CN107010947A - Lead-free ferroelectric ceramics material with critical brusque-switch effect and preparation method thereof - Google Patents
Lead-free ferroelectric ceramics material with critical brusque-switch effect and preparation method thereof Download PDFInfo
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- CN107010947A CN107010947A CN201710302249.1A CN201710302249A CN107010947A CN 107010947 A CN107010947 A CN 107010947A CN 201710302249 A CN201710302249 A CN 201710302249A CN 107010947 A CN107010947 A CN 107010947A
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- 239000000463 material Substances 0.000 title claims abstract description 22
- 239000000919 ceramic Substances 0.000 title claims abstract description 15
- 230000000694 effects Effects 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000009413 insulation Methods 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 238000007603 infrared drying Methods 0.000 claims description 6
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 238000005056 compaction Methods 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 229910052573 porcelain Inorganic materials 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 229910010293 ceramic material Inorganic materials 0.000 claims 1
- 230000005684 electric field Effects 0.000 abstract description 7
- -1 Compound ion Chemical class 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000005259 measurement Methods 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 230000010485 coping Effects 0.000 abstract description 2
- 230000001419 dependent effect Effects 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 230000006698 induction Effects 0.000 abstract 1
- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/49—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract
The invention discloses a kind of Lead-free ferroelectric ceramics material with critical brusque-switch effect and preparation method thereof, material prescription is：Bi1/2Na1/2Ti0.85(Li1/4Nb3/4)0.05(Zr1/2Zn1/2)0.10O3；Pass through B and Ti4+Compound ion (the Li of the identical chemical valence of ion1/4Nb3/4)4+, and different chemical valence compound ion (Zr1/2Zn1/2)3+, strictly with 1:2 ratio, replaces Ti at B4+Ion, produce different charged defects types, the arrangement of adjacent cell Defect Ordering is formed, the powered electricdomain (non-room or Lithium ions compensation effect) of electronics and hole offset-type is produced, thus the huge coping behavior of electric field induction of special critical switching effect occurs.The huge strain property that product is induced through experiment measurement with electric field is made, dependent variable is up to S%=0.47%, while having in critical switching electric fieldsE CThe huge strains of=56kV/cm occur, and the Δ in very narrow field regimeEComplete strain occurs for=2kV/cm, in critical zone, strain variation rateαUp to 2.8 × 103.These performances yet there are no report, can be in special applications.
Description
Technical field
The present invention relates to the Lead-free ferroelectric ceramics material of driving application, specifically a kind of ABO3Type perovskite structure, has
Bismuth-sodium titanate (BNT) base Lead-free ferroelectric ceramics material of critical brusque-switch effect and preparation method thereof.
Background technology
Ferroelectric material is wide due to characteristics such as its excellent dielectricity, piezoelectricity, electrostriction and performance Modulatory characters
It is general to be applied to the electronic components such as sensor, actuator, micro positioner, transducer, as intelligence structure (smart
Structure), Micro Electro Mechanical System (MEMS), bionical device (smart devices), compound and gradient function device
The core material of leading-edge fields such as (composite and functionally grade device).Leaded ferroelectric material tool
There is excellent electric property, but unleaded environmental requirement forces people to explore lead-free with all strength.Bismuth-sodium titanate (BNT) base is unleaded
Ceramics have stronger ferroelectricity, very with potentiality to be exploited, are to obtain one of material of extensive concern.Current BNT bases are unleaded
The good piezoelectric performance of ceramics, electric field induce huge strain, and high energy-storage property all has been reported that, but with critical brusque-switch effect
Electric field induce the BNT base ceramics of huge strain to have not been reported.
The content of the invention
It is an object of the invention to provide a kind of ABO3Type perovskite structure, induces huge strain, and have simultaneously with electric field
Bismuth-sodium titanate (BNT) base Lead-free ferroelectric ceramics material of critical brusque-switch effect and preparation method thereof.
A kind of Lead-free ferroelectric ceramics material with critical brusque-switch effect of the present invention, is formulated and is：Bi1/2Na1/2Ti0.85
(Li1/4Nb3/4)0.05(Zr1/2Zn1/2)0.10O3 ；
Pass through B and Ti4+Compound ion (the Li of the identical chemical valence of ion1/4Nb3/4)4+, and different chemical valence compound ions
(Zr1/2Zn1/2)3+, strictly with 1:2 ratio, replaces Ti at B4+Ion, produces different charged defects types, forms phase vincial faces
Born of the same parents' Defect Ordering is arranged, and produces the powered electricdomain (non-room or Lithium ions compensation effect) of electronics and hole offset-type, thus is gone out
The electric field of existing special critical switching effect induces huge coping behavior.
The preparation method of the above-mentioned Lead-free ferroelectric ceramics material with critical brusque-switch effect, comprises the following steps：
（1）According to Bi1/2Na1/2Ti0.85(Li1/4Nb3/4)0.05(Zr1/2Zn1/2)0.10O3 Stoichiometry to weigh purity respectively equal
For 99.99% raw material Bi2O3、Na2CO3、Li2CO3、Nb2O5、ZnO、ZrO2And TiO2, it is well mixed；
（2）Well mixed raw material is fitted into ball grinder, by abrading-ball of zirconium oxide, absolute ethyl alcohol be medium ball milling 12 hours,
Separate abrading-ball, the infrared drying at 60 DEG C, in 835 DEG C in high alumina crucible（Insulation is synthesized for 8 hours；
（3）The powder progress secondary ball milling of synthesis infrared drying at 12 hours, 60 DEG C, then in 920 DEG C of insulations 4 in high alumina crucible
Hour roasting；
（4）The PVA solution granulation of material quality 5% will be added in roasting powder；
（5）In 100Mpa cold isostatic compactions after granulation；
（6）The material of shaping sinters porcelain for 5 hours into 1100 DEG C of insulations, and thickness 0.4mm is worn on two sides, polishing, and then two sides is plated
Product is made in silver electrode.
The huge strain property that products obtained therefrom is induced through experiment measurement with electric field, dependent variable has simultaneously up to S%=0.47%
Have in critical switching electric fieldsE CThe huge strains of=56kV/cm occur, and the Δ in very narrow field regimeE=2kV/cm occurs complete
Strain, in critical zone, strain variation rateαUp to 2.8 × 103.These performances yet there are no report, can be in special field
Close application.
Brief description of the drawings
Fig. 1 is the strain curve figure of Lead-free ferroelectric ceramics material of the embodiment of the present invention.
Embodiment
Present invention is further described with reference to embodiment and accompanying drawing, but is not with the restriction of the present invention.
Embodiment
The Lead-free ferroelectric ceramics material with critical brusque-switch effect is prepared, step is as follows：
（1）According to Bi1/2Na1/2Ti0.85(Li1/4Nb3/4)0.05(Zr1/2Zn1/2)0.10O3 Stoichiometry to weigh purity respectively equal
For 99.99% raw material Bi2O3、Na2CO3、Li2CO3、Nb2O5、ZnO、ZrO2And TiO2, it is well mixed；
（2）Well mixed raw material is fitted into ball grinder, by abrading-ball of zirconium oxide, absolute ethyl alcohol be ball-milling medium, fully mix
Close ball milling 12 hours（Fixed value still has scope）, separate abrading-ball, by raw mixture at 60 DEG C infrared drying, then in high alumina
Synthesized within 8 hours in 835 DEG C of insulations in crucible；
（3）Synthetic powder secondary ball milling infrared drying at 12 hours, 60 DEG C, then in high alumina crucible in 920 DEG C be incubated 4 hours
Roasting；
（4）The PVA solution granulation of material quality 5% will be added in roasting powder；
（5）In 100Mpa cold isostatic compactions after granulation；
（6）The material of shaping sinters porcelain for 5 hours into 1100 DEG C of insulations, and thickness 0.4mm is worn on two sides, polishing, and then two sides is plated
Product is made in silver electrode.
Reference picture 1, is made product by embodiment and carries out electrical property measurement, as a result as follows：
。
Claims (2)
1. a kind of Lead-free ferroelectric ceramics material with critical brusque-switch effect, it is characterised in that：The ceramic material formula is：
Bi1/2Na1/2Ti0.85(Li1/4Nb3/4)0.05(Zr1/2Zn1/2)0.10O3。
2. the preparation method of the Lead-free ferroelectric ceramics material described in claim 1, it is characterised in that comprise the following steps：
（1）According to Bi1/2Na1/2Ti0.85(Li1/4Nb3/4)0.05(Zr1/2Zn1/2)0.10O3 Stoichiometry weigh purity respectively and be
99.99% raw material Bi2O3、Na2CO3、Li2CO3、Nb2O5、ZnO、ZrO2And TiO2, it is well mixed；
（2）Well mixed raw material is fitted into ball grinder, by abrading-ball of zirconium oxide, absolute ethyl alcohol be medium ball milling 12 hours,
Abrading-ball is separated, the infrared drying at 60 DEG C is synthesized for 8 hours in high alumina crucible in 835 DEG C of insulations；
（3）The powder progress secondary ball milling of synthesis infrared drying at 12 hours, 60 DEG C, then in 920 DEG C of insulations 4 in high alumina crucible
Hour roasting；
（4）The PVA solution granulation of material quality 5% will be added in roasting powder；
（5）In 100Mpa cold isostatic compactions after granulation；
（6）The material of shaping sinters porcelain for 5 hours into 1100 DEG C of insulations, and thickness 0.4mm is worn on two sides, polishing, and then two sides is plated
Product is made in silver electrode.
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| CN201710302249.1A CN107010947B (en) | 2017-05-02 | 2017-05-02 | Lead-free ferroelectric ceramic material with critical abrupt switching effect and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5561090A (en) * | 1994-07-19 | 1996-10-01 | Korea Institute Of Science And Technology | Dielectric ceramic composition for high frequencies and method for preparation of the same |
| CN101200369A (en) * | 2007-07-27 | 2008-06-18 | 桂林电子科技大学 | Titanium niobic zincic acid bismuth sodium system leadless piezo-electric ceramic and preparation method thereof |
| CN101857436A (en) * | 2010-06-12 | 2010-10-13 | 中国地质大学（武汉） | Potassium-sodium niobate base lead-free piezoelectric ceramic powder and preparation method thereof |
| CN103964844A (en) * | 2014-05-21 | 2014-08-06 | 宁波大学 | Dielectric energy storage ceramic material and preparation method thereof |
| CN104072129A (en) * | 2014-04-18 | 2014-10-01 | 济南大学 | B-position equivalent zirconium doped sodium bismuth titanate film |
-
2017
- 2017-05-02 CN CN201710302249.1A patent/CN107010947B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5561090A (en) * | 1994-07-19 | 1996-10-01 | Korea Institute Of Science And Technology | Dielectric ceramic composition for high frequencies and method for preparation of the same |
| CN101200369A (en) * | 2007-07-27 | 2008-06-18 | 桂林电子科技大学 | Titanium niobic zincic acid bismuth sodium system leadless piezo-electric ceramic and preparation method thereof |
| CN101857436A (en) * | 2010-06-12 | 2010-10-13 | 中国地质大学（武汉） | Potassium-sodium niobate base lead-free piezoelectric ceramic powder and preparation method thereof |
| CN104072129A (en) * | 2014-04-18 | 2014-10-01 | 济南大学 | B-position equivalent zirconium doped sodium bismuth titanate film |
| CN103964844A (en) * | 2014-05-21 | 2014-08-06 | 宁波大学 | Dielectric energy storage ceramic material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 刘维良等: "《先进陶瓷工艺学》", 31 August 2004, 武汉理工大学出版社 * |
| 汪济奎等: "《新型功能材料导论》", 31 October 2014, 华东理工大学出版社 * |
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