1/2) pure PZT piezoelectric ceramics is carried out the compound substituting modification in B position, obtain the piezoelectric ceramics of the compound substituting modification of niobium antimony.Wherein, niobium (Nb
5+), antimony (Sb
5+) metal ion enters after the sosoloid, according to the size of ionic radius, may occupy Pb
2+The position, also may occupy Zr
4+Or Ti
4+The position, thereby in lattice, produce cationvacancy (mainly being plumbous room).And after plumbous room occurring in the structure cell, lattice produces distortion, thereby is conducive to domain wall motion, just can carry out domain wall motion under less electric field or mechanical force stress, thereby improve the comprehensive piezoelectric property of material.
The embodiment of the invention also provides the preparation method of the piezoelectric ceramics of the compound substituting modification of a kind of Pb-based lanthanumdoped zirconate titanates B position niobium antimony, and described method operates in accordance with the following steps:
Step 3: moulding and plastic removal: the part Pb that step 2 is obtained
0.9Sr
0.1(Sb
1/2Nb
1/2) x(Zr
0.47Ti
0.53)
1-xO
3Then powder dries in 60～100 ℃ of loft drier according to the condition ball milling of step 1; According to Pb
0.9Sr
0.1(Sb
1/2Nb
1/2) x(Zr
0.47Ti
0.53)
1-xO
3Powder: the curtain coating aqua is the part by weight of 100:3, to the oven dry after Pb
0.9Sr
0.1(Sb
1/2Nb
1/2) x(Zr
0.47Ti
0.53)
1-xO
3Add the curtain coating aqua in the powder, after stirring in automatic casting machine curtain coating to become thickness be the diaphragm of 1-100um; Then the punching diameter is 17.20mm, and thickness is the base substrate of 12.5 ± 0.5um; Speed with 3 ℃/min is warming up to 200 ℃ with base substrate again, and 2 ℃/min speed is warming up to 400 ℃ with base substrate from 200 ℃, at 400 ℃ of insulation 30min, then with the speed of 5 ℃/min base substrate is warming up to 650 ℃ and be incubated 15min, in order to discharge organism.
Step 4, sintering: the part Pb that the base substrate behind the discharge organism that step 3 is obtained obtains with step 2 in encloses container
0.9Sr
0.1(Sb
1/2Nb
1/2) x(Zr
0.47Ti
0.53)
1-xO
3Powder buries burning, causes the variation of component in the product with the volatilization of avoiding Pb in the blank sintering process.Sintering condition is: described base substrate is warming up to 1250 ℃ with 5 ℃/min speed, is incubated 2 hours, and furnace cooling obtains the base substrate of sintering.
Step 5, coating silver electrode, silver ink firing: the base substrate of the sintering that step 4 is obtained at normal temperatures, ultrasonic washing 30min under the frequency of 20-100khz, then in 60～100 ℃ of loft drier, adopt silk-screen printing technique by silver after the oven dry, place again process furnace, naturally cool to room temperature after being warming up to 800 ℃ of insulation 10min, obtain the silver ink firing goods.
Step 6, polarization: the silver ink firing goods with step 5 obtains, in the polarization case, in 100 ℃ the air, apply the DC electric field of 1500V/mm, polarization 10min obtains piezoelectric ceramics.
The piezoelectric ceramics that the specific embodiment of the invention and Comparative Examples provide prepares according to the method described above, and that different is (Sb
1/2Nb
1/2) replacement amount and synthesis reaction temperature, design parameter is referring to table 1.
(Sb in table 1 embodiment and the Comparative Examples
1/2Nb
1/2) replacement amount and synthesis reaction temperature
| （Sb 1/2Nb 1/2) replacement amount X | Synthesis reaction temperature ℃ | |
| Embodiment 1-1 | 0.03 | 900 |
| Embodiment 1-2 | 0.05 | 900 |
| Embodiment 1-3 | 0.06 | 900 |
| Comparative Examples 1 | 0 | 900 |
| Embodiment 2-1 | 0.03 | 950 |
| Embodiment 2-2 | 0.05 | 950 |
| Embodiment 2-3 | 0.06 | 950 |
| Comparative Examples 2 | 0 | 950 |
| Embodiment 3-1 | 0.03 | 980 |
| Embodiment 3-2 | 0.05 | 980 |
| Embodiment 3-3 | 0.06 | 980 |
| Comparative Examples 3 | 0 | 980 |
In the embodiment of the invention and the Comparative Examples, used raw material is the commercially available prod, wherein Pb
3O
4, SrCO
3, ZrO
2, TiO
2, Sb
2O
5, and Nb
2O
5Be chemical pure.
The piezoelectric ceramics that the embodiment of the invention and Comparative Examples provide after placing 24 hours under the room temperature, is tested its piezoelectric property parameters loss value tan δ, DIELECTRIC CONSTANT ε
T 33/ ε
0, piezoelectric coefficient d
33With electromechanical coupling factor K
P, concrete testing method is as follows:
Loss value tan δ and DIELECTRIC CONSTANT ε
T 33/ ε
0Testing method: the 4225 type LCR automatic measuring instruments that can use wireless six factories in Tianjin City, China to produce, at room temperature measure the loss value tan δ of piezoelectric ceramics sample, test frequency is 1Kz; Under above-mentioned identical condition, testing capacitor calculates DIELECTRIC CONSTANT ε by following formula
T 33/ ε
0:
In the formula,
C-electric capacity, F,
The thickness of t-piezoelectric ceramics sample, cm,
The circular silver electrode diameter of Φ-piezoelectric ceramics sample, cm,
ε
0-permittivity of vacuum, F/m.
Piezoelectric coefficient d
33Testing method: can be according to the method for GB GB11309-89 regulation, the ZJ-3A type quasi static test instrument that adopts Chinese Academy of Sciences's acoustics to provide, test piezoelectric coefficient d
33, its unit is pC/N.
Electromechanical coupling factor K
PTesting method: can be by the difference Δ f=f of resonance and anti-resonance frequency
a-f
rComprehensively table look-up with Poisson ratioσ and to obtain electromechanical coupling factor K
PWherein Poisson ratioσ can calculate by following formula:
In the formula:
f
r--resonant frequency,
f
a--anti-resonance frequency,
f
R1--the first overtone resonant frequency,
f
r, f
a, f
R1All can adopt resonance-antiresonance method, XFG-7 high frequency signal generator of utilizing Shanghai Ya Mei electrical apparatus factory to provide records.
To the piezoelectric ceramics that the embodiment of the invention and Comparative Examples provide, adopt aforesaid method to test its piezoelectric property, its loss value tan δ, DIELECTRIC CONSTANT ε
T 33/ ε
0, piezoelectric coefficient d
33With electromechanical coupling factor K
PValue specifically is shown in Table 2.
The piezoelectric property test result of the piezoelectric ceramics of table 2 embodiment and Comparative Examples
| ε T 33/ε 0 | d 33（pC/N） | K P（%） | tanδ（%） | |
| Embodiment 1-1 | 1750 | 332 | 65 | 2.5 |
| Embodiment 1-2 | 1920 | 352 | 70 | 2.3 |
| Embodiment 1-3 | 1850 | 335 | 64 | 2.4 |
| Comparative Examples 1 | 1580 | 320 | 60 | 2.9 |
| Embodiment 2-1 | 1820 | 348 | 68 | 2.3 |
| Embodiment 2-2 | 1920 | 360 | 73 | 2.3 |
| Embodiment 2-3 | 1880 | 352 | 68 | 2.6 |
| Comparative Examples 2 | 1760 | 335 | 63 | 2.6 |
| Embodiment 3-1 | 1780 | 348 | 65 | 2.4 |
| Embodiment 3-2 | 1930 | 350 | 70 | 2.3 |
| Embodiment 3-3 | 1600 | 330 | 63 | 2.7 |
| Comparative Examples 3 | 1570 | 342 | 62 | 2.7 |
Draw its piezoelectric property of piezoelectric ceramics of different synthesis temperature preparations to the change curve of replacement amount X with the data in the table 2, see accompanying drawing 1-4 for details.
Fig. 1 is DIELECTRIC CONSTANT ε
T 33/ ε
0Variation diagram, wherein, X-axis is (Sb
1/2Nb
1/2) replacement amount X, Y-axis is DIELECTRIC CONSTANT ε
T 33/ ε
0Value.As can be seen from Figure 1, compare the DIELECTRIC CONSTANT ε of the piezoelectric ceramics of the compound substituting modification of Pb-based lanthanumdoped zirconate titanates B position niobium antimony with pure PZT piezoelectric ceramics
T 33/ ε
0Be improved.Under different synthesis temperatures, along with (Sb
1/2Nb
1/2) increase of replacement amount X, DIELECTRIC CONSTANT ε
T 33/ ε
0Present and increase progressively first the trend of successively decreasing afterwards, when replacement amount X=0.05, DIELECTRIC CONSTANT ε
T 33/ ε
0Reach maximum value, and when synthesis temperature is 950 ℃, DIELECTRIC CONSTANT ε
T 33/ ε
0Reaching maximum value is 1920.
Fig. 2 is piezoelectric coefficient d
33The variation collection of illustrative plates, wherein, X-axis is (Sb
1/2Nb
1/2) replacement amount X, Y-axis is piezoelectric coefficient d
33, unit is pC/N.As can be seen from Figure 2, compare the piezoelectric coefficient d of the piezoelectric ceramics of the compound substituting modification of Pb-based lanthanumdoped zirconate titanates B position niobium antimony with pure PZT piezoelectric ceramics
33Be improved.Under different synthesis temperatures, along with (Sb
1/2Nb
1/2) increase of replacement amount X, piezoelectric coefficient d
33Present and increase progressively first the trend of successively decreasing afterwards, when replacement amount X=0.05, piezoelectric coefficient d
33Reach maximum value, and when synthesis temperature is 950 ℃, piezoelectric coefficient d
33Reaching maximum value is 360pC/N.
Fig. 3 is electromechanical coupling factor K
PThe variation collection of illustrative plates, wherein, X-axis is (Sb
1/2Nb
1/2) replacement amount X, Y-axis is electromechanical coupling factor K
P, be percentage ratio.As can be seen from Figure 3, compare the electromechanical coupling factor K of the piezoelectric ceramics of the compound substituting modification of Pb-based lanthanumdoped zirconate titanates B position niobium antimony with pure PZT piezoelectric ceramics
PBe improved.Under different synthesis temperatures, along with (Sb
1/2Nb
1/2) increase of replacement amount X, electromechanical coupling factor K
PPresent and increase progressively first the trend of successively decreasing afterwards, when replacement amount X=0.05, electromechanical coupling factor K
PReach maximum value, and when synthesis temperature is 950 ℃, electromechanical coupling factor K
PReaching maximum value is 73%.
Fig. 4 is the variation collection of illustrative plates of loss value tan δ, and wherein, X-axis is (Sb
1/2Nb
1/2) replacement amount X, Y-axis is loss value tan δ, is percentage ratio.As can be seen from Figure 4, compare with pure PZT piezoelectric ceramics, the loss value tan δ of the piezoelectric ceramics of the compound substituting modification of Pb-based lanthanumdoped zirconate titanates B position niobium antimony has obtained reduction.Under different synthesis temperatures, along with (Sb
1/2Nb
1/2) increase of replacement amount X, loss value tan δ presents the trend of successively decreasing first and increasing progressively afterwards, and when replacement amount X=0.05, loss value tan δ reaches minimum value, and when synthesis temperature was 950 ℃, it was 2.3% that loss value tan δ reaches minimum value.
Pottery of the present invention can be used for ultrasonic transducer, piezoelectricity wide band filter, piezoelectricity Surface Mount hummer and piezoelectric ceramic actuator etc. to the electron device that the piezoelectric ceramics over-all properties has higher requirements, and can satisfy these electron devices to the high requirement of piezoelectric ceramics over-all properties.
The invention described above embodiment sequence number does not represent the quality of embodiment just to description.
The above only is preferred embodiment of the present invention, and is in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the piezoelectric ceramics of the compound substituting modification of Pb-based lanthanumdoped zirconate titanates B position niobium antimony is characterized in that, the compound substituent of described niobium antimony of described piezoelectric ceramics is: (Sb
1/2Nb
1/2), the composition of described piezoelectric ceramics and stoichiometric ratio thereof are: Pb
0.9Sr
0.1(Sb
1/2Nb
1/2) x(Zr
0.47Ti
0.53)
1-xO
3, 0＜X≤0.06 wherein.
2. piezoelectric ceramics as claimed in claim 1 is characterized in that, the composition of described piezoelectric ceramics and stoichiometric ratio thereof are: Pb
0.9Sr
0.1(Sb
1/2Nb
1/2) x(Zr
0.47Ti
0.53)
1-xO
3, X=0.04～0.055 wherein.
3. piezoelectric ceramics as claimed in claim 2 is characterized in that, the composition of described piezoelectric ceramics and stoichiometric ratio thereof are: Pb
0.9Sr
0.1(Sb
1/2Nb
1/2) x(Zr
0.47Ti
0.53)
1-xO
3, X=0.05 wherein.
4. a method for preparing such as each described piezoelectric ceramics of claim 1-3 is characterized in that, described method operates in accordance with the following steps:
1) batching: at first calculate according to the composition of described piezoelectric ceramics and stoichiometric ratio thereof and take by weighing raw material, then described raw material is mixed the powder that obtains mixing in ball grinder;
2) synthetic: after the powder oven dry of the mixing that step 1) is obtained, in alumina crucible, under the air-proof condition, 900 ℃～980 ℃ building-up reactions 2.5h, the material that obtains synthesizing;
3) moulding and plastic removal: at first with step 2) behind the synthetic material ball milling, oven dry that obtain casting film-forming, punching become base substrate, then described base substrate is warming up to 400 ℃ through two sections, behind the insulation 30min, speed with 5 ℃/min is warming up to 650 ℃ of insulation 15min with described base substrate, in order to discharge organism;
4) sintering: the base substrate PbTiO behind the discharge organism that step 3) is obtained
3-PbZrO
3Powder buries burning: be warming up to 1250 ℃ with 5 ℃/min speed, be incubated 2 hours, furnace cooling obtains the base substrate of sintering;
5) coating silver electrode, silver ink firing: by silver, place again process furnace after the ultrasonic washing oven dry of the base substrate of the sintering that step 4) is obtained, naturally cool to room temperature after being warming up to 800 ℃ of insulation 10min, obtain the silver ink firing goods;
6) polarization: the silver ink firing goods with step 5) obtains, in 100 ℃ air, apply the DC electric field of 1500V/mm, polarization 10min obtains piezoelectric ceramics.
5. method as claimed in claim 4 is characterized in that, the described raw material of step 1) comprises: Pb
3O
4, SrCO
3, ZrO
2, TiO
2, Sb
2O
5, and Nb
2O
5, the condition that this raw material mixes in ball grinder is: ball-milling medium is deionized water and ZrO
2Ball, raw material, ZrO
2The weight ratio of ball, deionized water is 1:2.5:1, and the rotating speed of ball grinder is 750r/min, and Ball-milling Time is 2.5h.
6. method as claimed in claim 5 is characterized in that step 2) temperature of described building-up reactions is 950 ℃.
7. method as claimed in claim 5 is characterized in that step 2) described in oven dry in 60～100 ℃ of loft drier, to dry.
8. method as claimed in claim 5 is characterized in that, the diameter of the described base substrate of step 3) is 17.20mm, and thickness is 12.5 ± 0.5um.
9. method as claimed in claim 5 is characterized in that, the described two sections intensifications of step 3) are: the speed with 3 ℃/min is warming up to 200 ℃ with base substrate first, with 2 ℃/min speed base substrate is warming up to 400 ℃ from 200 ℃ again.
10. method as claimed in claim 5 is characterized in that, step 5) is described to be adopted silk-screen printing technique by silver.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310301648.8A CN103360069B (en) | 2013-07-17 | 2013-07-17 | Lead zirconate titanate B-site niobium-antimony composite substitution modified piezoelectric ceramic and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310301648.8A CN103360069B (en) | 2013-07-17 | 2013-07-17 | Lead zirconate titanate B-site niobium-antimony composite substitution modified piezoelectric ceramic and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103360069A true CN103360069A (en) | 2013-10-23 |
| CN103360069B CN103360069B (en) | 2014-12-17 |
Family
ID=49362430
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310301648.8A Active CN103360069B (en) | 2013-07-17 | 2013-07-17 | Lead zirconate titanate B-site niobium-antimony composite substitution modified piezoelectric ceramic and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103360069B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103787656A (en) * | 2013-12-26 | 2014-05-14 | 常州波速传感器有限公司 | High-sensitivity piezoelectric ceramic piece formula and preparation method thereof |
| CN108104802A (en) * | 2017-12-08 | 2018-06-01 | 重庆举程科技发展有限公司 | A kind of ultrasonic wave transducer |
| CN114075073A (en) * | 2020-08-17 | 2022-02-22 | 中国科学院上海硅酸盐研究所 | PZT-Pb (Sb)1/2Nb1/2) Ternary system piezoelectric ceramic material and preparation method and application thereof |
| CN114591082A (en) * | 2022-04-19 | 2022-06-07 | 东莞理工学院 | PZT-PNN-PSN-PMN piezoelectric ceramic and preparation method thereof |
| CN114619132A (en) * | 2022-04-20 | 2022-06-14 | 无锡市惠丰电子有限公司 | High-thrust driving piece and preparation method thereof |
| CN116589278A (en) * | 2023-04-19 | 2023-08-15 | 哈尔滨工业大学 | Lead tantalate-lead zirconate titanate ceramic with high electromechanical performance and temperature stability, and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073289A (en) * | 2013-01-25 | 2013-05-01 | 瑞声声学科技(深圳)有限公司 | Piezoceramic material, sintering body, piezoceramic device and preparation method of piezoceramic material |
-
2013
- 2013-07-17 CN CN201310301648.8A patent/CN103360069B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073289A (en) * | 2013-01-25 | 2013-05-01 | 瑞声声学科技(深圳)有限公司 | Piezoceramic material, sintering body, piezoceramic device and preparation method of piezoceramic material |
Non-Patent Citations (1)
| Title |
|---|
| 黄新友等: "三方/四方相共存铌锑锆钛酸铅压电陶瓷极化的研究", 《硅酸盐学报》, vol. 29, no. 5, 31 October 2001 (2001-10-31) * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103787656A (en) * | 2013-12-26 | 2014-05-14 | 常州波速传感器有限公司 | High-sensitivity piezoelectric ceramic piece formula and preparation method thereof |
| CN108104802A (en) * | 2017-12-08 | 2018-06-01 | 重庆举程科技发展有限公司 | A kind of ultrasonic wave transducer |
| CN114075073A (en) * | 2020-08-17 | 2022-02-22 | 中国科学院上海硅酸盐研究所 | PZT-Pb (Sb)1/2Nb1/2) Ternary system piezoelectric ceramic material and preparation method and application thereof |
| CN114591082A (en) * | 2022-04-19 | 2022-06-07 | 东莞理工学院 | PZT-PNN-PSN-PMN piezoelectric ceramic and preparation method thereof |
| CN114619132A (en) * | 2022-04-20 | 2022-06-14 | 无锡市惠丰电子有限公司 | High-thrust driving piece and preparation method thereof |
| CN114619132B (en) * | 2022-04-20 | 2024-04-09 | 无锡市惠丰电子有限公司 | High-thrust driving piece and preparation method thereof |
| CN116589278A (en) * | 2023-04-19 | 2023-08-15 | 哈尔滨工业大学 | Lead tantalate-lead zirconate titanate ceramic with high electromechanical performance and temperature stability, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103360069B (en) | 2014-12-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103360069B (en) | Lead zirconate titanate B-site niobium-antimony composite substitution modified piezoelectric ceramic and preparation method thereof | |
| Guo et al. | (Na0. 5K0. 5) NbO3–LiTaO3 lead-free piezoelectric ceramics | |
| Feizpour et al. | Microwave-assisted synthesis and sintering of potassium sodium niobate lead-free piezoelectric ceramics | |
| CN102584229A (en) | Pb-based stibate niobium-Pb-based zirconate titanates piezoelectric ceramic doped with barium carbonate and preparation method thereof | |
| CN101648807A (en) | Calcium barium zirconate titanate base piezoceramics and preparation method thereof | |
| Chang et al. | The effects of sintering temperature on the properties of (Na0. 5K0. 5) NbO3–CaTiO3 based lead-free ceramics | |
| CN102850050A (en) | Low temperature sintering piezoelectric ceramic material and preparation method thereof | |
| Yoon et al. | Phase-formation, microstructure, and piezoelectric/dielectric properties of BiYO3-doped Pb (Zr0. 53Ti0. 47) O3 for piezoelectric energy harvesting devices | |
| CN101941840B (en) | B-site oxide precursor method for preparing lead niobate nickelate-zirconate titanate piezoelectric ceramic | |
| CN101302106A (en) | Potassium-sodium niobate-based leadless piezoelectric material and preparation thereof | |
| CN103360068A (en) | Manganese antimony-doped lead zirconate titanate piezoelectric ceramic | |
| CN105036736B (en) | A kind of bismuth-sodium titanate base lead-free electrostriction ceramics material and preparation method thereof | |
| JP2004300012A (en) | Piezoelectric ceramic composition, its production method, piezoelectric element, and dielectric element | |
| CN101219892A (en) | Solid-phase sintering technique for manufacturing bismuth titanate orientation ceramic | |
| CN102826846A (en) | Preparation method of high-performance aluminum oxide substrate lead niobate nickelate-lead zirconate titanate piezoelectric film | |
| Chang et al. | The effects of sintering temperature on the properties of lead-free (Na0. 5K0. 5) NbO3–SrTiO3 ceramics | |
| CN102584228A (en) | Cerium-oxide-doped niobium-stibium lead-zirconate-titanate piezoelectric ceramic | |
| CN110078508B (en) | Manganese-doped lead indium niobate zincate-lead titanate piezoelectric ceramic, and preparation method and application thereof | |
| CN102358699A (en) | Preparation method of lanthanum doped lead zincate niobate and lead zirconate titanate piezoelectric ceramic with high performance | |
| CN105236964B (en) | A kind of barium, magnesium, piezoelectric ceramics of tungsten substitution A modifications of lead zirconate titanate and preparation method thereof | |
| Weng et al. | Effects of LiNbO3-doping on properties of (Na0. 535K0. 48) NbO3 piezoelectric ceramics with high electromechanical coupling coefficient for application in surface acoustic wave devices | |
| CN102603294A (en) | Method for preparing high-performance lanthanum-doped lead zinc niobate and lead zirconate titanate piezoelectric ceramic under condition with excessive lead | |
| CN104230333A (en) | High-temperature piezoelectric ceramic material and preparation method thereof | |
| CN112919906A (en) | High-performance PZT piezoelectric ceramic based on 3D printing and preparation method thereof | |
| CN113563073A (en) | High-stability lead-free piezoelectric ceramic and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 526060 Guangdong city of Zhaoqing province Donggang Huanggang town Duanzhou District village before the Temple Road South Patentee after: GUANGDONG JC TECHNOLOGICAL INNOVATION ELECTRONICS Co.,Ltd. Address before: 526060 Guangdong city of Zhaoqing province Donggang Huanggang town Duanzhou District village before the Temple Road South Patentee before: Guangdong Jiecheng Kechuang Electronics Co. Address after: 526060 Guangdong city of Zhaoqing province Donggang Huanggang town Duanzhou District village before the Temple Road South Patentee after: Guangdong Jiecheng Kechuang Electronics Co. Address before: 526060 Guangdong city of Zhaoqing province Donggang Huanggang town Duanzhou District village before the Temple Road South Patentee before: JC ELECTRONIC TECHNOLOGY Co.,Ltd. |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Lead zirconate titanate B-site niobium antimony composite substitution modified piezoelectric ceramics and its preparation method Effective date of registration: 20210519 Granted publication date: 20141217 Pledgee: Zhaoqing Rural Commercial Bank Co.,Ltd. Chengxi sub branch Pledgor: GUANGDONG JC TECHNOLOGICAL INNOVATION ELECTRONICS Co.,Ltd. Registration number: Y2021980003778 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20230522 Granted publication date: 20141217 Pledgee: Zhaoqing Rural Commercial Bank Co.,Ltd. Chengxi sub branch Pledgor: GUANGDONG JC TECHNOLOGICAL INNOVATION ELECTRONICS Co.,Ltd. Registration number: Y2021980003778 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Piezoelectric Ceramics Modified by Lead Zirconate Titanate B Site Niobium Antimony Composite Substitution and Its Preparation Method Effective date of registration: 20230524 Granted publication date: 20141217 Pledgee: Zhaoqing Rural Commercial Bank Co.,Ltd. Chengxi sub branch Pledgor: GUANGDONG JC TECHNOLOGICAL INNOVATION ELECTRONICS Co.,Ltd. Registration number: Y2023980041618 |