CN107324804A - Leadless piezoelectric ceramics and preparation method thereof - Google Patents
Leadless piezoelectric ceramics and preparation method thereof Download PDFInfo
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- CN107324804A CN107324804A CN201710566793.7A CN201710566793A CN107324804A CN 107324804 A CN107324804 A CN 107324804A CN 201710566793 A CN201710566793 A CN 201710566793A CN 107324804 A CN107324804 A CN 107324804A
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- piezoelectric ceramics
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- leadless piezoelectric
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- 239000000919 ceramic Substances 0.000 title claims abstract description 126
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- 239000000203 mixture Substances 0.000 claims abstract description 103
- 150000001875 compounds Chemical group 0.000 claims abstract description 17
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims description 72
- 239000002994 raw material Substances 0.000 claims description 63
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 50
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 50
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 50
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 48
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 44
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 44
- 238000005245 sintering Methods 0.000 claims description 43
- 239000012254 powdered material Substances 0.000 claims description 42
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 32
- 230000010287 polarization Effects 0.000 claims description 31
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 27
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 26
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 claims description 25
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 25
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 25
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 25
- 239000011812 mixed powder Substances 0.000 claims description 24
- 229910004481 Ta2O3 Inorganic materials 0.000 claims description 20
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 19
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 19
- 238000005303 weighing Methods 0.000 claims description 18
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- 238000001035 drying Methods 0.000 claims description 14
- 239000003979 granulating agent Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical group O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000000463 material Substances 0.000 description 21
- 239000011734 sodium Substances 0.000 description 12
- 230000008859 change Effects 0.000 description 11
- 230000002441 reversible effect Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000011575 calcium Substances 0.000 description 8
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- 230000002269 spontaneous effect Effects 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
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- 229910002976 CaZrO3 Inorganic materials 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical group [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
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- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
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- 239000013078 crystal Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
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- 229960002415 trichloroethylene Drugs 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- C04B35/495—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 vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
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- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
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Abstract
The invention discloses a kind of leadless piezoelectric ceramics and preparation method thereof.The ceramics are with following represented by formula I：(KaNabBicLidNb1‑e‑f‑gSbeTifTagO3)(1‑x)(Ba1‑ jCajZrO3)x‑Gy(I) wherein, 0≤x≤0.10,0≤y≤2.0, the ＜ b ＜ 0.8 of 0 ＜ a ＜ 0.8,0,0≤c≤0.08,0≤d≤0.08,0≤e≤0.06,0≤f≤0.08,0≤g≤0.08,0≤j≤1.0, wherein, oxides of the G selected from rare earth element, one or more kinds of mixtures in CuO, ZnO, wherein, y is compound (K shared by GaNabBicLidNb1‑e‑f‑gSbeTifTagO3)(1‑x)(Ba1‑ jCajZrO3)xMolar percentage.The leadless piezoelectric ceramics has good piezoelectric property.
Description
Technical field
The present invention relates to piezoelectric ceramic technology field, more particularly, to a kind of leadless piezoelectric material material and preparation method thereof.
Background technology
Piezoelectric is used as one due to forward and inverse piezoelectric property, the mutual conversion of mechanical energy and electric energy can be achieved
Plant important functional material and be widely used in piezo-electric resonator, piezoelectric buzzer, piezoelectric filter, piezoelectric transformer, piezoelectricity
The high-technology fields such as loudspeaker, piezoelectrics and piezo-electric motor.
At present, lead base piezoelectric ceramics is lead oxide in most widely used piezoelectric, but lead base piezoelectric ceramics raw material
Content is typically up to more than 60%.It is well known that lead is a kind of noxious material, accumulates in human body and be difficult discharge, and to human body
Health causes serious harm health.Meanwhile, easily environment is polluted during production, use.Therefore, study
High performance leadless piezoelectric ceramics is significant.
Base metal niobate (K0.5Na0.5NbO3：KNN) there is higher Curie temperature and larger electromechanical coupling factor,
It is considered as the lead-free piezoceramic material for being most hopeful to replace lead base piezoelectric ceramics.However, the sintering temperature of the material is high, and
And alkali metal source is readily volatilized under high temperature sintering, the compactness and piezoelectric property of ceramics are reduced.While temperature stability
It is also to limit its wide variety of key factor, therefore the sintering temperature of reduction KNN based leadless piezoelectric ceramics, while lifting temperature
Stability is most important for leadless piezoelectric ceramics.
The content of the invention
It is an object of the present invention to provide a kind of new solution of leadless piezoelectric ceramics.
There is provided a kind of leadless piezoelectric ceramics according to the first aspect of the invention.The ceramics are with following represented by formula I：
(KaNabBicLidNb1-e-f-gSbeTifTagO3)(1-x)(Ba1-jCajZrO3)x-Gy (I)
Wherein, 0≤x≤0.10,0≤y≤2.0,0 ＜ a ＜ 0.8,0 ＜ b ＜ 0.8,0≤c≤0.08,0≤d≤0.08,
0≤e≤0.06,0≤f≤0.08,0≤g≤0.08,0≤j≤1.0,
Wherein, oxides of the G selected from rare earth element, one or more kinds of mixtures in CuO, ZnO,
Wherein, y is compound (K shared by GaNabBicLidNb1-e-f-gSbeTifTagO3)(1-x) (Ba1-jCajZrO3)xRub
That percentage.
Alternatively, wherein, 0≤x≤0.04,0≤y≤1.5,0.32≤a≤0.60,0.40≤b≤0.68, and 0.6
≤ a/b≤1.3,0≤c≤0.02,0≤d≤0.02,0≤e≤0.04,0≤f≤0.02,0≤g≤0.02,0≤j≤1.0.
Alternatively, the oxide of the rare earth element is CeO2。
Alternatively, the leadless piezoelectric ceramics is perovskite structure.
There is provided a kind of preparation method of leadless piezoelectric ceramics according to the second aspect of the invention.The preparation method bag
Include following steps：
S1, dispensing：
With K2CO3、Na2CO3、Bi2O3、Li2CO3、Nb2O5、Sb2O3、TiO2、Ta2O3、BaCO3、 CaCO3、ZrO2And G is
Raw material, various raw materials are according to chemical formula (KaNabBicLidNb1-e-f-gSbeTifTagO3)(1-x)(Ba1-jCajZrO3)x-GyIn a,
B, c, d, e, f, g, j, x, y setting value carry out weighing dispensing,
Wherein, 0≤x≤0.10,0≤y≤2.0,0 ＜ a ＜ 0.8,0 ＜ b ＜ 0.8,0≤c≤0.08,0≤d≤0.08,
0≤e≤0.06,0≤f≤0.08,0≤g≤0.08,0≤j≤1.0,
Wherein, oxides of the G selected from rare earth element, one or more kinds of mixtures in CuO, ZnO,
Wherein, y is compound (K shared by GaNabBicLidNb1-e-f-gSbeTifTagO3)(1-x) (Ba1-jCajZrO3)xRub
That percentage；
S2, preparation
S21, by K2CO3、Na2CO3、Bi2O3、Li2CO3、Nb2O5、Sb2O3、TiO2、Ta2O3、BaCO3、 CaCO3And ZrO2's
Mixture carries out pre-burning, to obtain the first preburning powdered material,
S22, add G into first preburning powdered material, and be prepared into mixed powder,
S23, into the mixed powder granulating agent is added, to form the powder of good fluidity, and prepared by the powder
Into the crude green body of setting shape,
S24, by the crude green body carry out dumping processing,
S25, dumping is handled after the crude green body be sintered, to obtain ceramic component；
S3, polarization
Ceramic component is polarized, to obtain leadless piezoelectric ceramics device.
Alternatively, in S21 steps, including：
To K2CO3、Na2CO3、Bi2O3、Li2CO3、Nb2O5、Sb2O3、TiO2、Ta2O3、BaCO3、 CaCO3And ZrO2Mixing
Absolute ethyl alcohol is added in thing, and carries out first time mix grinding；
Mixture after first time mix grinding is dried；
Mixture after drying is subjected to pre-burning, to obtain the first preburning powdered material.
Alternatively, the first time mix grinding time is 10-30 hours, and calcined temperature is 850-900 DEG C, and burn-in time is that 3-8 is small
When.
Alternatively, in S22 steps, including：Absolute ethyl alcohol is added into the first preburning powdered material for adding G, and carries out the
Secondary mix grinding；
Powder after second of mix grinding is dried, to obtain mixed powder.
Alternatively, in S23 steps, the granulating agent is the aqueous solution of polyvinyl alcohol, the aqueous solution of the polyvinyl alcohol
Mass concentration be 4%-12%.
Alternatively, in S25 steps, sintering temperature is 920-1120 DEG C, and sintering time is 2-6 hours.
Alternatively, in S3 steps, including：Top electrode is plated on the ceramic component, and is put into silicone oil and applies 2-
4kV/mm direct current, to be polarized, the polarization time is 15-30 minutes.
There is provided a kind of preparation method of leadless piezoelectric ceramics according to the third aspect of the invention we.The preparation method includes
Following steps：
SS1, dispensing：
With K2CO3、Na2CO3、Bi2O3、Li2CO3、Nb2O5、Sb2O3、TiO2、Ta2O3、BaCO3、 CaCO3、ZrO2And G is
Raw material, various raw materials are according to chemical formula (KaNabBicLidNb1-e-f-gSbeTifTagO3)(1-x)(Ba1-jCajZrO3)x-GyIn a,
B, c, d, e, f, g, j, x, y setting value carry out weighing dispensing,
Wherein, 0≤x≤0.10,0≤y≤2.0,0 ＜ a ＜ 0.8,0 ＜ b ＜ 0.8,0≤c≤0.08,0≤d≤0.08,
0≤e≤0.06,0≤f≤0.08,0≤g≤0.08,0≤j≤1.0,
Wherein, oxides of the G selected from rare earth element, one or more kinds of mixtures in CuO, ZnO,
Wherein, y is compound (K shared by GaNabBicLidNb1-e-f-gSbeTifTagO3)(1-x) (Ba1-jCajZrO3)xRub
That percentage；
SS2, preparation
SS21, by K2CO3、Na2CO3、Bi2O3、Li2CO3、Nb2O5、Sb2O3、TiO2、Ta2O3、BaCO3、 CaCO3、ZrO2With
G mixture carries out pre-burning, to obtain the second preburning powdered material,
SS22, into second preburning powdered material granulating agent is added, to form the powder of good fluidity, and by the powder
The crude green body of setting shape is prepared into,
SS23, by the crude green body carry out dumping processing,
SS24, dumping is handled after the crude green body be sintered, to obtain ceramic component；
SS3, polarization
Ceramic component is polarized, to obtain leadless piezoelectric ceramics device.
Alternatively, in SS21 steps, calcined temperature is 850-900 DEG C, and burn-in time is 3-8 hours.
Alternatively, in SS22 steps, the granulating agent is the aqueous solution of polyvinyl alcohol, the aqueous solution of the polyvinyl alcohol
Mass concentration be 4%-12%.
Alternatively, in SS24 steps, sintering temperature is 920-1120 DEG C, and sintering time is 2-6 hours.
Alternatively, in SS3 steps, including：Top electrode is plated on the ceramic component, and is put into silicone oil and applies 2-
4kV/mm direct current, to be polarized, the polarization time is 15-30 minutes.
It was found by the inventors of the present invention that in the prior art, base metal niobate (K0.5Na0.5NbO3：KNN) have compared with
High Curie temperature and larger electromechanical coupling factor.However, the sintering temperature of the material is high, and alkali metal source is in high temperature
It is readily volatilized under sintering, cause compactness and the piezoelectric property reduction of ceramics.Therefore, the technical assignment to be realized of the present invention or
Person's technical problem to be solved be it is that those skilled in the art never expect or it is not expected that, therefore the present invention is a kind of
New technical scheme.
Embodiment
The description only actually at least one exemplary embodiment is illustrative below, never as to the present invention
And its any limitation applied or used.
It may be not discussed in detail for technology, method and apparatus known to person of ordinary skill in the relevant, but suitable
In the case of, the technology, method and apparatus should be considered as a part for specification.
In shown here and discussion all examples, any occurrence should be construed as merely exemplary, without
It is as limitation.Therefore, other examples of exemplary embodiment can have different values.
There is provided a kind of leadless piezoelectric ceramics according to one embodiment of present invention.The leadless piezoelectric ceramics is with followingization
Formulas I is learned to represent：
(KaNabBicLidNb1-e-f-gSbeTifTagO3)(1-x)(Ba1-jCajZrO3)x-Gy (I)
Wherein, 0≤x≤0.10,0≤y≤2.0,0 ＜ a ＜ 0.8,0 ＜ b ＜ 0.8,0≤c≤0.08,0≤d≤0.08,
0≤e≤0.06,0≤f≤0.08,0≤g≤0.08,0≤j≤1.0,
Wherein, oxides of the G selected from rare earth element, one or more kinds of mixtures in CuO, ZnO.In the preparation, G
Added as sintering aid in raw material so that the sintering temperature of leadless piezoelectric ceramics is significantly reduced, and reduces waving for alkali metal source
Hair.
Wherein, y is compound (K shared by GaNabBicLidNb1-e-f-gSbeTifTagO3)(1-x) (Ba1-jCajZrO3)xRub
That percentage.
It should be noted that G can be one or more kinds of mixtures in the oxide of rare earth element, CuO, ZnO.
Preferably, the oxide of rare earth element is cerium oxide (CeO2)。CeO2The obtained compound I that adulterates has more excellent pressure
Electrical property.
Y span is compound (K shared by 0-2.0, i.e. GaNabBicLidNb1-e-f-gSbeTifTagO3) (1-x)(Ba1- jCajZrO3)xMolar percentage be 0-2.0%.
The leadless piezoelectric ceramics that the present invention is provided has piezoelectric constant d33 high, the reverse ﹡ of piezoelectric coefficient d 33 in room temperature extremely
Fluctuation range within the temperature range of 170 DEG C is small, the characteristics of Curie temperature Tc is high.
In addition, the compactness of the leadless piezoelectric ceramics is high.
In addition, the practicality of the leadless piezoelectric ceramics is wide.
Preferably, in Formula I parameters scope, wherein, 0≤x≤0.04,0≤y≤1.5,0.32≤a≤
0.60,0.40≤b≤0.68, and 0.6≤a/b≤1.3,0≤c≤0.02,0≤d≤0.02,0≤e≤0.04,0≤f≤
0.02,0≤g≤0.02,0≤j≤1.0.
In the span, the combination property of leadless piezoelectric ceramics is more excellent, and piezoelectric constant d33 is higher, reversely pressure
The stability of electrostrictive coefficient d33 ﹡ at different temperatures is more preferable.
Preferably, the leadless piezoelectric ceramics is perovskite structure.The ceramic material of the structure, piezoelectric effect is good.
According to another embodiment of the invention there is provided a kind of preparation method of leadless piezoelectric ceramics, wherein, including with
Lower step：
S1, dispensing
With K2CO3、Na2CO3、Bi2O3、Li2CO3、Nb2O5、Sb2O3、TiO2、Ta2O3、BaCO3、 CaCO3、ZrO2And G is
Raw material, various raw materials are according to Formula I (KaNabBicLidNb1-e-f-gSbeTifTagO3)(1-x)(Ba1-jCajZrO3)x-GyIn
A, b, c, d, e, f, g, j, x, y setting value carry out weighing dispensing,
Wherein, 0≤x≤0.10,0≤y≤2.0,0 ＜ a ＜ 0.8,0 ＜ b ＜ 0.8,0≤c≤0.08,0≤d≤0.08,
0≤e≤0.06,0≤f≤0.08,0≤g≤0.08,0≤j≤1.0,
Wherein, oxides of the G selected from rare earth element, one or more kinds of mixtures in CuO, ZnO,
Wherein, y is compound (K shared by GaNabBicLidNb1-e-f-gSbeTifTagO3)(1-x) (Ba1-jCajZrO3)xRub
That percentage.
Specifically, above-mentioned various raw materials are powder.Weighing is carried out according to the proportionate relationship of the element of each in Formula I to match somebody with somebody
Material.G can be one or more kinds of mixtures in the oxide of rare earth element, CuO, ZnO.
By sintering aid G addition, the sintering temperature of leadless piezoelectric ceramics is reduced, is existed so as to greatly reduce alkali metal
Volatilization under high temperature sintering, improves the compactness and piezoelectric property of leadless piezoelectric ceramics.
Those skilled in the art can set the consumption of various raw materials according to actual needs.
S2, preparation
S21, by K2CO3、Na2CO3、Bi2O3、Li2CO3、Nb2O5、Sb2O3、TiO2、Ta2O3、BaCO3、 CaCO3And ZrO2's
Mixture carries out pre-burning, to obtain the first preburning powdered material.
For example, in this step, first, to K2CO3、Na2CO3、Bi2O3、Li2CO3、Nb2O5、 Sb2O3、TiO2、Ta2O3、
BaCO3、CaCO3And ZrO2Mixture in add absolute ethyl alcohol, and carry out first time mix grinding.The addition of absolute ethyl alcohol can increase
Plus the viscosity of raw material, so that first time mix grinding is more abundant, obtained powder is more finely, evenly.First time mix grinding uses ball
The method of mill is carried out.Preferably, the first time mix grinding time is 10-30 hours.Further, the time of first time mix grinding is
20 hours.In intergrinding process, powder becomes more finely, evenly.
Then, the mixture after first time mix grinding is dried, to exclude absolute ethyl alcohol.
Finally, the mixture after drying is subjected to pre-burning, to obtain the first preburning powdered material.The purpose of pre-burning is：Make each
Fully, uniformly, the solid solution that generation constituent is fixed forms principal crystalline phase to the solid state reaction of raw material；And exclude raw material
In carbon dioxide and moisture, reduce crude green body burns till contractions, deform, in order to control the appearance and size of ceramic.
Preferably, calcined temperature is 850-900 DEG C.Burn-in time is 3-8 hours.Under the conditions of the pre-burning, each is former
The solid state reaction of material is more fully, evenly.Further, burn-in time is 5 hours.
S22, G is added into the first preburning powdered material, and be prepared into mixed powder.
For example, in this step, including：Absolute ethyl alcohol is added into the first preburning powdered material for adding G, and is carried out second
Mix grinding.Similarly, the addition of absolute ethyl alcohol can increase the viscosity of the first preburning powdered material, so that second of mix grinding is more abundant, obtain
The first preburning powdered material arrived is more finely, evenly.
Powder after second of mix grinding is dried, to obtain mixed powder.Absolute ethyl alcohol can be excluded by drying,
Absolute ethyl alcohol is avoided to adversely affect follow-up sintering.For example, the method that second of mix grinding also uses ball milling.It is preferred that
It is that the time of second of mix grinding is 20 hours.Through second of mix grinding, thinner, mixed powder evenly has been obtained.
S23, granulating agent is added into mixed powder, to form the powder of good fluidity, and by the powder system after granulating
The standby crude green body into setting shape.For example, the method suppressed using mould is shaped, the size of obtained crude green body is Ф 10*2mm.Slightly
The shape of base is prepared according to the structure of piezoelectric patches.
Preferably, granulating agent is the aqueous solution of polyvinyl alcohol.The mass concentration of the aqueous solution of polyvinyl alcohol is 4%-
12%.The granulating agent has viscosity high, the characteristics of consumption is few.
S24, by crude green body carry out dumping processing.The purpose of dumping is that the producing high-molecular such as polyvinyl alcohol removed in crude green body is closed
Thing, to avoid adversely affecting sintering.The phosphorus content of high-molecular compound is more, and when oxygen is not enough, burning produces reduction
Property very strong carbon monoxide.Oxide in raw material can be reduced to metal or low oxide by carbon monoxide.Metal is low
The color of valency oxide influence ceramics, into performances such as porcelain, electrodepositable and polarization.
In one example, pre- dumping is carried out using organic solvent first.Optionally, organic solvent is trichlorine to pre- dumping
One kind in ethene, carbon tetrachloride, chloroform, acetone.
Then, the crude green body after pre- dumping is subjected to dumping processing at high temperature, the organic matters such as polyvinyl alcohol is thoroughly arranged
Remove.The temperature of dumping processing is 500-700 DEG C.
In another example, crude green body is directly subjected to dumping processing at high temperature, in this way, can also be excluded
The high-molecular compounds such as polyvinyl alcohol.
S25, dumping is handled after crude green body be sintered, to obtain ceramic component.Sintering can be to enter in air sintering furnace
OK.Preferably, sintering temperature is 920-1120 DEG C, and sintering time is 2-6 hours.Crude green body is sintered under this condition, most
Ceramic component of the end form into perovskite structure.The ceramic component is represented with compound I.There is each side in the crystal of ceramic component
To spontaneous polarization, from polarity is not externally macroscopically presented.Spontaneous polarization direction identical region is referred to as electricdomain.
S3, polarization
Ceramic component is polarized, to obtain leadless piezoelectric ceramics device.Occur by the electricdomain of polarized ceramics element
Turn to, i.e. polarization forces the spontaneous polarization of electricdomain to align, so that polarity is presented in ceramic component.
Preferably, in this step, including：First, Top electrode is plated on ceramic component, in order to be polarized.
Then, ceramic component is put into the direct current for applying 2-4kV/mm in silicone oil, to be polarized, the polarization time is
15-30 minutes.
By polarization, ceramic component turns into the piezoelectric ceramic devices with piezoelectric property.
In other examples, ceramic component is directly polarized under atmospheric environment, ceramic component is had pressure
Electrical property.
There is provided a kind of preparation method of leadless piezoelectric ceramics according to still another embodiment of the invention.This method includes
Following steps：
SS1, dispensing
With K2CO3、Na2CO3、Bi2O3、Li2CO3、Nb2O5、Sb2O3、TiO2、Ta2O3、BaCO3、CaCO3、ZrO2And G is
Raw material, various raw materials are according to chemical formula (KaNabBicLidNb1-e-f-gSbeTifTagO3)(1-x)(Ba1-jCajZrO3)x-GyIn a,
B, c, d, e, f, g, j, x, y setting value carry out weighing dispensing,
Wherein, 0≤x≤0.10,0≤y≤2.0,0 ＜ a ＜ 0.8,0 ＜ b ＜ 0.8,0≤c≤0.08,0≤d≤0.08,
0≤e≤0.06,0≤f≤0.08,0≤g≤0.08,0≤j≤1.0,
Wherein, oxides of the G selected from rare earth element, one or more kinds of mixtures in CuO, ZnO,
Wherein, y is compound (K shared by GaNabBicLidNb1-e-f-gSbeTifTagO3)(1-x) (Ba1-jCajZrO3)xRub
That percentage.
Specifically, above-mentioned various raw materials are powder.Weighing is carried out according to the proportionate relationship of the element of each in Formula I to match somebody with somebody
Material.G can be one or more kinds of mixtures in the oxide of rare earth element, CuO, ZnO.G is being prepared as sintering aid
When, the sintering temperature of leadless piezoelectric ceramics can be significantly reduced.
Those skilled in the art can set the consumption of various raw materials according to actual needs.
SS2, preparation
SS21, by K2CO3、Na2CO3、Bi2O3、Li2CO3、Nb2O5、Sb2O3、TiO2、Ta2O3、BaCO3、 CaCO3、ZrO2With
G mixture carries out pre-burning, to obtain the second preburning powdered material.
In the method, all raw materials mix and directly carry out pre-burning, to obtain the second preburning powdered material.
For example, adding absolute ethyl alcohol into the mixture of all raw materials.Using the method for ball milling, mixture is fully mixed
Mill.For example, the mix grinding time is 20 hours, so that mixture is more finely, evenly.After mix grinding, mixture is dried first, with
Exclude absolute ethyl alcohol.Then, mixture is subjected to pre-burning.By pre-burning, the second preburning powdered material is finally given.The purpose of pre-burning is such as
It is preceding described.
Preferably, in this step, calcined temperature is 850-900 DEG C, and burn-in time is 3-8 hours.
SS22, into the second preburning powdered material granulating agent is added, to form the powder of good fluidity, and powder is prepared into set
The crude green body of setting shape.
Preferably, granulating agent is the aqueous solution of polyvinyl alcohol, and the mass concentration of the aqueous solution of polyvinyl alcohol is 4%-
12%.
For example, the method suppressed using mould is shaped, the size of obtained crude green body is Ф 10*2mm.
SS23, by crude green body carry out dumping processing.The purpose of dumping is as previously described.
In one example, pre- dumping is carried out using organic solvent first.Optionally, organic solvent be trichloro ethylene,
One kind in carbon tetrachloride, chloroform, acetone.
Then, the crude green body after pre- dumping is subjected to dumping processing at high temperature, the organic matters such as polyvinyl alcohol is thoroughly arranged
Remove.The temperature of dumping processing is 500-700 DEG C.
In another example, crude green body is directly subjected to dumping processing at high temperature, in this way, can also be excluded
The organic matters such as polyvinyl alcohol.
SS24, dumping is handled after crude green body be sintered, to obtain ceramic component.Sintering can be to enter in air sintering furnace
OK.Preferably, sintering temperature is 920-1120 DEG C, and sintering time is 2-6 hours.Under the sintering condition, calcium can be obtained
The ceramic component of perovskite like structure.The ceramic component is represented with compound I.There is the spontaneous pole of all directions in the crystal of ceramic component
Change, from polarity is not externally macroscopically presented.Spontaneous polarization identical region is referred to as electricdomain.
SS3, polarization
Ceramic component is polarized, to obtain leadless piezoelectric ceramics device.Occur by the electricdomain of polarized ceramics element
Turn to, i.e. polarization forces the spontaneous polarization of electricdomain to align, so that polarity is presented in ceramic component.
Preferably, in this step, including：First, Top electrode is plated on ceramic component, in order to be polarized.
Then, ceramic component is put into the direct current for applying 2-4kV/mm in silicone oil, to be polarized, the polarization time is
15-30 minutes.
By polarization, ceramic component is referred to as the piezoelectric ceramic devices with piezoelectric property.
In other examples, ceramic component is directly polarized under atmospheric environment, ceramic component is had pressure
Electrical property.
In the preparation method that the present invention is provided, constructed using Bi, Li element doping with compound A perovskite
Structure.
In addition, by introducing Ba1-jCajZrO3The high-T_c superconductors temperature of potassium-sodium niobate bismuth can be reduced to room temperature,
So that leadless piezoelectric ceramics obtains good piezoelectric property.
Tripartite-four directions is lifted in addition, introducing while the high-T_c superconductors temperature of potassium-sodium niobate can be down to Sb room temperature
Phase transition temperature finally obtains the ceramics with tripartite-cubic new interphase structure, and then improve the nothing to room temperature in room-temperature zone
The temperature stability of lead piezoelectric ceramics.
In addition, the sintering temperature of leadless piezoelectric ceramics is reduced by sintering aid G, so as to reduce because alkali metal source is in height
Temperature sintering is lower to volatilize, caused by ceramic compactness and piezoelectric property reduction.
Embodiment 1
It is (K to prepare by chemical formula0.48Na0.48Bi0.01Nb0.96Sb0.04O3)0.96(CaZrO3)0.04-(CeO2)yUnleaded pressure
Y=0.75 in electroceramics material, formula.
Preparation method includes：
S1-1, dispensing
With analytically pure K2CO3、Na2CO3、Bi2O3、Nb2O5、Sb2O3、CaCO3、ZrO2、CeO2For raw material, according to accordingly matching somebody with somebody
The chemical formula of side carries out weighing dispensing.
S2-1, preparation
S21-1, to prepare raw material (remove CeO2Absolute ethyl alcohol is added in outside), and carries out first time mix grinding, it is mixed for the first time
Consume time as 20 hours；
Raw material after first time mix grinding is dried；
By the raw material after drying in 850 DEG C of pre-burnings 5 hours, the first preburning powdered material is obtained.
S22-1, into the first preburning powdered material add CeO2Second of mix grinding is carried out with absolute ethyl alcohol, the mix grinding time 20 is small
When；
Powder after second of mix grinding is dried, to obtain mixed powder.
S23-1, the polyvinyl alcohol water solution for being 6% to mixed powder addition mass concentration are granulated, and use mould pressure
Type is made, to obtain Ф 10*2mm crude green body.
S24-1, crude green body is subjected to dumping processing at a temperature of 600 DEG C.
S25-1, in air sintering furnace, the crude green body after dumping is handled sinters 4h at 1100 DEG C, to obtain ceramic member
Part.
S3-1, polarization
First, the plated electrode on ceramic component；Then, the direct current for being put into application 3kV/mm in silicone oil is polarized, pole
The change time is 30 minutes, that is, obtains leadless piezoelectric ceramics device.
In this embodiment, obtained leadless piezoelectric ceramics device, performance test is carried out after standing 24 hours at normal temperatures.
Its density is 4.435g/cm3.Piezoelectric coefficient d 33 is 220pC/N, temperature of its reverse ﹡ of piezoelectric coefficient d 33 in room temperature to 170 DEG C
In the range of fluctuation be 7%.Dielectric loss tan δ are 0.03.Curie temperature Tc is 414 DEG C.
Embodiment 2
It is (K to prepare by chemical formula0.48Na0.48Bi0.01Nb0.96Sb0.04O3)0.96(CaZrO3)0.04-(CeO2)yUnleaded pressure
Y=1.5 in electroceramics material, formula.
Preparation method includes：
S1-2, dispensing
With analytically pure K2CO3、Na2CO3、Bi2O3、Nb2O5、Sb2O3、CaCO3、ZrO2、CeO2For raw material, according to accordingly matching somebody with somebody
The chemical formula of side carries out weighing dispensing.
S2-2, preparation
S21-2, to prepare raw material (remove CeO2Absolute ethyl alcohol is added in outside), and carries out first time mix grinding, it is mixed for the first time
Consume time as 20 hours；
Raw material after first time mix grinding is dried；
By the raw material after drying in 850 DEG C of pre-burnings 5 hours, the first preburning powdered material is obtained.
S22-2, into the first preburning powdered material add CeO2Second of mix grinding is carried out with absolute ethyl alcohol, the mix grinding time 20 is small
When；
Powder after second of mix grinding is dried, to obtain mixed powder.
S23-2, the polyvinyl alcohol water solution for being 6% to mixed powder addition mass concentration are granulated, and use mould pressure
Type is made, to obtain Ф 10*2mm crude green body.
S24-2, first, pre- dumping is carried out by crude green body in carbon tetrachloride；
Then, dumping processing is carried out at a temperature of 500 DEG C.
S25-2, in air sintering furnace, the crude green body after dumping is handled sinters 4h at 1100 DEG C, to obtain ceramic member
Part.
S3-2, polarization
First, the plated electrode on ceramic component；Then, the direct current for being put into application 3kV/mm in silicone oil is polarized, pole
The change time is 30 minutes, that is, obtains leadless piezoelectric ceramics device.
In this embodiment, obtained leadless piezoelectric ceramics device, after standing 24 hours at normal temperatures, carries out performance survey
Examination.Its density is 4.385g/cm3.Piezoelectric coefficient d 33 is 168pC/N, and its reverse ﹡ of piezoelectric coefficient d 33 is in room temperature to 170 DEG C
Fluctuation in temperature range is 9%.Dielectric loss tan δ are 0.04.Curie temperature Tc is 395 DEG C.
Embodiment 3
It is (K to prepare by chemical formula0.48Na0.48Bi0.01Nb0.96Sb0.02Ti0.02O3)0.96(Ba0.5Ca0.5ZrO3) 0.04-
(CuO)yLead-free piezoceramic material, y=1.5 in formula.
Preparation method includes：
S1-3, dispensing
With analytically pure K2CO3、Na2CO3、Bi2O3、Nb2O5、Sb2O3、TiO2、BaCO3、CaCO3、 ZrO2, CuO be raw material,
Weighing dispensing is carried out according to the chemical formula being accordingly formulated.
S2-3, preparation
S21-3, the addition absolute ethyl alcohol into the raw material (in addition to CuO) prepared, and carry out first time mix grinding, first time mix grinding
Time is 20 hours；
Raw material after first time mix grinding is dried；
By the raw material after drying in 800 DEG C of pre-burnings 5 hours, the first preburning powdered material is obtained.
S22-3, addition CuO and absolute ethyl alcohol second of mix grinding of progress, 20 hours mix grinding time into the first preburning powdered material；
Powder after second of mix grinding is dried, to obtain mixed powder.
S23-3, the polyvinyl alcohol water solution for being 4% to mixed powder addition mass concentration are granulated, and use mould pressure
Type is made, to obtain Ф 10*2mm crude green body.
S24-3, first, pre- dumping is carried out by crude green body in chloroform；
Then, dumping processing is carried out at a temperature of 700 DEG C.
S25-3, in air sintering furnace, the crude green body after dumping is handled sinters 4h at 1020 DEG C, to obtain ceramic member
Part.
S3-3, polarization
First, the plated electrode on ceramic component；Then, the direct current for being put into application 4kV/mm in silicone oil is polarized, pole
The change time is 15 minutes, that is, obtains leadless piezoelectric ceramics device.
In this embodiment, obtained leadless piezoelectric ceramics device, after standing 24 hours at normal temperatures, carries out performance survey
Examination.Its density is 4.183g/cm3.Piezoelectric coefficient d 33 is 264pC/N, and its reverse ﹡ of piezoelectric coefficient d 33 is in room temperature to 170 DEG C
Fluctuation in temperature range is 10%.Dielectric loss tan δ are 0.03.Curie temperature Tc is 380 DEG C.
Embodiment 4
It is (K to prepare by chemical formula0.48Na0.48Bi0.01Nb0.96Sb0.02Ta0.02O3)0.96(Ba0.5Ca0.5ZrO3) 0.04-
(ZnO)yLead-free piezoceramic material, y=1.5 in formula.
Preparation method includes：
S1-4, dispensing
With analytically pure K2CO3、Na2CO3、Bi2O3、Nb2O5、Sb2O3、Ta2O3、BaCO3、CaCO3、 ZrO2, ZnO for original
Material, weighing dispensing is carried out according to the chemical formula being accordingly formulated.
S2-4, preparation
S21-4, the addition absolute ethyl alcohol into the raw material (in addition to ZnO) prepared, and carry out first time mix grinding, first time mix grinding
Time is 20 hours；
Raw material after first time mix grinding is dried；
By the raw material after drying in 800 DEG C of pre-burnings 5 hours, the first preburning powdered material is obtained.
S22-4, addition ZnO and absolute ethyl alcohol second of mix grinding of progress, 20 hours mix grinding time into the first preburning powdered material；
Powder after second of mix grinding is dried, to obtain mixed powder.
S23-4, the polyvinyl alcohol water solution for being 12% to mixed powder addition mass concentration are granulated, and use mould pressure
Type is made, to obtain Ф 10*2mm crude green body.
S24-4, first, pre- dumping is carried out by crude green body in chloroform；
Then, dumping processing is carried out at a temperature of 550 DEG C.
S25-4, in air sintering furnace, the crude green body after dumping is handled, at 920 DEG C sinter 6 hours, to be made pottery
Porcelain element.
S3-4, polarization
First, the plated electrode on ceramic component；Then, the direct current for being put into application 2kV/mm in silicone oil is polarized, pole
The change time is 30 minutes, that is, obtains leadless piezoelectric ceramics device.
In this embodiment, obtained leadless piezoelectric ceramics device, after standing 24 hours at normal temperatures, carries out performance survey
Examination.Its density is 4.120g/cm3.Piezoelectric coefficient d 33 is 264pC/N, and its reverse ﹡ of piezoelectric coefficient d 33 is in room temperature to 170 DEG C
Fluctuation in temperature range is 8%.Dielectric loss tan δ are 0.04.Curie temperature Tc is 395 DEG C.
Embodiment 5
It is (K to prepare by chemical formula0.46Na0.47Bi0.02Nb0.96Sb0.04O3)0.96(CaZrO3)0.04-(ZnO)yUnleaded pressure
Y=1.0 in electroceramics material, formula.
Preparation method includes：
S1-5, dispensing
With analytically pure K2CO3、Na2CO3、Bi2O3、Nb2O5、Sb2O3、CaCO3、ZrO2, ZnO be raw material, according to accordingly matching somebody with somebody
The chemical formula of side carries out weighing dispensing.
S2-5, preparation
S21-5, the addition absolute ethyl alcohol into the raw material (in addition to ZnO) prepared, and carry out first time mix grinding, first time mix grinding
Time is 20 hours；
Raw material after first time mix grinding is dried；
By the raw material after drying in 800 DEG C of pre-burnings 5 hours, the first preburning powdered material is obtained.
S22-5, addition ZnO and absolute ethyl alcohol second of mix grinding of progress, 20 hours mix grinding time into the first preburning powdered material；
Powder after second of mix grinding is dried, to obtain mixed powder.
S23-5, the polyvinyl alcohol water solution for being 8% to mixed powder addition mass concentration are granulated, and use mould pressure
Type is made, to obtain Ф 10*2mm crude green body.
S24-5, first, pre- dumping is carried out by crude green body in chloroform；
Then, dumping processing is carried out at a temperature of 660 DEG C.
S25-5, in air sintering furnace, the crude green body after dumping is handled sinters 2h at 1120 DEG C, to obtain ceramic member
Part.
S3-5, polarization
First, the plated electrode on ceramic component；Then, the direct current for being put into application 2kV/mm in silicone oil is polarized, pole
The change time is 30 minutes, that is, obtains leadless piezoelectric ceramics device.
In this embodiment, obtained leadless piezoelectric ceramics device, after standing 24 hours at normal temperatures, carries out performance survey
Examination.Its density is 4.260g/cm3.Piezoelectric coefficient d 33 is 286pC/N, and its reverse ﹡ of piezoelectric coefficient d 33 is in room temperature to 170 DEG C
Fluctuation in temperature range is 9%.Dielectric loss tan δ are 0.036.Curie temperature Tc is 415 DEG C.
Embodiment 6
It is (K to prepare by chemical formula0.5Na0.5Nb0.96Sb0.04O3)0.96(Ba0.5Ca0.5ZrO3)0.04-(ZnO)yUnleaded pressure
Y=1.0 in electroceramics material, formula.
Preparation method includes：
S1-6, dispensing
With analytically pure K2CO3、Na2CO3、Nb2O5、Sb2O3、BaCO3、CaCO3、ZrO2, ZnO be raw material, according to accordingly matching somebody with somebody
The chemical formula of side carries out weighing dispensing.
S2-6, preparation
S21-6, the addition absolute ethyl alcohol into the raw material (in addition to ZnO) prepared, and carry out first time mix grinding, first time mix grinding
Time is 20 hours；
Raw material after first time mix grinding is dried；
By the raw material after drying in 800 DEG C of pre-burnings 5 hours, the first preburning powdered material is obtained.
S22-6, addition ZnO and absolute ethyl alcohol second of mix grinding of progress, 20 hours mix grinding time into the first preburning powdered material；
Powder after second of mix grinding is dried, to obtain mixed powder.
S23-6, the polyvinyl alcohol water solution for being 12% to mixed powder addition mass concentration are granulated, and use mould pressure
Type is made, to obtain Ф 10*2mm crude green body.
S24-6, first, pre- dumping is carried out by crude green body in acetone；
Then, dumping processing is carried out at a temperature of 700 DEG C.
S25-6, in air sintering furnace, the crude green body after dumping is handled, at 1020 DEG C sinter 2 hours, to be made pottery
Porcelain element.
S3-6, polarization
First, the plated electrode on ceramic component；Then, the direct current for being put into application 3kV/mm in silicone oil is polarized, pole
The change time is 30 minutes, that is, obtains leadless piezoelectric ceramics device.
In this embodiment, obtained leadless piezoelectric ceramics device, after standing 24 hours at normal temperatures, carries out performance survey
Examination.Its density is 4.260g/cm3.Piezoelectric coefficient d 33 is 280pC/N, and its reverse ﹡ of piezoelectric coefficient d 33 is in room temperature to 170 DEG C
Fluctuation in temperature range is 7%.Dielectric loss tan δ are 0.03.Curie temperature Tc is 397 DEG C.
Embodiment 7
It is (K to prepare by chemical formula0.47Na0.47Bi0.01Li0.02Nb0.96Sb0.02Ta0.02O3)0.96
(Ba0.5Ca0.5ZrO3)0.04-(ZnO)yLead-free piezoceramic material, y=1.0 in formula.
Preparation method includes：
S1-7, dispensing
With analytically pure K2CO3、Na2CO3、Bi2O3、Li2CO3、Nb2O5、Sb2O3、Ta2O3、BaCO3、 CaCO3、ZrO2、ZnO
For raw material, weighing dispensing is carried out according to the chemical formula being accordingly formulated.
S2-7, preparation
S21-7, the addition absolute ethyl alcohol into the raw material (in addition to ZnO) prepared, and carry out first time mix grinding, first time mix grinding
Time is 20 hours；
Raw material after first time mix grinding is dried；
By the raw material after drying in 800 DEG C of pre-burnings 5 hours, the first preburning powdered material is obtained.
S22-7, addition ZnO and absolute ethyl alcohol second of progress mix grinding 20 hours into the first preburning powdered material；
Powder after second of mix grinding is dried, to obtain mixed powder.
S23-7, the polyvinyl alcohol water solution for being 12% to mixed powder addition mass concentration are granulated, and use mould pressure
Type is made, to obtain Ф 10*2mm crude green body.
S24-7, first, pre- dumping is carried out by crude green body in trichloro ethylene；
Then, dumping processing is carried out at a temperature of 620 DEG C.
S25-7, in air sintering furnace, the crude green body after dumping is handled, at 1020 DEG C sinter 4 hours, to be made pottery
Porcelain element.
S3-7, polarization
First, the plated electrode on ceramic component；Then, the direct current for being put into application 2kV/mm in silicone oil is polarized, pole
The change time is 30 minutes, that is, obtains leadless piezoelectric ceramics device.
In this embodiment, obtained leadless piezoelectric ceramics device, after standing 24 hours at normal temperatures, carries out performance survey
Examination.Its density is 4.220g/cm3.Piezoelectric coefficient d 33 is 280pC/N, and its reverse ﹡ of piezoelectric coefficient d 33 is in room temperature to 170 DEG C
Fluctuation in temperature range is 9%.Dielectric loss tan δ are 0.04.Curie temperature Tc is 389 DEG C.
Embodiment 8
It is (K to prepare by chemical formula0.47Na0.47Bi0.01Li0.02Nb0.96Sb0.02Ta0.02O3)0.96
(Ba0.5Ca0.5ZrO3)0.04-(ZnO)yLead-free piezoceramic material, y=1.0 in formula.
Preparation method includes：
SS1-8, dispensing
With analytically pure K2CO3、Na2CO3、Bi2O3、Li2CO3、Nb2O5、Sb2O3、Ta2O3、BaCO3、 CaCO3、ZrO2、ZnO
For raw material, weighing dispensing is carried out according to the chemical formula being accordingly formulated.
SS2-8, preparation
SS21-8, add absolute ethyl alcohol into the raw material prepared, and carry out mix grinding, the mix grinding time is 20 hours；
Raw material after mix grinding is dried；
By the raw material after drying in 800 DEG C of pre-burnings 5 hours, the second preburning powdered material is obtained.
SS22-8, the polyvinyl alcohol water solution for being 12% to the second preburning powdered material addition mass concentration are granulated, and are used in combination
Mould is compressing, to obtain Ф 10*2mm crude green body.
SS23-8, the progress dumping processing at a temperature of 620 DEG C.
SS24-8, in air sintering furnace, the crude green body after dumping is handled sinters 4h at 1020 DEG C, to obtain ceramics
Element.
SS3-8, polarization
First, the plated electrode on ceramic component；Then, the direct current for being put into application 2kV/mm in silicone oil is polarized, pole
The change time is 30 minutes, that is, obtains leadless piezoelectric ceramics device.
In this embodiment, obtained leadless piezoelectric ceramics device, after standing 24 hours at normal temperatures, carries out performance survey
Examination.Its density is 4.120g/cm3.Piezoelectric coefficient d 33 is 268pC/N, and its reverse ﹡ of piezoelectric coefficient d 33 is in room temperature to 170 DEG C
Fluctuation in temperature range is 9%.Dielectric loss tan δ are 0.043.Curie temperature Tc is 399 DEG C.
Embodiment 9
It is (K to prepare by chemical formula0.47Na0.47Bi0.01Li0.02Nb0.96Sb0.02Ta0.02O3)0.96
(Ba0.5Ca0.5ZrO3)0.04-(CuO)yLead-free piezoceramic material, y=1.0 in formula.
Preparation method includes：
SS1-9, dispensing
With analytically pure K2CO3、Na2CO3、Bi2O3、Li2CO3、Nb2O5、Sb2O3、Ta2O3、BaCO3、 CaCO3、ZrO2、CuO
For raw material, weighing dispensing is carried out according to the chemical formula being accordingly formulated.
SS2-9, preparation
SS21-9, add absolute ethyl alcohol into the raw material prepared, and carry out mix grinding, the mix grinding time is 20 hours；
Raw material after mix grinding is dried；
By the raw material after drying in 800 DEG C of pre-burnings 5 hours, the second preburning powdered material is obtained.
SS22-9, the polyvinyl alcohol water solution for being 8% to the second preburning powdered material addition mass concentration are granulated, and use mould
Tool is compressing, to obtain Ф 10*2mm crude green body.
SS23-9, the progress dumping processing at a temperature of 600 DEG C.
SS24-9, in air sintering furnace, the crude green body after dumping is handled sinters 4h at 1020 DEG C, to obtain ceramics
Element.
SS3-9, polarization
First, the plated electrode on ceramic component；Then, the direct current for being put into application 3kV/mm in silicone oil is polarized, pole
The change time is 30 minutes, that is, obtains leadless piezoelectric ceramics device.
In this embodiment, obtained leadless piezoelectric ceramics device, after standing 24 hours at normal temperatures, carries out performance survey
Examination.Its density is 4.120g/cm3.Piezoelectric coefficient d 33 is 258pC/N, and its reverse ﹡ of piezoelectric coefficient d 33 is in room temperature to 170 DEG C
Fluctuation in temperature range is 10%.Dielectric loss tan δ are 0.04.Curie temperature Tc is 379 DEG C.
Embodiment 10
It is (K to prepare by chemical formula0.47Na0.47Bi0.01Li0.02Nb0.96Sb0.02Ta0.02O3)0.96
(Ba0.5Ca0.5ZrO3)0.04-(CeO2)yLead-free piezoceramic material, y=1.0 in formula.
Preparation method includes：
SS1-10, dispensing
With analytically pure K2CO3、Na2CO3、Bi2O3、Li2CO3、Nb2O5、Sb2O3、Ta2O3、BaCO3、 CaCO3、ZrO2、
CeO2For raw material, weighing dispensing is carried out according to the chemical formula being accordingly formulated.
SS2-10, preparation
SS21-10, add absolute ethyl alcohol into the raw material prepared, and carry out mix grinding, the mix grinding time is 20 hours；
Raw material after mix grinding is dried；
By the raw material after drying in 800 DEG C of pre-burnings 5 hours, the second preburning powdered material is obtained.
SS22-10, the polyvinyl alcohol water solution for being 12% to the second preburning powdered material addition mass concentration are granulated, and are used in combination
Mould is compressing, to obtain Ф 10*2mm crude green body.
SS23-10, the progress dumping processing at a temperature of 700 DEG C.
SS24-10, in air sintering furnace, the crude green body after dumping is handled sinters 4h at 1020 DEG C, to be made pottery
Porcelain element.
SS3-10, polarization
First, the plated electrode on ceramic component；Then, the direct current for being put into application 2kV/mm in silicone oil is polarized, pole
The change time is 30 minutes, that is, obtains leadless piezoelectric ceramics device.
In this embodiment, obtained leadless piezoelectric ceramics device, after standing 24 hours at normal temperatures, carries out performance survey
Examination.Its density is 4.020g/cm3.Piezoelectric coefficient d 33 is 240pC/N, and its reverse ﹡ of piezoelectric coefficient d 33 is in room temperature to 170 DEG C
Fluctuation in temperature range is 9%.Dielectric loss tan δ are 0.041.Curie temperature Tc is 385 DEG C.
Although some specific embodiments of the present invention are described in detail by example, the skill of this area
Art personnel are it should be understood that example above is merely to illustrate, the scope being not intended to be limiting of the invention.The skill of this area
Art personnel to above example it should be understood that can modify without departing from the scope and spirit of the present invention.This hair
Bright scope is defined by the following claims.
Claims (15)
1. a kind of leadless piezoelectric ceramics, with following represented by formula I：
(KaNabBicLidNb1-e-f-gSbeTifTagO3)(1-x)(Ba1-jCajZrO3)x-Gy (I)
Wherein, 0≤x≤0.10,0≤y≤2.0,0 ＜ a ＜ 0.8,0 ＜ b ＜ 0.8,0≤c≤0.08,0≤d≤0.08,0≤e
≤ 0.06,0≤f≤0.08,0≤g≤0.08,0≤j≤1.0,
Wherein, oxides of the G selected from rare earth element, one or more kinds of mixtures in CuO, ZnO,
Wherein, y is compound (K shared by GaNabBicLidNb1-e-f-gSbeTifTagO3)(1-x)(Ba1-jCajZrO3)xMole percent
Than.
2. leadless piezoelectric ceramics according to claim 1, wherein, 0≤x≤0.04,0≤y≤1.5,0.32≤a≤
0.60,0.40≤b≤0.68, and 0.6≤a/b≤1.3,0≤c≤0.02,0≤d≤0.02,0≤e≤0.04,0≤f≤
0.02,0≤g≤0.02,0≤j≤1.0.
3. leadless piezoelectric ceramics according to claim 1, wherein, the oxide of the rare earth element is CeO2。
4. leadless piezoelectric ceramics according to claim 1, wherein, the leadless piezoelectric ceramics is perovskite structure.
5. a kind of preparation method of leadless piezoelectric ceramics, wherein, comprise the following steps：
S1, dispensing：
With K2CO3、Na2CO3、Bi2O3、Li2CO3、Nb2O5、Sb2O3、TiO2、Ta2O3、BaCO3、CaCO3、ZrO2And G is raw material,
Various raw materials are according to chemical formula (KaNabBicLidNb1-e-f-gSbeTifTagO3)(1-x)(Ba1-jCajZrO3)x-GyIn a, b, c, d,
E, f, g, j, x, y setting value carry out weighing dispensing,
Wherein, 0≤x≤0.10,0≤y≤2.0,0 ＜ a ＜ 0.8,0 ＜ b ＜ 0.8,0≤c≤0.08,0≤d≤0.08,0≤e
≤ 0.06,0≤f≤0.08,0≤g≤0.08,0≤j≤1.0,
Wherein, oxides of the G selected from rare earth element, one or more kinds of mixtures in CuO, ZnO,
Wherein, y is compound (K shared by GaNabBicLidNb1-e-f-gSbeTifTagO3)(1-x)(Ba1-jCajZrO3)xMoles hundred
Divide ratio；
S2, preparation
S21, by K2CO3、Na2CO3、Bi2O3、Li2CO3、Nb2O5、Sb2O3、TiO2、Ta2O3、BaCO3、CaCO3And ZrO2Mixing
Thing carries out pre-burning, to obtain the first preburning powdered material,
S22, add G into first preburning powdered material, and be prepared into mixed powder,
S23, into the mixed powder granulating agent is added, set with forming the powder of good fluidity, and the powder being prepared into
The crude green body of setting shape,
S24, by the crude green body carry out dumping processing,
S25, dumping is handled after the crude green body be sintered, to obtain ceramic component；
S3, polarization
Ceramic component is polarized, to obtain leadless piezoelectric ceramics device.
6. preparation method according to claim 5, wherein, in S21 steps, including：
To K2CO3、Na2CO3、Bi2O3、Li2CO3、Nb2O5、Sb2O3、TiO2、Ta2O3、BaCO3、CaCO3And ZrO2Mixture in
Absolute ethyl alcohol is added, and carries out first time mix grinding；
Mixture after first time mix grinding is dried；
Mixture after drying is subjected to pre-burning, to obtain the first preburning powdered material.
7. preparation method according to claim 6, wherein, mix grinding time first time is 10-30 hours, and calcined temperature is
850-900 DEG C, burn-in time is 3-8 hours.
8. preparation method according to claim 5, wherein, in S22 steps, including：To the first preburning powdered material for adding G
Middle addition absolute ethyl alcohol, and carry out second of mix grinding；
Powder after second of mix grinding is dried, to obtain mixed powder.
9. preparation method according to claim 5, wherein, in S23 steps, the granulating agent is water-soluble for polyvinyl alcohol
Liquid, the mass concentration of the aqueous solution of the polyvinyl alcohol is 4%-12%.
10. preparation method according to claim 5, wherein, in S25 steps, sintering temperature is 920-1120 DEG C, sintering
Time is 2-6 hours.
11. preparation method according to claim 5, wherein, in S3 steps, including：Plated on the ceramic component
Electrode, and the direct current for applying 2-4kV/mm in silicone oil is put into, to be polarized, the polarization time is 15-30 minutes.
12. a kind of preparation method of leadless piezoelectric ceramics, wherein, comprise the following steps：
SS1, dispensing：
With K2CO3、Na2CO3、Bi2O3、Li2CO3、Nb2O5、Sb2O3、TiO2、Ta2O3、BaCO3、CaCO3、ZrO2And G is raw material,
Various raw materials are according to chemical formula (KaNabBicLidNb1-e-f-gSbeTifTagO3)(1-x)(Ba1-jCajZrO3)x-GyIn a, b, c, d,
E, f, g, j, x, y setting value carry out weighing dispensing,
Wherein, 0≤x≤0.10,0≤y≤2.0,0 ＜ a ＜ 0.8,0 ＜ b ＜ 0.8,0≤c≤0.08,0≤d≤0.08,0≤e
≤ 0.06,0≤f≤0.08,0≤g≤0.08,0≤j≤1.0,
Wherein, oxides of the G selected from rare earth element, one or more kinds of mixtures in CuO, ZnO,
Wherein, y is compound (K shared by GaNabBicLidNb1-e-f-gSbeTifTagO3)(1-x)(Ba1-jCajZrO3)xMole percent
Than；
SS2, preparation
SS21, by K2CO3、Na2CO3、Bi2O3、Li2CO3、Nb2O5、Sb2O3、TiO2、Ta2O3、BaCO3、CaCO3、ZrO2With mixing for G
Compound carries out pre-burning, to obtain the second preburning powdered material,
SS22, into second preburning powdered material granulating agent is added, to form the powder of good fluidity, and prepared by the powder
Into the crude green body of setting shape,
SS23, by the crude green body carry out dumping processing,
SS24, dumping is handled after the crude green body be sintered, to obtain ceramic component；
SS3, polarization
Ceramic component is polarized, to obtain leadless piezoelectric ceramics device.
13. preparation method according to claim 12, wherein, in SS21 steps, calcined temperature is 850-900 DEG C, in advance
The burning time is 3-8 hours.
14. preparation method according to claim 12, wherein, in SS22 steps, the granulating agent is polyvinyl alcohol
The aqueous solution, the mass concentration of the aqueous solution of the polyvinyl alcohol is 4%-12%.
15. preparation method according to claim 12, wherein, in SS24 steps, sintering temperature is 920-1120 DEG C, is burnt
The knot time is 2-6 hours.
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