CN100347123C - High dielectric contant flexible piezoelectric ceramic material and preparation process thereof - Google Patents
High dielectric contant flexible piezoelectric ceramic material and preparation process thereof Download PDFInfo
- Publication number
- CN100347123C CN100347123C CNB2005101124337A CN200510112433A CN100347123C CN 100347123 C CN100347123 C CN 100347123C CN B2005101124337 A CNB2005101124337 A CN B2005101124337A CN 200510112433 A CN200510112433 A CN 200510112433A CN 100347123 C CN100347123 C CN 100347123C
- Authority
- CN
- China
- Prior art keywords
- piezoelectric ceramic
- ceramic material
- high dielectric
- flexible piezoelectric
- hours
- 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.)
- Expired - Fee Related
Links
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
The present invention relates to high dielectric constant flexible piezoelectric ceramic material, and a preparation process thereof. The composition formula of the piezoelectric ceramic material provided by the present invention is Pb<1-y-z>Sr<y>Ba<z>(Mg<1/3>Nb<2/3>)<x>Ti<m>Zr<n>O<3>+ pwt%La<2>O<3>, wherein 0.2<x<0.4; 0.05<y<0.1; 0.0<z<0.05; 0.25<m<0.4; 0.25<n<0.4; 0.1<p<1.0. The preparation process comprises the following steps that the raw materials are proportioned according to stoichiometric ratio; then, the raw materials are milled by balls in a wet method and mixed for 6 to 8 hours; next, the raw materials are dried, pressed into blocks and synthesized, and the synthesizing condition is that the temperature of the raw materials is preserved for 2 to 3 hours at 800 to 850 DEGC. Then, the synthesized raw material blocks are milled by balls in a wet method so that the mid position particle diameter of the powder is about 0.8 mum, the PVA binding agent is added into the powder to be granulated and molded, and next, the glue in the granules is removed, and the granules are heated for 2 to 3 hours in oxidizing atmosphere and then are sintered. Next, the granules are oxygenized for 0.5 to 2 hours in a furnace of which the temperature is higher than 800DEGC. The dielectric constant epsilon of the piezoelectric ceramic material is 7500; the piezoelectric strain constant d<33> is 850 pc/N; the mechanical quality factor Qm is 20 to 30. Thus, the piezoelectric ceramic material has wide application prospect.
Description
Technical field
The present invention relates to a kind of high dielectric contant flexible piezoelectric ceramic material and preparation method, relate to a kind of high-k ε, high voltage electric strain constant d or rather
33, low mechanical quality factor Q
mPiezoceramic material and preparation method thereof, be mainly used in aspects such as medical ultrasonic and piezoelectric power supplies, belong to electronic devices and components manufacturing technology field.
Technical background
In recent years, fast development along with computer technology, information technology and microelectronics, the disconnected equipment of ultrasonic treasure also constantly develops towards miniaturization, portable direction, this just requires the size of ultrasound probe also must correspondingly develop towards the mini-direction, piezoelectric chip is the core parts of ultrasound probe, the microminiaturization of ultrasound probe, thereupon certainly will require the performance need of piezoelectric chip further to improve, especially the specific inductivity of piezoelectric chip wants enough big, to satisfy the performance requriements of mini-ultrasound probe.On the other hand, along with the development of modern fuse technology, the requirement to power supply in the Fuze Design is more and more higher, and the miniaturization of fuze power supply, high-energy-density and the storage life-span of living forever etc. becomes the technical bottleneck of the particularly small-bore fuse development of fuse; It is found that by test piezoceramic material is made fuze power supply aspect long storage property, anti-HI high impact, the machine-shaping its special advantages being arranged with piezoelectric ceramics, can produce bigger energy under the T-time HI high impact, the ENERGY E that PZT (piezoelectric transducer) produces
gCan be expressed as: E
g=1/2 ∈
γ∈
oShp
2g
2 33In the formula: s-piezoelectric stressed area; H-piezoelectric total thickness; P-acts on the pressure on the piezoelectric; g
33The piezoelectric constant of-piezoelectric; ∈
γThe relative permittivity of-piezoelectric; ∈
o-permittivity of vacuum; By following formula as can be known, the relative permittivity of piezoelectric is high more, and the energy that PZT (piezoelectric transducer) produced is just big more; Yet, in the market obtainable high dielectric constant piezoelectric ceramic material the PZT-5K type piezoceramic material of Morgan company, its DIELECTRIC CONSTANT: 6200 are arranged; d
33: 870pc/N; Qm:65; The HK1 type piezoceramic material of TRS company, its DIELECTRIC CONSTANT: 6300; d
33: 800pc/N; The 6500HD type piezoceramic material of CTS Corp., its DIELECTRIC CONSTANT: 6500.Purpose of the present invention just is being based on the application demand of above-mentioned this two aspect and is carrying out.
Summary of the invention
Piezoceramic material that provides a kind of high-k, high voltage electric strain constant, low Qm and preparation method thereof is provided the object of the invention.
Pb (Mg
1/3Nb
2/3) O
3-Pb (Ti-Zr) O
3System's piezoceramic material has unusual outstanding dielectric and piezoelectric property near accurate homotype phase boundary (MPS), electrical major cause is suppressed in generation: one, accurate homotype phase boundary place, the structure of material generally is three parts and cubic two-phase coexistent mutually, the three parts has 8 possible direction of polarization mutually, the four directions has 6 possible direction of polarization mutually, at the phase boundary place of two-phase coexistent 14 possible direction of polarization is just arranged, and helps electricdomain and is orientated along direction of an electric field; Its two, room and defective in the phase boundary place structure are more, outside under the effect of electric field, electricdomain is easy to orientation, big polarization property can occur; They are three years old, tripartite energy with cubic two kinds of crystalline structure mutually is very approaching, and when extraneous condition variation, as apply electric field or stress, a kind of expansion of structure then takes place, dwindling of another kind of structure, this just structure reactivity make near the composition of phase boundary have the maximum value of dielectricity and piezoelectricity.
Based on above-mentioned principle, the present invention is intended to incorporating modified by Sr, Ba and La, and purpose is to provide a kind of high-k, high d for Application Areass such as medical ultrasonic and piezoelectric power supplies
33With low Q
mFlexible piezoelectric ceramic material prescription and technology, this material is formed general formula and is: Pb
1-y-zSr
yBa
z(Mg
1/3Nb
2/3)
xTi
mZr
nO
3+ pwt%La
2O
3In the formula: 0.2＜x＜0.4; 0.05＜y＜0.1; 0.0＜z＜0.05; 0.25＜m＜0.4; 0.25＜n＜0.4; 0.1＜p＜1.0; In above-mentioned prescription was formed, x, y, z, m, n were mole number, and x+m+n=1; And La
2O
3Then be with Pb
1-y-zSr
yBa
z(Mg
1/3Nb
2/3)
xTi
mZr
nO
3The weight percentage that adds for benchmark.
Its step of preparation process is: form according to above-mentioned prescription, prepare burden by stoichiometric ratio, as grinding medium, it is synthetic that wet ball grinding batch mixing 6-8 hour, wet feed are dried the back briquetting with agate ball, and pressure is 80-100Mpa; Synthesis temperature was 800-850 ℃ of insulation 2-3 hour, the synthetic material piece uses agate ball as grinding medium after coarse reduction again, wet ball grinding 24 hours, discharging oven dry back adds 1-3wt%PVA (polyvinyl alcohol), the binding agent granulation, the add-on of binding agent is dried powder with the synthetic piezoceramic material behind wet ball grinding be that benchmark adds.Dry-pressing formed pressure is 100-150Mpa, and molding blank places A1 with biscuit then at 2-5 hour binder removal of 800-850 ℃ of insulation
2O
3In the crucible, speed with 2-3 ℃/minute in oxidizing atmosphere is warming up to 1280-1330 ℃, be incubated 2-3 hour sintering, the sintering porcelain body is processed into φ 17 * 1mm size, after ultrasonic cleaning, dry, and place 800-900 ℃ of furnace temperature to keep 0.5-2 hour oxide treatment, top electrode polarization and performance test then.The meta particle diameter of oven dry back powder is about 0.8 μ m, and Sr, Ba are respectively with Sr (Mg during batching
1/3Nb
2/3) O
3And Ba (Mg
1/3Nb
2/3O
3) form adds, or equally with La add by stoichiometric form by oxide compound.
The invention has the advantages that and adopt Material formula makeup of the present invention and preparation technology, can obtain specific inductivity 7500, d
33850pc/N and Qm are the soft high dielectric constant piezoelectric ceramic material about 20-30.Its over-all properties obviously is higher than the value that the Morgam company introduced in the background technology and TRS company are reported.
Embodiment
Below by embodiment this outbreak is further described, further to show substantive distinguishing features of the present invention and obvious improvement.
Embodiment 1
Material consists of: Pb
0.90Sr
0.09Ba
0.01(Mg
1/3Nb
2/3)
0.245Ti
0.371Zr
0.384O
3+ 0.6wt%La
2O
3Form according to above-mentioned prescription, by the stoichiometric ratio 1000g for preparing burden, with agate ball as grinding medium, wet ball grinding batch mixing 6 hours, after the discharging oven dry, pressure briquetting with 80Mpa is synthetic, and synthesis condition is 850 ℃ of insulations 3 hours, and the synthetic material piece uses agate ball as grinding medium after coarse crushing again, wet ball grinding 24 hours, the D of powder
50Be 0.8 μ m, material oven dry back adds 1-3wt%PVA (polyvinyl alcohol), the binding agent granulation, and the add-on of binding agent is dried powder with the synthetic piezoceramic material behind wet ball grinding be that benchmark adds.Dry-pressing formed pressure is 150Mpa, and molding blank is placed the binder removal stove, slowly is warming up to 2 hours binder removals of 850 ℃ of insulations, then biscuit is put into Al
2O
3In the crucible, add a cover and be placed in the oxygen atmosphere sintering stove, be warming up to 1310 ℃ with 2-3 ℃/minute speed, be incubated 3 hours sintering, the sintering porcelain body is processed into φ 17 * 1mm size, after ultrasonic cleaning, dry, and place 860 ℃ of furnace temperature to keep 2 hours oxide treatment, take out back top electrode polarization and performance test.Piezoelectric property sees Table one.
Table one
| Specific inductivity | d 33(pc/N) | tgδ(％) | Kp | Qm |
| 7526 | 863 | 3.5 | 0.57 | 21 |
In the table: Kp: piezoelectric coupling coefficient
Tg δ: dielectric loss
Embodiment 2
Material consists of: Pb
0.89Sr
0.085Ba
0.025(Mg
1/3Nb
2/3)
0.37Ti
0.36Zr
0.27O
3+ 0.4wt%La
2O
3Form according to above-mentioned prescription, by the stoichiometric ratio 1000g for preparing burden, with agate ball as grinding medium, wet ball grinding batch mixing 8 hours, after the discharging oven dry, pressure briquetting with 100Mpa is synthetic, and synthesis condition is 850 ℃ of insulations 3 hours, and the synthetic material piece uses agate ball as grinding medium after coarse crushing again, wet ball grinding 24 hours, the D of powder
50Be 0.8 μ m, material oven dry back adds the granulation of 1%PVA binding agent, and dry-pressing formed pressure is 120Mpa, and molding blank is placed the binder removal stove, slowly is warming up to 2 hours binder removals of 850 ℃ of insulations, then biscuit is put into Al
2O
3In the crucible, add a cover and be placed in the oxygen atmosphere sintering stove, be warming up to 1285 ℃ with 2-3 ℃/minute speed, be incubated 2 hours sintering, the sintering porcelain body is processed into φ 17 * 1mm size, after ultrasonic cleaning, dry, and place 880 ℃ of furnace temperature to keep 2 hours oxide treatment, take out back top electrode polarization and performance test.Piezoelectric property sees Table two.
Table two
| Specific inductivity | d 33(pc/N) | tgδ(％) | Kp | Qm |
| 7512 | 851 | 3.7 | 0.56 | 26 |
Claims (7)
1, a kind of high-k, flexible piezoelectric ceramic material, its composition characteristic are that composition formula is: Pb
1-y-zSr
yBa
z(Mg
1/3Nb
2/3)
xTi
mZr
nO
3+ pwt%La
2O
3, in the formula: 0.2＜x＜0.4; 0.05＜y＜0.1; 0＜z＜0.05; 0.25＜m＜0.4; 0.25＜n＜0.4; 0.1＜p＜1.0; X, y, z, m, n are mole number, and x+m+n=1, La
2O
3Be with Pb
1-y-zSr
yBa
z(Mg
1/3Nb
2/3)
xTi
mZr
nO
3The weight percentage that adds for benchmark.
2, by the described high dielectric contant flexible piezoelectric ceramic material of claim 1, it is characterized in that described material consists of: Pb
0.90Sr
0.09Ba
0.01(Mg
1/3Nb
2/3)
0.245Ti
0.371Zr
0.384O
3+ 0.6wt%La
2O
3
3, by the described high dielectric contant flexible piezoelectric ceramic material of claim 1, it is characterized in that described material consists of: Pb
0.89Sr
0.85Ba
0.025(Mg
1/3Nb
2/3)
0.37Ti
0.36Zr
0.27O
3+ 0.4wt%La
2O
3
4, the method for preparation high dielectric contant flexible piezoelectric ceramic material as claimed in claim 1 is characterized in that processing step is:
A) prepare burden by the described composition general formula of claim 1;
B) wet ball grinding batch mixing 6-8 hour, oven dry back briquetting was synthetic, and synthesis condition is 800-850 ℃ of insulation 2-3 hour;
C) the synthetic material piece is through wet ball grinding, and oven dry adds the polyvinyl alcohol adhesive granulation, and forming pressure is 100-150Mpa;
D) after the moulding base substrate 800-850 ℃ of insulation, 2-5 hour binder removal;
E) then biscuit is placed Al
2O
3In the crucible, in oxidizing atmosphere, be incubated 2-3 hour sintering in 1280-1330 ℃;
F) the agglomerating porcelain body places 800-900 ℃ of furnace temperature to keep 0.5-2 hour oxide treatment.
5, by the described method for preparing high dielectric contant flexible piezoelectric ceramic material of claim 4, it is characterized in that synthetic after behind the wet ball grinding oven dry powder meta particle diameter be 0.8 μ m.
6, by the described method for preparing high dielectric contant flexible piezoelectric ceramic material of claim 4, the adding weight that it is characterized in that polyvinyl alcohol adhesive is 1-3%, and it is to be benchmark with the powder weight of drying behind the wet ball grinding.
7, the described method for preparing high dielectric contant flexible piezoelectric ceramic material of claim 4, the heat-up rate when it is characterized in that sintering is 2-3 ℃/minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101124337A CN100347123C (en) | 2005-12-30 | 2005-12-30 | High dielectric contant flexible piezoelectric ceramic material and preparation process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101124337A CN100347123C (en) | 2005-12-30 | 2005-12-30 | High dielectric contant flexible piezoelectric ceramic material and preparation process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1793000A CN1793000A (en) | 2006-06-28 |
| CN100347123C true CN100347123C (en) | 2007-11-07 |
Family
ID=36804666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101124337A Expired - Fee Related CN100347123C (en) | 2005-12-30 | 2005-12-30 | High dielectric contant flexible piezoelectric ceramic material and preparation process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100347123C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100463970C (en) * | 2006-11-07 | 2009-02-25 | 江南大学 | Solid state fermentation process for producing product with rich probiotics polypeptide |
| CN101475373B (en) * | 2009-01-22 | 2012-01-25 | 中国科学院上海硅酸盐研究所 | High piezoelectric strain constant d31, low piezoelectric strain constant g31 piezoelectric ceramic material and preparation thereof |
| CN102515758A (en) * | 2011-12-12 | 2012-06-27 | 中国振华集团红云器材厂 | Preparation method of piezoelectric ceramic atomizer medium |
| CN102850050B (en) * | 2012-08-31 | 2014-03-12 | 华中科技大学 | Low temperature sintering piezoelectric ceramic material and preparation method thereof |
| CN103435346B (en) * | 2013-08-26 | 2015-03-04 | 江苏大学 | Piezoceramic material for ultrasonic receiver-type transducer |
| CN111146329B (en) * | 2019-12-30 | 2023-09-19 | 平拓(上海)新材料科技有限公司 | High-dielectric piezoelectric material for nuclear power austenitic weld joint detection and preparation method thereof |
| CN112885954A (en) * | 2021-01-11 | 2021-06-01 | 中国科学院声学研究所 | Piezoelectric interlayer |
| CN115490512B (en) * | 2022-09-19 | 2023-10-20 | 大富科技(安徽)股份有限公司 | 5G microwave dielectric ceramic material, preparation method thereof and microwave dielectric ceramic device |
| CN115819082B (en) * | 2022-09-23 | 2023-12-05 | 中国船舶重工集团公司第七一五研究所 | Piezoelectric ceramic material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1281212A (en) * | 2000-08-22 | 2001-01-24 | 姜知水 | Technology for making piezoelectric ceramic sounder medium |
| CN1323043A (en) * | 2000-05-04 | 2001-11-21 | 三星电机株式会社 | Piezoelectric ceramics composition and high-output power transformer produced with the same composition |
| CN1424283A (en) * | 2002-12-27 | 2003-06-18 | 中国科学院上海硅酸盐研究所 | High-temperature piezoelectric ceramic compositions |
| CN1562877A (en) * | 2004-03-30 | 2005-01-12 | 中国科学院上海硅酸盐研究所 | Doped and modified piezoelectric ceramic of potassium sodium bismuth titanate and preparation method |
| CN1587206A (en) * | 2004-08-04 | 2005-03-02 | 武汉理工大学 | Process for preparing piezoelectric ceramic and polymer piezoelectric composite material |
-
2005
- 2005-12-30 CN CNB2005101124337A patent/CN100347123C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323043A (en) * | 2000-05-04 | 2001-11-21 | 三星电机株式会社 | Piezoelectric ceramics composition and high-output power transformer produced with the same composition |
| CN1281212A (en) * | 2000-08-22 | 2001-01-24 | 姜知水 | Technology for making piezoelectric ceramic sounder medium |
| CN1424283A (en) * | 2002-12-27 | 2003-06-18 | 中国科学院上海硅酸盐研究所 | High-temperature piezoelectric ceramic compositions |
| CN1562877A (en) * | 2004-03-30 | 2005-01-12 | 中国科学院上海硅酸盐研究所 | Doped and modified piezoelectric ceramic of potassium sodium bismuth titanate and preparation method |
| CN1587206A (en) * | 2004-08-04 | 2005-03-02 | 武汉理工大学 | Process for preparing piezoelectric ceramic and polymer piezoelectric composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1793000A (en) | 2006-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100347123C (en) | High dielectric contant flexible piezoelectric ceramic material and preparation process thereof | |
| CN101648807A (en) | Calcium barium zirconate titanate base piezoceramics and preparation method thereof | |
| CN109180181B (en) | Lead-free relaxation antiferroelectric ceramic energy storage material and preparation method thereof | |
| CN111978082B (en) | Strontium magnesium niobate doped modified sodium bismuth titanate based energy storage ceramic material and preparation method thereof | |
| CN101215168B (en) | Doping modifying method for lead magnesio-tantalate lead zirconate lead titanate | |
| CN100448796C (en) | Low temperature synthesized no-lead piezoelectric Mg doped sodium potassium niobate ceramic and its prepn process | |
| CN101423391B (en) | Novel potassium niobate sodium base leadless piezoelectric ceramics and preparation method thereof | |
| CN105272233A (en) | Dielectric material for ceramic capacitor and preparation method of dielectric material | |
| CN101429027A (en) | Potassium sodium niobate based leadless piezoelectric ceramic and low-temperature sintering production process | |
| CN114133243A (en) | High-dielectric-constant high-voltage electric strain emission type piezoelectric ceramic material and preparation method thereof | |
| CN101337815A (en) | Leadless piezoelectric ceramics and method for preparing the same | |
| CN102795854A (en) | High-power density piezoceramic material and method for preparing same | |
| CN109320236B (en) | Composite material with high energy storage density and charge-discharge performance and preparation method thereof | |
| CN1821173A (en) | High piezoelectric strain constant piezoelectric ceramic material and its preparing method | |
| KR101866845B1 (en) | Lead-free piezoelectric ceramic composition with excellent electric field-induced strain property and preparation method of the same | |
| CN114292102B (en) | Bismuth ferrite-barium titanate-based lead-free piezoelectric ceramic material and preparation method thereof | |
| CN106565239B (en) | Low-sintering-temperature power type piezoelectric ceramic material and preparation method thereof | |
| CN110078508B (en) | Manganese-doped lead indium niobate zincate-lead titanate piezoelectric ceramic, and preparation method and application thereof | |
| CN114213121A (en) | High-voltage, high-dielectric and high-curie piezoelectric ceramic piece | |
| CN113292340B (en) | High-piezoelectricity low-loss donor-acceptor co-doped piezoelectric ceramic, and preparation method and application thereof | |
| CN103539447B (en) | Low-temperature sintered piezoelectric ceramic material and preparation method thereof | |
| CN113233891A (en) | Lead-free piezoelectric ceramic material and preparation method thereof | |
| KR20180003277A (en) | Producing method of lead-free piezoelectric ceramics with high strains | |
| KR101806207B1 (en) | Ternary lead-free piezoelectric ceramics with high strains and low temperature sintering and preparing method thereof | |
| JPH04337681A (en) | Lamination-type solid-state displacement element |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20071107 Termination date: 20171230 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |