CN105130419B - A kind of high electric field induced strain lead-free piezoceramic material and preparation method and application - Google Patents
A kind of high electric field induced strain lead-free piezoceramic material and preparation method and application Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 147
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 230000005684 electric field Effects 0.000 title claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000000498 ball milling Methods 0.000 claims abstract description 24
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 14
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006073 displacement reaction Methods 0.000 claims abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 58
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 44
- 239000000843 powder Substances 0.000 claims description 44
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 35
- 229910002113 barium titanate Inorganic materials 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 25
- 239000011780 sodium chloride Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 18
- 238000010792 warming Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 13
- 239000000853 adhesive Substances 0.000 claims description 13
- 230000001070 adhesive effect Effects 0.000 claims description 13
- 239000007790 solid phase Substances 0.000 claims description 13
- 238000000748 compression moulding Methods 0.000 claims description 12
- 229910010293 ceramic material Inorganic materials 0.000 claims description 11
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 9
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 5
- 239000000919 ceramic Substances 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 18
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 7
- 238000004321 preservation Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 4
- 229910010252 TiO3 Inorganic materials 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 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 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
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Abstract
The present invention relates to a kind of high electric field induced strain lead-free piezoceramic materials and preparation method and application, the chemical general formula of the material is (1 x) [0.94BNT 0.06BT] xBiT, wherein, x is the mass content of BiT, 0 < x≤0.15, during preparation, the bismuth laminated Bi of sheet is prepared using molten-salt growth method4Ti3O12Material, then by Bi4Ti3O12Compare dispensing by certain mass with the 0.94BNT 0.06BT base-materials of perovskite structure, it is placed in ball grinder, it is granulated after ball milling, using solid sintering technology, (1 x) [0.94BNT 0.06BT] xBiT lead-free piezoceramic materials are prepared, available for preparing piezoelectric transducer, piezoelectric motors or displacement controller.Compared with prior art, preparation method of the present invention is simple, and technology stability is good, at low cost, and lead-free piezoceramic material obtained has excellent piezoelectric property, and compactness is good, and electric field induced strain value has good application prospect up to 0.37%.
Description
Technical field
The invention belongs to lead-free piezoelectric material technical field, be related to a kind of high electric field induced strain lead-free piezoceramic material and its
Preparation method and application.
Background technology
Piezoelectric material is since its superior piezoelectric property is widely used in aerospace, medicine and industrial brake, changes
The fields such as energy device, sensor.Lead zirconate titanate (PZT) base piezoelectric material of the present widely applied Ca-Ti ore type for being lead base.But
It is, since lead oxide is a kind of volatile noxious material, serious volatilization to be generated in high temperature sintering, is caused to environment
Lead contamination brings very big harm to human health;Sealed sintering is needed in preparation process, not only increases product cost,
The consistency of performance for causing product is poor.Therefore, environmentally friendly lead-free piezoelectric material substitution plumbum-based material is researched and developed
Through being a task that is urgent and having important realistic meaning.
Leadless piezoelectric ceramics refers to not only there is preferable performance but also the good piezoelectric ceramics to environment, it requires material
System do not contain in itself may to ecological environment hurtful substance.There are mainly four types of the leadless piezoelectric systems reported at present:
BaTiO3(BT) base leadless piezoelectricity material, (Bi0.5Na0.5)TiO3(BNT) base leadless piezoelectricity material, niobate base lead-free piezoresistive material
Expect (KNN) and bismuth laminated leadless piezoelectric material.Wherein, BNT and KNN bases are several recently due to its superior emergent property
Year by countries in the world scholar extensive concern.Its research is concentrated on improving on piezoelectric property, for BNT base leadless piezoelectricities
Ceramic systems are concentrated mainly on following two methods at present:First, using doping or compound method, on the basis of BNT bases
Second yuan and third member of identical perovskite structure are introduced, the emergent property of material is improved with this.Heranut et al are studied
Rare-earth elements La, Sm, Nd and Nb replace the BNT bases ceramics of A and B respectively, the results showed that and the consistency of material gets a promotion,
Relative density reaches more than 95%, and La, Nb can improve piezoelectric and dielectric properties:d33=100pC/N, kp=0.14, kt=
0.46。[A Herabut et al,Processing and electromechanical properties of
(Bi0.5Na0.5)(1-1.5x)LaxTiO3ceramics,Journal of the American Ceramic Society,80
(1997):2954].But the strain value of ceramics is contributed little;ShanTao Zhang introduced on the basis of BNT BT and
KNN has constructed (1-x-y) Bi0.5Na0.5TiO3-xBaTiO3-yK0.5Na0.5NbO3Ternary system, it is electroluminescent by the optimization of component
Strain obtains maximum value 0.45% at x=0.06, y=0.02, and corresponding dynamic piezoelectric coefficient is 560pm/V.[ShanTao
Zhang et al, Giant strain in lead-free piezoceramics Bi0.5Na0.5TiO3-BaTiO3-
K0.5Na0.5NbO3System,Applied Physics Letters,91(2007):112906].But the performance of material is
Bottleneck is encountered, it is difficult to be greatly improved;Second is that textured ceramics material is prepared using the tape casting using mould material,
Chenggen Ye are prepared for the textured ceramic of 0.79BNT-0.02BKT-0.01KNN, and texture degree can reach 94%, obtain most
Big strain value 0.45%.[Chenggen Ye et al,Large strain response in<001>
textured0.79BNT-0.20BKT-0.01NKN Lead-free piezoelectric ceramics,Journal of
the American Ceramic Society,95,11(2012):3577].But the preparation method of textured ceramic is very multiple
It is miscellaneous, cost is higher, it is necessary first to prepare mould material, and technology stability is bad, as a result be difficult repeat.
The perovskite that the present invention breaks the normal procedure and the compound ABO of perovskite3Tactic pattern, using bismuth laminated
Bi4Ti3O12The 0.94BNT-0.06BT materials of material and perovskite structure are mutually compound, using simple conventional solid sintering process,
It obtains with the leadless piezoelectric ceramics new system strained greatly, strain value is up to 0.37%.
Invention content
It is answered it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of novel height is electroluminescent
Become lead-free piezoceramic material and preparation method and application, it is compound with perovskite structure to have broken conventional perovskite structure
ABO3Traditional mode, it is mutually compound using perovskite and bismuth layer structure, larger electric field induced strain value is obtained with this, and do not have
Dephasign exists, and compactness is good.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of high electric field induced strain lead-free piezoceramic material, the chemical general formula of the material is (1-x) [0.94BNT-
0.06BT]-xBiT, wherein, mass contents of the x for BiT, 0 < x≤0.15.
Preferably, the x=0.06-0.1.
A kind of preparation method of high electric field induced strain lead-free piezoceramic material, this method specifically include following steps:
(1) the 0.94BNT-0.06BT matrix of powder material of perovskite structure is prepared;
(2) bismuth laminated Bi is prepared4Ti3O12Flaky powder material;
(3) by 0.94BNT-0.06BT matrix of powder material and Bi4Ti3O12Flaky powder is (1-x) in mass ratio:X is mixed,
In, 0 < x≤0.15, ball milling, drying, after sieving, addition adhesive, then through granulation, compression molding, green body is made, by solid phase
Sintering, obtains (1-x) [0.94BNT-0.06BT]-xBiT ceramic materials.
Adhesive described in step (3) is polyvinyl alcohol, quality and the (Bi of the polyvinyl alcohol0.5Na0.5Ti)O3Base-material with
BaTiO3The ratio between gross mass of base-material is 2:1.
The treatment conditions of compression molding described in step (3) are:Control pressure is 4-5MPa, is pressed into a diameter of 10mm's
Disk green body.
The condition of solid-phase sintering described in step (3) is:In silicon carbide rod furnace, at 1100-1200 DEG C, constant temperature processing 2-
4h, then with stove cooled to room temperature.
Preferably, the condition of the solid-phase sintering described in step (3) is:It is permanent at 1150-1200 DEG C in silicon carbide rod furnace
Temperature processing 3h, then with stove cooled to room temperature.
In the present invention, the 0.94BNT-0.06BT matrix of powder material for preparing perovskite structure specifically includes following steps:
(A)(Bi0.5Na0.5Ti)O3The preparation of base-material:With NaCO3、Bi2O3And TiO2For raw material, according to (Bi0.5Na0.5Ti)
O3The stoichiometric ratio of middle Na, Bi and Ti element weighs NaCO3、Bi2O3And TiO2, successively through dispensing, batch mixing and heat treatment, i.e.,
(Bi is made0.5Na0.5Ti)O3Base-material;
(B)BaTiO3The preparation of base-material:With BaCO3、TiO2For raw material, according to BaTiO3The chemistry meter of middle Ba and Ti elements
Amount ratio weighs BaCO3And TiO2, successively through dispensing, batch mixing and heat treatment, obtain BaTiO3Base-material;
(C)0.94(Bi0.5Na0.5)TiO3-0.06BaTiO3The preparation of base-material:By (Bi0.5Na0.5Ti)O3Base-material with
BaTiO3Base-material is 0.94 in molar ratio:0.06 mixing, adds in absolute ethyl alcohol, ball milling, and drying crosses 80 mesh sieve, obtains 0.94
(Bi0.5Na0.5)TiO3-0.06BaTiO3Base-material;
Heat treatment described in step (A) is to handle 4-6h in 840-860 DEG C of constant temperature.
Preferably, the heat treatment described in step (A) is to handle 5h in 850 DEG C of constant temperature.
Heat treatment described in step (B) is to handle 4-6h in 900-920 DEG C of constant temperature.
Preferably, the heat treatment described in step (B) is to handle 5h in 900 DEG C of constant temperature.
In the present invention, bismuth laminated Bi is prepared4Ti3O12The method of flaky powder material is as follows:
With Bi2O3、TiO2And NaCl is raw material, first according to Bi4Ti3O12The stoichiometric ratio of middle Bi and Ti elements weighs
Bi2O3And TiO2, NaCl, absolute ethyl alcohol, ball milling mixing are added in, drying is transferred in crucible, after sintering processes, is cooled to room
Temperature is rinsed with deionized water, removes NaCl, and drying obtains Bi4Ti3O12Flaky powder.
Wherein, the condition of the sintering processes is:800-820 DEG C, Isothermal sinter 1-2h is first warming up to, then is warming up to
1000-1100 DEG C, Isothermal sinter 2-3h.
Preferably, the condition of the sintering processes is:805 DEG C, Isothermal sinter 1h are first warming up to, then is warming up to 1050
DEG C, Isothermal sinter 2h.
In the present invention, the Bi4Ti3O12Flaky powder is made by molten-salt growth method, i.e., using Bi2O3、TiO2It is with NaCl
Bi is made by molten-salt growth method in raw material4Ti3O12Flaky powder template, specific reaction equation are as follows:
Wherein, Bi2O3With TiO2According to Bi4Ti3O12The stoichiometric ratio of flaky powder, NaCl mass are Bi2O3And TiO2
1.2 times of gross mass, sintering temperature are 1000-1100 DEG C.
A kind of application of high electric field induced strain lead-free piezoceramic material, the lead-free piezoceramic material are used to prepare pressure
In electric transducer, piezoelectric motors or displacement controller.
0.94BNT-0.06BT base-material and bismuth laminated BiT flaky powder material phase of the present invention using perovskite structure
It is compound, ceramics are prepared using simple conventional solid sintering process, have been successfully prepared the leadless piezoelectric ceramics with big strain value
Material.
Compared with prior art, the invention has the characteristics that:
1) it is mutually multiple with bismuth laminated BiT flaky powders material using the 0.94BNT-0.06BT base-materials of perovskite structure
It closes, is successfully prepared (1-x) [0.94BNT-0.06BT]-xBiT lead-free piezoceramic materials of pure perovskite structure, breaks
Conventional perovskite and the compound ABO of perovskite structure3Pattern has opened up new research direction for leadless piezoelectric ceramics field;
2) using conventional solid sintering process in preparation process, fairly simple, technology stability is good, at low cost, is conducive to reality
Existing industrialization, and (1-x) [0.94BNT-0.06BT]-xBiT lead-free piezoceramic materials of gained are prepared, have excellent
Piezoelectric property, electric field induced strain value is up to 0.37%;
3) (1-x) [the 0.94BNT-0.06BT]-xBiT lead-free piezoceramic materials for preparing gained can be widely applied to press
In electric transducer, piezoelectric motors and high precision position shift controller, there is good application prospect.
Description of the drawings
Fig. 1 is the Bi prepared in embodiment 1 using molten-salt growth method4Ti3O12The SEM figures of flaky powder material;
Fig. 2 is the Bi prepared in embodiment 1 using molten-salt growth method4Ti3O12The X ray diffracting spectrum of flaky powder material;
Fig. 3 is Bi in embodiment 24Ti3O12Content be 6wt% 0.94 [0.94BNT-0.06BT] -0.06BiT and
The X ray diffracting spectrum of 0.9% [0.94BNT-0.06BT] -0.1BiT ceramics of 10wt%;
Fig. 4 is the SEM figures of 0.94 [0.94BNT-0.06BT] -0.06BiT ceramics in embodiment 2;
Fig. 5 is the electric field induced strain curve of 0.94 [0.94BNT-0.06BT] -0.06BiT ceramics in embodiment 2;
Fig. 6 is the SEM figures of 0.9 [0.94BNT-0.06BT] -0.1BiT ceramics in embodiment 3;
Fig. 7 is the electric field induced strain curve of 0.9 [0.94BNT-0.06BT] -0.1BiT ceramics in embodiment 3.
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also be based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under the spirit of the present invention.
Embodiment 1:
Prepare Bi4Ti3O12Flaky powder material.
Weigh 11.356g Bi2O3Powder, 2.607g TiO2Powder, then weigh 16.756g NaCl powders, zirconium ball
Mixed material is dried, is packed into alumina crucible by 36.863g by all powders and absolute ethyl alcohol ball milling mixing ball milling 24 hours
It is put into stove after being first warming up to 805 DEG C of heat preservation 1h and is to slowly warm up to 1050 DEG C of heat preservation 2h again, be put into Buchner funnel after cooling
Net NaCl is washed with deionized water, drying obtains Bi4Ti3O12Flaky powder material.
Fig. 1 is the Bi prepared4Ti3O12The X ray diffracting spectrum of powder body material.It can be seen that it is bismuth stratiform knot from figure
Structure does not observe other dephasigns.
Fig. 2 is the Bi prepared4Ti3O12The SEM figures of powder body material.It is upper significantly it can be seen that Bi from figure4Ti3O12Powder body material
For laminated structure, and about 20 microns of average-size.
Embodiment 2:
0.94(Bi0.5Na0.5)TiO3-0.06BaTiO3The preparation of base-material:Using NaCO3、Bi2O3And TiO2It is first for raw material
According to (Bi0.5Na0.5Ti)O3The stoichiometric ratio of middle Na, Bi and Ti element weighs NaCO3、Bi2O3And TiO2, successively through dispensing,
Batch mixing, precompressed and heat treatment step prepare (Bi0.5Na0.5Ti)O3Base-material;According still further to BaTiO3The chemistry of middle Ba and Ti elements
Metering ratio weighs BaCO3And TiO2, successively BaTiO is prepared through dispensing, batch mixing, precompressed and heat treatment step3Base-material;Finally
By (the Bi of acquisition0.5Na0.5Ti)O3And BaTiO3Base-material is according to 0.94 (Bi0.5Na0.5)TiO3-0.06BaTiO3Ratio weigh up
The i.e. available 0.94 (Bi of 80 mesh sieve is crossed after ball milling mixing is dried afterwards for 24 hours after material0.5Na0.5)TiO3-0.06BaTiO3Base-material.
Wherein, (Bi0.5Na0.5)TiO3Heat treatment temperature be 850 DEG C of soaking times be 5h;BaTiO3Heat treatment temperature
It is 900 DEG C, soaking time 5h.
Weigh 0.94 (Bi of the above-mentioned preparations of 9.4g0.5Na0.5)TiO3-0.06BaTiO3Base-material is prepared in 0.6g embodiments 1
Bi4Ti3O12Flaky powder material, 12g zirconium balls are put into ball grinder plus alcohol ball milling is dried afterwards for 24 hours, cross 80 mesh sieve.Expected with 1g
The ratios of two drop adhesives are granulated after adding in PVA adhesives, are pressed into the disk of diameter 10mm after granulation, pressure 4Mpa, will be into
Idiosome after type is viscous in 550 DEG C of rows, is finally heat-treated at 1180 DEG C in silicon carbide rod furnace, prepares fine and close 0.94
[0.94BNT-0.06BT] -0.06BiT ceramic materials.
Fig. 3 is the X ray diffracting spectrum of 0.94 [0.94BNT-0.06BT] -0.06BiT lead-free piezoceramic materials, from figure
It is upper to can be seen that only Perovskite Phase structure, other dephasigns are not observed, due to Bi4Ti3O12Content it is seldom, ceramics not
It will appear the dephasign of bismuth stratiform.
Fig. 4 is the SEM figures of 0.94 [0.94BNT-0.06BT] -0.06BiT lead-free piezoceramic materials, and pottery is found out from figure
Porcelain compactness is high, and with the presence of apparent big crystal grain, this is Bi4Ti3O12Laminated structure, in sintering process with powder base
Material produces solid molten well.
Fig. 5 is the electric field induced strain curve of 0.94 [0.94BNT-0.06BT] -0.06BiT lead-free piezoceramic materials, by scheming
It can be seen that its strain value has reached 0.37%.
Embodiment 3:
It weighs 9.0g and implements the 2 0.94 (Bi prepared0.5Na0.5)TiO3-0.06BaTiO3Base-material and 1.0g implement 1 preparation
Bi4Ti3O12Flaky powder material, 12g zirconium balls, be put into ball grinder with absolute ethyl alcohol ball milling mixing ball milling 24 hours, will mix
80 mesh sieve is crossed after material drying afterwards.Then be granulated, after in 4Mpa pressure lower sheetings, green body after molding is viscous in 550 DEG C of rows, most
It is heat-treated at 1160 DEG C in silicon carbide rod furnace afterwards, prepares compactness good 0.9 [0.94BNT-0.06BT] -0.1BiT
Lead-free piezoceramic material.
Fig. 6 is the SEM figures of 0.9 [0.94BNT-0.06BT] -0.1BiT leadless piezoelectric ceramics, and ceramic dense is found out from figure
Property it is high, occur without any hole, and crystallite dimension is small compared with embodiment 2.
Fig. 7 is the electric field induced strain curve of 0.9 [0.94BNT-0.06BT] -0.1BiT leadless piezoelectric ceramics, electric field induced strain
It is 0.27% to be worth, and is illustrated with Bi4Ti3O12Amount increase, ceramic strain be reduce.
Embodiment 4:
A kind of high electric field induced strain lead-free piezoceramic material of the present embodiment, the chemical general formula of the material is 0.9 [0.94BNT-
0.06BT] -0.1BiT, wherein, x represents the mass ratio of BiT.
Preparation method specifically includes following steps:
(1)Bi4Ti3O12The preparation of flaky powder:With Bi2O3、TiO2And NaCl is raw material, first according to Bi4Ti3O12Middle Bi and
The stoichiometric ratio of Ti elements weighs Bi2O3And TiO2, NaCl, absolute ethyl alcohol, ball milling mixing are added in, drying is transferred to crucible
In, it after sintering processes, is cooled to room temperature, is rinsed with deionized water, remove NaCl, drying obtains Bi4Ti3O12Flake powder
Body;
(2)(Bi0.5Na0.5Ti)O3The preparation of base-material:With NaCO3、Bi2O3And TiO2For raw material, according to (Bi0.5Na0.5Ti)
O3The stoichiometric ratio of middle Na, Bi and Ti element weighs NaCO3、Bi2O3And TiO2, successively through dispensing, batch mixing and heat treatment, i.e.,
(Bi is made0.5Na0.5Ti)O3Base-material;
(3)BaTiO3The preparation of base-material:With BaCO3、TiO2For raw material, according to BaTiO3The chemistry meter of middle Ba and Ti elements
Amount ratio weighs BaCO3And TiO2, successively through dispensing, batch mixing and heat treatment, obtain BaTiO3Base-material;
(4)0.94(Bi0.5Na0.5)TiO3-0.06BaTiO3The preparation of base-material:By (Bi0.5Na0.5Ti)O3Base-material with
BaTiO3Base-material is 0.94 in molar ratio:0.06 mixing, adds in absolute ethyl alcohol, ball milling, and drying crosses 80 mesh sieve, obtains 0.94
(Bi0.5Na0.5)TiO3-0.06BaTiO3Base-material;
(5) preparation of lead-free piezoceramic material:By 0.94 (Bi0.5Na0.5)TiO3-0.06BaTiO3Base-material with
Bi4Ti3O12Flaky powder is 0.9 in mass ratio:0.1 mixing adds in absolute ethyl alcohol, ball milling, and 80 mesh sieve is crossed in drying, is added in viscous
Mixture is granulated, by compression molding, green body is made, and green body at 600 DEG C is arranged and is glued, by solid-phase sintering, obtains 0.9
[0.94BNT-0.06BT] -0.1BiT ceramic materials.
Wherein, in step (1), the condition of sintering processes is:820 DEG C, Isothermal sinter 1h are first warming up to, then is warming up to 1100
DEG C, Isothermal sinter 2h.
In step (2), it is heat-treated to handle 4h in 860 DEG C of constant temperature.
In step (3), it is heat-treated to handle 4h in 920 DEG C of constant temperature.
In step (5), adhesive is polyvinyl alcohol, quality and the (Bi of the polyvinyl alcohol0.5Na0.5Ti)O3Base-material with
BaTiO3The ratio between gross mass of base-material is 2:1.
The treatment conditions of compression molding are:Control pressure is 5MPa, is pressed into the disk green body of a diameter of 10mm.
The condition of solid-phase sintering is:In silicon carbide rod furnace, at 1200 DEG C, constant temperature processing 2h, then naturally cooled to stove
Room temperature.
0.9 [0.94BNT-0.06BT] -0.1BiT ceramic materials that the present embodiment prepares gained are used to prepare piezoelectric sensing
Device, piezoelectric motors or displacement controller.
Embodiment 5:
A kind of high electric field induced strain lead-free piezoceramic material of the present embodiment, the chemical general formula of the material is 0.85
[0.94BNT-0.06BT] -0.15BiT, wherein, x represents the mass ratio of BiT.
Preparation method specifically includes following steps:
(1)Bi4Ti3O12The preparation of flaky powder:With Bi2O3、TiO2And NaCl is raw material, first according to Bi4Ti3O12Middle Bi and
The stoichiometric ratio of Ti elements weighs Bi2O3And TiO2, NaCl, absolute ethyl alcohol, ball milling mixing are added in, drying is transferred to crucible
In, it after sintering processes, is cooled to room temperature, is rinsed with deionized water, remove NaCl, drying obtains Bi4Ti3O12Flake powder
Body;
(2)(Bi0.5Na0.5Ti)O3The preparation of base-material:With NaCO3、Bi2O3And TiO2For raw material, according to (Bi0.5Na0.5Ti)
O3The stoichiometric ratio of middle Na, Bi and Ti element weighs NaCO3、Bi2O3And TiO2, successively through dispensing, batch mixing and heat treatment, i.e.,
(Bi is made0.5Na0.5Ti)O3Base-material;
(3)BaTiO3The preparation of base-material:With BaCO3、TiO2For raw material, according to BaTiO3The chemistry meter of middle Ba and Ti elements
Amount ratio weighs BaCO3And TiO2, successively through dispensing, batch mixing and heat treatment, obtain BaTiO3Base-material;
(4)0.94(Bi0.5Na0.5)TiO3-0.06BaTiO3The preparation of base-material:By (Bi0.5Na0.5Ti)O3Base-material with
BaTiO3Base-material is 0.94 in molar ratio:0.06 mixing, adds in absolute ethyl alcohol, ball milling, and drying crosses 80 mesh sieve, obtains 0.94
(Bi0.5Na0.5)TiO3-0.06BaTiO3Base-material;
(5) preparation of lead-free piezoceramic material:By 0.94 (Bi0.5Na0.5)TiO3-0.06BaTiO3Base-material with
Bi4Ti3O12Flaky powder is 0.85 in mass ratio:0.15 mixing, adds in absolute ethyl alcohol, ball milling, and drying is crossed 80 mesh sieve, added in
Adhesive is granulated, by compression molding, green body is made, and green body is warming up to 600 DEG C with 3 DEG C/min, and heat preservation 10h carries out row and glues,
By solid-phase sintering, 0.85 [0.94BNT-0.06BT] -0.15BiT ceramic materials are obtained.
Wherein, in step (1), the condition of sintering processes is:800 DEG C, Isothermal sinter 2h are first warming up to, then is warming up to 1000
DEG C, Isothermal sinter 3h.
In step (2), it is heat-treated to handle 6h in 840 DEG C of constant temperature.
In step (3), it is heat-treated to handle 6h in 900 DEG C of constant temperature.
In step (5), adhesive is polyvinyl alcohol, quality and the (Bi of the polyvinyl alcohol0.5Na0.5Ti)O3Base-material with
BaTiO3The ratio between gross mass of base-material is 2:1.
The treatment conditions of compression molding are:Control pressure is 4MPa, is pressed into the disk green body of a diameter of 10mm.
The condition of solid-phase sintering is:In silicon carbide rod furnace, at 1100 DEG C, constant temperature processing 4h, then naturally cooled to stove
Room temperature.
0.85 [0.94BNT-0.06BT] -0.15BiT ceramic materials that the present embodiment prepares gained are used to prepare piezoelectricity biography
Sensor, piezoelectric motors or displacement controller.
Embodiment 6:
A kind of high electric field induced strain lead-free piezoceramic material of the present embodiment, the chemical general formula of the material is 0.88
[0.94BNT-0.06BT] -0.12BiT, wherein, x represents the mass ratio of BiT.
Preparation method specifically includes following steps:
(1)Bi4Ti3O12The preparation of flaky powder:With Bi2O3、TiO2And NaCl is raw material, first according to Bi4Ti3O12Middle Bi and
The stoichiometric ratio of Ti elements weighs Bi2O3And TiO2, NaCl, absolute ethyl alcohol, ball milling mixing are added in, drying is transferred to crucible
In, it after sintering processes, is cooled to room temperature, is rinsed with deionized water, remove NaCl, drying obtains Bi4Ti3O12Flake powder
Body;
(2)(Bi0.5Na0.5Ti)O3The preparation of base-material:With NaCO3、Bi2O3And TiO2For raw material, according to (Bi0.5Na0.5Ti)
O3The stoichiometric ratio of middle Na, Bi and Ti element weighs NaCO3、Bi2O3And TiO2, successively through dispensing, batch mixing and heat treatment, i.e.,
(Bi is made0.5Na0.5Ti)O3Base-material;
(3)BaTiO3The preparation of base-material:With BaCO3、TiO2For raw material, according to BaTiO3The chemistry meter of middle Ba and Ti elements
Amount ratio weighs BaCO3And TiO2, successively through dispensing, batch mixing and heat treatment, obtain BaTiO3Base-material;
(4)0.94(Bi0.5Na0.5)TiO3-0.06BaTiO3The preparation of base-material:By (Bi0.5Na0.5Ti)O3Base-material with
BaTiO3Base-material is 0.94 in molar ratio:0.06 mixing, adds in absolute ethyl alcohol, ball milling, and drying crosses 80 mesh sieve, obtains 0.94
(Bi0.5Na0.5)TiO3-0.06BaTiO3Base-material;
(5) preparation of lead-free piezoceramic material:By 0.94 (Bi0.5Na0.5)TiO3-0.06BaTiO3Base-material with
Bi4Ti3O12Flaky powder is 0.88 in mass ratio:0.12 mixing, adds in absolute ethyl alcohol, ball milling, and drying is crossed 80 mesh sieve, added in
Adhesive is granulated, by compression molding, green body is made, and green body is warming up to 500 DEG C with 3 DEG C/min, and heat preservation 10h carries out row and glues,
By solid-phase sintering, 0.88 [0.94BNT-0.06BT] -0.12BiT ceramic materials are obtained.
Wherein, in step (1), the condition of sintering processes is:815 DEG C, Isothermal sinter 1.5h are first warming up to, then is warming up to
1050 DEG C, Isothermal sinter 2.5h.
In step (2), it is heat-treated to handle 5h in 850 DEG C of constant temperature.
In step (3), it is heat-treated to handle 5h in 910 DEG C of constant temperature.
In step (5), adhesive is polyvinyl alcohol, quality and the (Bi of the polyvinyl alcohol0.5Na0.5Ti)O3Base-material with
BaTiO3The ratio between gross mass of base-material is 2:1.
The treatment conditions of compression molding are:Control pressure is 4.5MPa, is pressed into the disk green body of a diameter of 10mm.
The condition of solid-phase sintering is:In silicon carbide rod furnace, at 1150 DEG C, constant temperature processing 3h, then naturally cooled to stove
Room temperature.
0.88 [0.94BNT-0.06BT] -0.12BiT ceramic materials that the present embodiment prepares gained are used to prepare piezoelectricity biography
Sensor, piezoelectric motors or displacement controller.
Embodiment 7:
A kind of high electric field induced strain lead-free piezoceramic material of the present embodiment, the chemical general formula of the material is 0.92
[0.94BNT-0.06BT] -0.08BiT, wherein, x represents the mass ratio of BiT.
Preparation method specifically includes following steps:
(1)Bi4Ti3O12The preparation of flaky powder:With Bi2O3、TiO2And NaCl is raw material, first according to Bi4Ti3O12Middle Bi and
The stoichiometric ratio of Ti elements weighs Bi2O3And TiO2, NaCl, absolute ethyl alcohol, ball milling mixing are added in, drying is transferred to crucible
In, it after sintering processes, is cooled to room temperature, is rinsed with deionized water, remove NaCl, drying obtains Bi4Ti3O12Flake powder
Body;
(2)(Bi0.5Na0.5Ti)O3The preparation of base-material:With NaCO3、Bi2O3And TiO2For raw material, according to (Bi0.5Na0.5Ti)
O3The stoichiometric ratio of middle Na, Bi and Ti element weighs NaCO3、Bi2O3And TiO2, successively through dispensing, batch mixing and heat treatment, i.e.,
(Bi is made0.5Na0.5Ti)O3Base-material;
(3)BaTiO3The preparation of base-material:With BaCO3、TiO2For raw material, according to BaTiO3The chemistry meter of middle Ba and Ti elements
Amount ratio weighs BaCO3And TiO2, successively through dispensing, batch mixing and heat treatment, obtain BaTiO3Base-material;
(4)0.94(Bi0.5Na0.5)TiO3-0.06BaTiO3The preparation of base-material:By (Bi0.5Na0.5Ti)O3Base-material with
BaTiO3Base-material is 0.94 in molar ratio:0.06 mixing, adds in absolute ethyl alcohol, ball milling, and drying crosses 80 mesh sieve, obtains 0.94
(Bi0.5Na0.5)TiO3-0.06BaTiO3Base-material;
(5) preparation of lead-free piezoceramic material:By 0.94 (Bi0.5Na0.5)TiO3-0.06BaTiO3Base-material with
Bi4Ti3O12Flaky powder is 0.92 in mass ratio:0.08 mixing, adds in absolute ethyl alcohol, ball milling, and drying is crossed 80 mesh sieve, added in
Adhesive is granulated, by compression molding, green body is made, and green body is warming up to 540 DEG C with 3 DEG C/min, and heat preservation 10h carries out row and glues,
By solid-phase sintering, 0.92 [0.94BNT-0.06BT] -0.08BiT ceramic materials are obtained.
Wherein, in step (1), the condition of sintering processes is:812 DEG C, Isothermal sinter 1h are first warming up to, then is warming up to 1080
DEG C, Isothermal sinter 3h.
In step (2), it is heat-treated to handle 6h in 845 DEG C of constant temperature.
In step (3), it is heat-treated to handle 6h in 905 DEG C of constant temperature.
In step (5), adhesive is polyvinyl alcohol, quality and the (Bi of the polyvinyl alcohol0.5Na0.5Ti)O3Base-material with
BaTiO3The ratio between gross mass of base-material is 2:1.
The treatment conditions of compression molding are:Control pressure is 4.8MPa, is pressed into the disk green body of a diameter of 10mm.
The condition of solid-phase sintering is:In silicon carbide rod furnace, at 1180 DEG C, constant temperature processing 2.5h, then with stove natural cooling
To room temperature.
0.92 [0.94BNT-0.06BT] -0.08BiT ceramic materials that the present embodiment prepares gained are used to prepare piezoelectricity biography
Sensor, piezoelectric motors or displacement controller.
Claims (2)
1. a kind of preparation method of high electric field induced strain lead-free piezoceramic material, which is characterized in that the chemistry of the material leads to
Formula is (1-x) [0.94 (Bi0.5Na0.5)TiO3-0.06BaTiO3]-xBi4Ti3O12, wherein, x Bi4Ti3O12Mass content,
0 < x≤0.15, the preparation method specifically include following steps:
(1) 0.94 (Bi of perovskite structure is prepared0.5Na0.5)TiO3-0.06BaTiO3Matrix of powder material;
(2) bismuth laminated Bi is prepared4Ti3O12Flaky powder material;
(3) by 0.94 (Bi0.5Na0.5)TiO3-0.06BaTiO3Matrix of powder material and Bi4Ti3O12Flaky powder is (1- in mass ratio
x):X is mixed, wherein, 0 < x≤0.15, ball milling, drying, after sieving, addition adhesive, then through granulation, compression molding, base is made
Body by solid-phase sintering, obtains (1-x) [0.94 (Bi0.5Na0.5)TiO3-0.06BaTiO3]-xBi4Ti3O12Ceramic material;
Bismuth laminated Bi in step (2)4Ti3O12The preparation method of flaky powder material is as follows:
With Bi2O3、TiO2And NaCl is raw material, first according to Bi4Ti3O12The stoichiometric ratio of middle Bi and Ti elements weighs Bi2O3And
TiO2, NaCl, absolute ethyl alcohol, ball milling mixing are added in, drying is transferred in crucible, after sintering processes, is cooled to room temperature, and uses
Deionized water is rinsed, and removes NaCl, and drying obtains Bi4Ti3O12Flaky powder;
Wherein, the condition of the sintering processes is:800-820 DEG C, Isothermal sinter 1-2h is first warming up to, then is warming up to 1000-
1100 DEG C, Isothermal sinter 2-3h;
Adhesive described in step (3) is polyvinyl alcohol, quality and the (Bi of the polyvinyl alcohol0.5Na0.5Ti)O3Base-material and BaTiO3
The ratio between gross mass of base-material is 2:1;The treatment conditions of the compression molding are:Control pressure is 4-5MPa, is pressed into diameter
Disk green body for 10mm;The condition of the solid-phase sintering is:In silicon carbide rod furnace, at 1100-1200 DEG C, constant temperature processing
2-4h, then with stove cooled to room temperature.
2. the application of high electric field induced strain lead-free piezoceramic material being prepared using method described in claim 1, special
Sign is that the lead-free piezoceramic material is used to prepare piezoelectric transducer, piezoelectric motors or displacement controller.
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