CN106977195A - It is a kind of to have without the BNT base ternary lead-free ferroelectric ceramics of delayed big electric field induced strain and preparation - Google Patents
It is a kind of to have without the BNT base ternary lead-free ferroelectric ceramics of delayed big electric field induced strain and preparation Download PDFInfo
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Abstract
It is a kind of to have without the BNT base ternary lead-free ferroelectric ceramics of delayed big electric field induced strain and preparation, belong to ceramic technology field.Chemical general formula is (1 x y) Bi0.5Na0.5TiO3‑xBaTiO3‑yBiMg0.5Ti0.5O3, 0.10≤x≤0.14,0.04≤y≤0.10.The ternary lead-free ferroelectric ceramics shows have the electric field induced strain without hysteresis characteristic, can meet requirement of the micro-displacement device to material.Now, electric field induced strain S reaches 0.2%~0.3%, electrostriction coefficient Q33Reach (2.0~2.8) × 10‑2m4/C2A kind of ferroelectric ceramics without delayed big strain.
Description
Technical field
Have the present invention relates to a kind of without the BNT base ternary lead-free ferroelectric ceramics of delayed big electric field induced strain and preparation, i.e., it is new
Type (1-x-y) Na0.5Bi0.5TiO3-xBaTiO3-yBi(Mg0.5Ti0.5)O3Ternary lead-free ferroelectric ceramics, belongs to ceramic technology neck
Domain.
Technical background
Ferroelectric ceramics with big electric field induction strain is widely used in micro positioner, brake, smart material and
In terms of other devices.Lead base ferroelectric ceramics such as Pb (Zr, Ti) O3,Pb(Mg,Nb)O3With big electric field induced strain characteristic, account for always
According to the leading position in electric field induced strain device market.But its big lead content pollution environment, health is harmful to, it is and environment-friendly
Type society runs in the opposite direction.Therefore research and development at present has very important significance without lead base ferroelectric ceramics tool.
With flourishing for modern science and technology, new micro-displacement device is in precision optics, microelectronics, aviation boat
My god, the demand of the high-tech sector such as precision machine tool, micro motor, biomedicine and scanning-tunnelling effect microscope increasingly increases
It is long, requirements at the higher level are proposed to the location accuracy of precision components in process.However, outside environmental elements are such as：Temperature
Degree, vibrations, the change of noise can all be impacted to the micro Process of device.Therefore, with small volume, bearing capacity be big, displacement point
Resolution is high, fast response time, and do not generate heat, noise, low energy consumption do not produced, without electromagnetic interference the advantages of electrostriction material
Occupy more and more consequence in micro-move device and Micro-control Technology, cause the extensive concern of domestic and international scientific research personnel.With
The raising of application demand, particularly astronomy, optical field to can adjust to microsecond speed angular, light path position
Move element and propose requirements at the higher level, the research of electrostriction material is paid much attention to.At present, most studied electrostriction
Ceramics are Relaxation Ferroelectrics ceramic materials.Although electrostriction effect generally existing in solid dielectric, its size
It is different.From application, relatively large strain, and strain and electric field can be just produced under relatively low current field condition
Relation does not have delayed, and repeatability will get well, while also requiring that temperature effect is small.Because strain is proportional to square of dielectric constant, again
Because ferroelectric has very big dielectric constant near its phase transition temperature, so ferroelectric should have near its phase transition temperature
Larger strain.
During electrostriction is a tetradic, the solid for being present in various symmetry；It is ion deflection equilbrium position
One mark of production polarization, so as to form the change of lattice constant, that is, produces strain.Since Cross etc. is in 0.9Pb (Mg1/ 3Nb2/3)O3–0.1PbTiO3Since observing big electrostriction in relaxation ferroelectric, ferroelectric, which turns into, makes actuator and micro-
One of critical material of shifter.In recent years, researcher finds in non-plumbum ferroelectric system always has big strain, it is small delayed and
The electrostriction material of high-temperature stability.
Bi1/2Na1/2TiO3(NBT) it is a kind of ABO3The ferroelectric material of type complex perovskite structure.In aspect of performance, BNT bases
Ferroelectricity ferroelectric ceramics has good temperature stability, excellent ferroelectric properties, higher frequency constant, less dielectric system
Number, very big anisotropy, is particularly suitable for use in high frequency and uses.NBT is a kind of typical A complex perovskite structure relaxor ferroelectrics
Body.Early in 1998, Chiang etc. observed 0.25% small delayed electric field induced strain in NBT-BT systems.The proposition such as Jo, NBT
The big electric field induced strain of matrix system, be due to exist in NBT matrixes system special polar micro (polar nanoregions,
PNRs), apply and be changed into ferroelectric state after electric field, and the state that electric field is returned to after removing before polarization.Han etc. is by NBT matrixes system
PNRs point be non-ergodic state (low temperature) and ergodic state (high temperature)：Ergodic state PNRs can only form long-range under the induction of electric field
Sequence, but electric field remove after then recover nonpolar equilibrium state, so as to produce without delayed big electric field induced strain.At present, ergodic state with it is non-
Transformation between ergodic state turns into the main points of view for explaining NBT matrixes system's dielectric and ferroelectricity behavior, although other researchers carry
Some other explanations are gone out.For obtain it is big, without delayed electric field induced strain, researcher be directed to obtaining have non-ergodic state with
The NBT matrixes system of ergodic state PNRs coexisting structures.
Based on considerations above, we are with the Na in cubic phase region0.5Bi0.5TiO3-BaTiO3Binary solid solution system is base
Bottom material, adds the Bi (Mg of Emission in Cubic0.5Ti0.5)O3Constitute ternary lead-free system solid solution (1-x-y) 0.875Na0.5Bi0.5TiO3-
xBaTiO3-yBi(Mg0.5Ti0.5)O3.Pass through this design, it is therefore desirable to be able to ferroelectric ceramics of the construction in ergodic state, obtain
Electric field induced strain material with zero lag and the big coefficient of strain.
The content of the invention
The purpose of the present invention is to obtain a kind of novel B NT Quito member Lead-free ferroelectric ceramics body without delayed big electric field induced strain
System.
To reach goal of the invention, the present invention is a kind of to have the BNT base ternary lead-free ferroelectric ceramics without delayed big electric field induced strain,
Characterized in that, containing Na0.5Bi0.5TiO3、BaTiO3With Bi (Mg0.5Ti0.5)O3, by introducing perovskite structure BaTiO3With
BiMg0.5Ti0.5O3, with Bi0.5Na0.5TiO3Ternary lead-free system is formed, system has cubic mutually coexists knot with counterfeit cubic perovskite
Structure；Ergodic state relaxation ferroelectric can be obtained near room temperature.
The chemical general formula for the Lead-free ferroelectric ceramics that the present invention is obtained is (1-x-y) Bi0.5Na0.5TiO3-xBaTiO3-
yBiMg0.5Ti0.5O3(0.10≤x≤0.14,0.04≤y≤0.10), it can be represented with (1-x-y) BNT-xBT-yBMT.
The present invention uses traditional ceramic preparation technology, and the formula is (1-x-y) Bi0.5Na0.5TiO3-xBaTiO3-
yBiMg0.5Ti0.5O3The raw material that can use of Lead-free ferroelectric ceramics for the pure or electron level Na of chemistry2CO3、Bi2O3、TiO2、
BaCO3、(MgCO3)4·Mg(OH)2·5H2O etc..Specific preparation method is, according to the chemistry mole metering of chemical general formula than weighing
Raw material, by raw material ball milling 12h in ethanol, so that raw material is sufficiently mixed uniformly, loads oxygen after raw material stoving that will be well mixed
Change in aluminium crucible, calcined at 800-950 DEG C, soaking time 2h；Powder after calcining is levigate by 12h ball milling again, dries
It is dry, adhesive PVB is mixed, base substrate (disk that a diameter of 11.5mm is such as pressed under 400MPa pressure), base substrate is pressed into
After 650 DEG C of dumpings, it is warming up to 1100 DEG C~1200 DEG C with 3 DEG C/min speed and is sintered, be incubated 1~3h, obtains (1-x-
Y) BNT-xBT-yBMT ceramics.Potsherd after sintering is by upper silver electrode, the test for carrying out properties to sample.
The present invention is successfully realized to BNT base electrostriction hysteretic properties by the structure of BNT base ternary lead-free systems
Improvement, electric field induced strain is improved, and S is in 0.2%~0.3% for strain, and electrostriction coefficient reaches (2.0~2.8) × 10- 2m4/C2.The present invention is by building (1-x-y) Bi0.5Na0.5TiO3-xBaTiO3-yBiMg0.5Ti0.5O3Ternary lead-free solid solution, is obtained
It is 0.30%, electrostriction coefficient Q to obtain electric field induced strain S33Reach 2.8 × 10-2m4/C2Without delayed strain gauge material, realize
With lead base 0.9Pb (Mgl/3Nb2/3)O3-0.1PbTiO3The ceramic analogous Lead-free ferroelectric ceramics of strain property.
Brief description of the drawings
Fig. 1 is that present component composition is x=0.12, and y=0.04 electric hysteresis stretches curve.
Embodiment
With reference to embodiment, the present invention will be further described, but the present invention is not limited to following examples.
Formula of the present invention is prepared for (1-x-y) Bi0.5Na0.5TiO3-xBaTiO3-yBiMg0.5Ti0.5O3It is unleaded
Ferroelectric ceramics, can use the pure or electron level Na of chemistry2CO3, Bi2O3, TiO2, BaCO3, (MgCO3)4·Mg(OH)2·5H2O etc.
For raw material, it is made according to traditional ceramic preparation technology.Specific preparation method is to be weighed according to chemical general formula and stoichiometric proportion
Raw material, by raw material ball milling 12h in ethanol, so that raw material is sufficiently mixed uniformly, loads oxygen after raw material stoving that will be well mixed
Change in aluminium crucible, calcined at 800-950 DEG C, soaking time 2h.The powder for calcining synthesis is levigate by 12h ball milling again.
The adding additives in the powder of drying, in 400Mpa forming under the pressure, are pressed into diameter 11.5mm, thickness
1.5mm or so article shaped.By article shaped dumping, the potsherd after 2h, sintering is finally sintered at 1100-1200 DEG C by upper silver
Electrode and then the test that properties are carried out to sample.Using equipped with electrostrictive ferroelectricity tester (Premier II,
Radiant Technologies, USA), test electric field induced strain.
The formula of the Lead-free ferroelectric ceramics prepared according to the method described above is as follows：
Embodiment 1：
Formula：
0.84Bi0.5Na0.5TiO3-0.12BaTiO3-0.04BiMg0.5Ti0.5O3
Technique：850 DEG C of calcining heat, 1150 DEG C of sintering temperature.
Embodiment 2：
Formula：
0.80Bi0.5Na0.5TiO3-0.14BaTiO3-0.06BiMg0.5Ti0.5O3
Technique：900 DEG C of calcining heat, 1100 DEG C of sintering temperature.
Embodiment 3：
Formula：
0.80Bi0.5Na0.5TiO3-0.10BaTiO3-0.10BiMg0.5Ti0.5O3
Technique：850 DEG C of calcining heat, 1150 DEG C of sintering temperature.
Embodiment 4：
Formula：
0.79Bi0.5Na0.5TiO3-0.13BaTiO3-0.08BiMg0.5Ti0.5O3
Technique：900 DEG C of calcining heat, 1200 DEG C of sintering temperature.
Each embodiment performance table：
Claims (3)
1. a kind of have the BNT base ternary lead-free ferroelectric ceramics without delayed big electric field induced strain, it is characterised in that contains
Na0.5Bi0.5TiO3、BaTiO3With Bi (Mg0.5Ti0.5)O3, by introducing perovskite structure BaTiO3And BiMg0.5Ti0.5O3, with
Bi0.5Na0.5TiO3Ternary lead-free system is formed, system has cubic and counterfeit cubic perovskite phase coexisting structure.
2. according to a kind of with the BNT base ternary lead-free ferroelectric ceramics without delayed big electric field induced strain, its spy described in claim 1
Levy and be, chemical general formula is (1-x-y) Bi0.5Na0.5TiO3-xBaTiO3-yBiMg0.5Ti0.5O3, 0.10≤x≤0.14,0.04
≤ y≤0.10, is represented with (1-x-y) BNT-xBT-yBMT.
3. the system with the BNT base ternary lead-free ferroelectric ceramics without delayed big electric field induced strain described in claim any one of 1-3
Preparation Method, it is characterised in that formula is (1-x-y) Bi0.5Na0.5TiO3-xBaTiO3-yBiMg0.5Ti0.5O3Non-plumbum ferroelectric pottery
Porcelain, the raw material used is the pure or electron level Na of chemistry2CO3、Bi2O3、TiO2、BaCO3、(MgCO3)4·Mg(OH)2·5H2O；Tool
Preparation is：According to the chemistry mole metering of chemical general formula than weighing raw material, by raw material ball milling 12h in ethanol, so that
Raw material is sufficiently mixed uniformly, will be loaded after well mixed raw material stoving in alumina crucible, is calcined at 800-950 DEG C,
Soaking time 2h；Powder after calcining is levigate by 12h ball milling again, and drying mixes adhesive PVB, is pressed into base substrate, base substrate
After 650 DEG C of dumpings, it is warming up to 1100 DEG C~1200 DEG C with 3 DEG C/min speed and is sintered, be incubated 1~3h, obtains unleaded
Ferroelectric ceramics.
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Cited By (2)
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| CN112062555A (en) * | 2020-09-17 | 2020-12-11 | 广西大学 | Preparation method of BNT-BT-based lead-free negative electricity card material by doping induction of functional groups |
| CN113999004A (en) * | 2021-11-08 | 2022-02-01 | 西安电子科技大学 | Lead-free high-energy-storage-density ceramic material and preparation method thereof |
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| CN102757220A (en) * | 2012-07-13 | 2012-10-31 | 北京工业大学 | Bi0.5, Na0.5 and TiO3 based ternary-system lead-free piezoelectric ceramic and preparation thereof |
| CN103102154A (en) * | 2013-02-03 | 2013-05-15 | 北京工业大学 | Bi0.5Na0.5TiO3-BaTiO3-BiMg0.5Ti0.5O3 lead-free piezoelectric ceramic material |
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| CN112062555A (en) * | 2020-09-17 | 2020-12-11 | 广西大学 | Preparation method of BNT-BT-based lead-free negative electricity card material by doping induction of functional groups |
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