CN101657394A - Piezoelectric, lead-free ceramic composition, method for producing the same and piezoelectric component comprising said material - Google Patents
Piezoelectric, lead-free ceramic composition, method for producing the same and piezoelectric component comprising said material Download PDFInfo
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- CN101657394A CN101657394A CN200880011297.4A CN200880011297A CN101657394A CN 101657394 A CN101657394 A CN 101657394A CN 200880011297 A CN200880011297 A CN 200880011297A CN 101657394 A CN101657394 A CN 101657394A
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- 239000000203 mixture Substances 0.000 title claims abstract description 66
- 239000000919 ceramic Substances 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 239000013078 crystal Substances 0.000 claims abstract description 41
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 150000001768 cations Chemical class 0.000 claims abstract description 7
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 6
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 6
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 6
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 6
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 6
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 6
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 6
- 229910052738 indium Inorganic materials 0.000 claims abstract description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 6
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 6
- 229910052716 thallium Inorganic materials 0.000 claims abstract description 6
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 239000004615 ingredient Substances 0.000 claims description 9
- -1 oxyhydroxide Chemical compound 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical compound [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 abstract 1
- 150000002506 iron compounds Chemical class 0.000 abstract 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 58
- 238000005245 sintering Methods 0.000 description 18
- 229910052742 iron Inorganic materials 0.000 description 13
- 239000010955 niobium Substances 0.000 description 9
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 241000894007 species Species 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052728 basic metal Inorganic materials 0.000 description 3
- 150000003818 basic metals Chemical class 0.000 description 3
- 238000010316 high energy milling Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- LDHMAVIPBRSVRG-UHFFFAOYSA-O 1-methylnicotinamide Chemical compound C[N+]1=CC=CC(C(N)=O)=C1 LDHMAVIPBRSVRG-UHFFFAOYSA-O 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 229940126062 Compound A Drugs 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 229910013641 LiNbO 3 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- UTBYQPSPFXHANA-UHFFFAOYSA-N [K].[Na].[Li] Chemical compound [K].[Na].[Li] UTBYQPSPFXHANA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical group O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- PSVBHJWAIYBPRO-UHFFFAOYSA-N lithium;niobium(5+);oxygen(2-) Chemical compound [Li+].[O-2].[O-2].[O-2].[Nb+5] PSVBHJWAIYBPRO-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002822 niobium compounds Chemical class 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical group [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910001460 tantalum ion Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/495—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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- C01G33/006—Compounds containing, besides niobium, two or more other elements, with the exception of oxygen or hydrogen
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- H10N30/00—Piezoelectric or electrostrictive devices
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Abstract
The invention relates to a piezoelectric, lead-free potassium sodium niobate mixed-crystal ceramic composition (PSN mixed crystal base), said composition being characterized in that it can be producedfrom the components i) NaxKyLiz(Nb1-wTaw)O3 ii) at least one iron component and iii) optionally at least one additional component AB, wherein 0 < x, y, z = 1, 0.9 = x+y+z = 1.1, 0 = w = 0.3 and A isa compound of trivalent metal cations, selected from the group including Bi, La, Sc, Y, Ce, Pr, Nd, Sm, Eu, Gd, Er, Yb, In, Tl or a combination of said cations, and B is a bivalent and/or trivalent iron compound. The invention also relates to a method for producing the piezoelectric PSN mixed-crystal ceramic composition and to a piezoelectric component comprising said piezoelectric, lead-free PSNmixed-crystal ceramic composition.
Description
The present invention relates to a kind of of specific definition class in the claim 1 based on KNN uhligite mixed crystal (KNN, potassium-sodium-niobate, (K
1-mNa
m) NbO
3) lead-free piezoelectric ceramic composition, it for example is used to prepare triggering device.What relate to a kind of claim 8 in addition is used to prepare the method for this KNN pottery and the piezoelectric member of claim 11.
Background technology
Piezoelectric ceramics is useful especially as transmitter in the various members or triggering device, for example is used for injection system.As transmitter or triggering device the time, piezoelectric ceramics can be used to cause big mechanical deflection or be used to produce high voltage by pressure-controlling by voltage control.
When the preparation piezoelectric ceramics, the normal stupalith of using based on Pb-based lanthanumdoped zirconate titanates (PZT) mixed crystal is because it has extraordinary property combination aspect high temperature tolerance, high piezoelectric charge constant, high-curie temperature, low-k and the coercive field strength under the situation that adds some additive.At these is that the correct balance that is between the characteristic of difference all plays an important role to each piezoelectric sometimes.But some optimal properties that can reach are normally repelled mutually under some doping situation.In addition, Tao Ci sintering characteristic has also determined economically reasonably applicability.
This in principle piezoelectric ceramic composition with perovskite structure is the useful material of a class.Its available general formula ABO
3Expression, wherein can be following valence state: A can be monovalence, divalence or trivalent for A and B, and B is pentavalent, tetravalence or is trivalent equally.A also can respectively be corresponding a kind of element or the multiple element that occupies the identical valence state of A position or B position in lattice with B in addition.For example this perovskite-like material is (Pb
2+) (Zr
4+ xTi
4+ 1-x) O
3(PZT) or (K
+ xNa
+ 1-x) (Nb
5+) O
3(KNN, potassium-sodium-niobate).
This class is as existing a large amount of description of the piezoelectricity composition of triggering device.Recently because strict environment regulations particularly provides unleaded material fully in the auto industry field strong request.A kind of lead-free piezoelectricity composition example has been described in EP1702906.Wherein for improving piezoelectric property and improving sintering characteristic, described a kind of by first oxide compound with perovskite structure be KNN, second oxide compound with perovskite structure is the mixture that alkaline-earth metal Zirconium oxide and the oxide compound with tungsten bronze(s) crystalline structure are formed.Described various doping agents in addition, it can be selected from the oxide compound of wide series of the 3-14 family element of chemical element periodic system.
Unadulterated KNN material is poor fine and close characteristic when sintering, it is owing to the alkali metal component of the low thermostability of this material and this material high easy volatile of potassium composition particularly.Easily form hygroscopic impurity phase in addition, so that under the standard pressure condition, may prepare closely knit sample hardly.
Summary of the invention
Compared with prior art, can be the piezoelectric ceramic composition that can obtain in sintering process, to have the stability improved by the advantage based on the lead-free piezoelectric ceramic composition of the present invention of KNN mixed crystal of the claim 1 of the inventive method of claim 8 preparation.
In addition, advantageously this piezoelectric ceramic composition not only to have extraordinary electric charge constant be d
33＞160pm/V also has improved especially polarization condition and the weak interaction between electrode materials and pottery of the present invention.Can avoid short circuit thus.
In addition advantageously, avoided using lead by piezoelectric ceramic composition of the present invention, and can realize technology controlling and process safer and that environment is more friendly thus.
Other advantages of theme of the present invention and advantageous embodiment can be referring to specification sheets, embodiment and claims.
Find,, can make the overall maintenance of this adulterated hole concentration very little by in KNN mixed crystal matrix, adding at least a iron-based composition.With the iron ion B of this mixed crystal that mix at lattice
5+Take place on the position and/or on crystal boundary, take place.This can reach the useful charge compensation in A position and hole, B position, so that observes piezoelectric activity and thermostability that this stability of structure increases and improve thus this material.
Therefore the purpose of this invention is to provide a kind of lead-free piezoelectric ceramic composition, it is characterized in that said composition can be prepared by following ingredients based on potassium-sodium-niobate mixed crystal (KNN mixed crystal):
i)Na
xK
yLi
z(Nb
1-wTa
w)O
3
Ii) at least a ferrous components and
Iii) randomly at least a other composition AB,
Wherein, 0＜x, y, z≤1,0.9≤x+y+z≤1.1,0≤w≤0.3 and A are the compound of trivalent metal cation, and these positively charged ions are selected from Bi, La, Sc, Y, Ce, Pr, Nd, Sm, Eu, Gd, Er, Yb, In, Tl or these cationic combinations, and B is divalence and/or ferric iron compound.
By the present invention, use component i based on the KNN mixed crystal) the preparation lead-free piezoelectric ceramic composition.In the KNN mixed crystal, the perovskite structure XYO of existence
3By the univalent alkalimetal ion Na that presses the symbol X in the perovskite structure
+, K
+Also may be Li
+With by the pentavalent niobium ion Nb that presses the symbol Y in the perovskite structure
5+Also may be Ta
5+And realize.Component i in the present invention) except that the compound that uses stoichiometric quantity, also can use the compound that has light basic metal metachemistry calculated amount compound or owe stoichiometric quantity.
Term among the present invention " is owed stoichiometric quantity " or " metachemistry calculated amount " means because with XYO
3The X position of the KNN mixed crystal that uhligite exists and the doping of Y position, it is (Li that the alkali metal content of composition is below or above empirical formula
yK
xNa
1-x-y) NbO
3The alkali metal content of the pure KNN mixed crystal of stoichiometric quantity of undoped.
In addition, in a preferred embodiment, as the component i of in empirical formula, having represented by stoichiometric quantity data z) the KNN mixed crystal in lithium content by used KNN mixed crystal component i) molar weight for example can be 〉=0.1 mole of %-≤20 mole %, particularly 〉=2 mole %-≤6 mole %.
X position in perovskite crystalline lattice is introduced lithium ion and is advantageously prevented to form the moisture absorption phase, and improves the Curie temperature of said composition simultaneously.
Because LiNbO
3Usually with the ilmenite structure crystallization, so the solubleness of Lithium niobium trioxide in the KNN uhligite is limited.
In another embodiment preferred, as the component i of in empirical formula, having represented by stoichiometric quantity data w) the KNN mixed crystal in the content of tantalum ion by used KNN mixed crystal component i) molar weight for example can be 〉=1 mole of %-≤30 mole %.
As component i i), the present invention plans the iron-based doping and introduces in the composition.As previously mentioned, this iron mixes and occurs in the Y position of KNN mixed crystal and/or on crystal boundary.Can preferably using wherein among the present invention, iron is the iron cpd of divalence and/or the existence of trivalent oxidation state as ferrous components.The amount of this ferrous components is by used KNN mixed crystal component i) molar weight be preferably 〉=0.1 mole of %-≤15 mole %.
In another embodiment preferred, this ferrous components ii) is Powdered with metal, oxide compound, halogenide, carbonate, nitrate, oxyhydroxide, Citrate trianion and/or complex form and salts solution uses.
Component i i) adding can be advantageously as the additional closely knit fusing assistant in the sintering process, and the position, hole that is produced has increased diffusion.This iron ion enters the Y position of structure, and replaces Nb
5+Ion and Ta
5+Ion.Therefore adding ferrous components also can improve density under lower sintering temperature.
Can randomly use at least a general formula ii) to prepare composition of the present invention as component i among the present invention as other component of AB, wherein A is the compound of trivalent metal cation, these positively charged ions be selected from Bi, La, Sc, Y, Ce, Pr, Nd, Sm, Eu, Gd, Er, Yb, In, Tl or these sun from combination, B is divalence and/or ferric iron compound.Counterion that all are known and commonly used such as oxonium ion, chlorion, carbonate, nitrate radical, hydroxide ion or citrate all can be used as counterion.Component i ii) in the ratio of compound of representing with A and the compound of representing with B can in wide scope, change.So also can use the A of calculated amount ratio non-chemically and B ii) as component i.
This component i is perovskite structure equally preferably ii).But it also can have other crystalline structure.
In another embodiment preferred of the present invention, said composition can contain another component i ii), and its content is by used KNN mixed crystal component i) molar weight count 〉=0.01 mole of %-＜10 mole %.
In another embodiment preferred, this another component i ii) can be through the mixing cpd such as the mixed oxide ABO of the stoichiometric quantity of pre-reaction
3Form adds, or equally also can be preferably with each compound such as single oxide compound A
2O
3And B
2O
3Add without the form of mixtures of pre-reaction.In this scheme, also can use the calculated amount non-chemically of compd A and B.
In addition, this lead-free piezoelectric ceramic composition of the present invention does not preferably contain other ceramics component and/or oxide components.
Another object of the present invention provides the method for a kind of preparation based on the lead-free piezoelectric ceramic composition of potassium-sodium-niobate mixed crystal (KNN mixed crystal base), wherein following ingredients is mixed mutually and is sintered into calcined body:
i)Na
xK
yLi
z(Nb
1-wTa
w)O
3
Ii) at least a ferrous components and
Iii) randomly at least a other composition AB,
Wherein, 0＜x, y, z≤1,0.9≤x+y+z≤1.1,0≤w≤0.3 and A are the compound of trivalent metal cation, and these positively charged ions are selected from Bi, La, Sc, Y, Ce, Pr, Nd, Sm, Eu, Gd, Er, Yb, In, Tl or these cationic combinations, and B is divalence and/or ferric iron compound.
In embodiment of the present invention, this ferrous components ii) is ionic species or is form of pure metal and be added to the mixture in the initial composition of KNN or after calcining, be ionic species or be in the high energy fine grainding body that form of pure metal is added to all the other compositions.
What this was based on us on the one hand studies show that ferrous components ii) needs to exist with ionic species, to diffuse in the KNN material when the sintering.In addition, our research also shows, also can use metallic iron, as long as it is ionic species in the intermediate stage when diffusion.For example it can be this situation, if i.e. this reaction or be diffused in redox couple exist carry out down and/or in the oxidisability condition as in oxidizing atmosphere, carrying out 200 ℃-800 ℃ temperature range.In addition, the present invention shows, pure metallic iron is added to the oxidation that also can cause this metallic iron in the high energy milling body of calcined body.Therefore the required effect of the grain growing when sintering and required thus electromechanical properties improvement in the present invention can be by ii) being added to ferrous components in the starting mixt with ionic species or metallic forms before calcining or by with pure metallic iron or be added to ionic iron cpd form in the high energy milling body of calcined body and realize.Equally also can use this ionic ferrous components ii) in water and/or the salts solution in pure medium.
By the present invention, the mean particle size of the high energy milling body of this calcined body is 〉=0.1 μ m-≤1.5 μ m, particularly 〉=0.8 μ m-≤1.2 μ m.
In another preferred embodiment of the present invention, this ferrous components ii), Fe particularly
2+Salt and/or Fe
3+The add-on of salt is by used KNN mixed crystal component i) molar weight count 〉=0.3 mole of %-≤15 mole %, particularly 〉=0.5 mole %-≤15 mole %.This ferrous components with Powdered or as in water and/or the salts solution in pure medium to add be suitable.
In the present invention, can use all material known to those skilled in the art as component i) the KNN base-material prepare the KNN mixed crystal.This KNN mixed crystal component i) preparation can be by mixing and the reaction or by preparation compound such as NaNbO through pre-reaction of the technology known to those skilled in the art by single composition
3Or KNbO
3And the compound that then makes pre-reaction reacts and carries out.
Preparation method of the present invention is importantly so calculated said composition, and promptly doped element will be positioned at or occupy the X position and the Y position of perovskite structure in theory.Produce alkali metal content thus and be the KNN mixed crystal composition of obviously owing stoichiometric quantity, this is formed by doped element such as Fe
2+And/or Fe
3+Compensation.By using Fe
2+And/or Fe
3+Replace Nb
5+Realize with producing position, basic metal hole at XYO
3It is very important for the purpose of the present invention that niobium ion on the Y position of structure or Ta ionic are owed stoichiometric quantity.
Cause stable technology controlling and process with ferrous components doping of the present invention, because reduced the rich basic metal liquid phase that in sintering process, forms, the deal of particularly rich potassium liquid phase, and can shoot more a spot of this phase composition thus.
Composition of the present invention both can also can prepare by mixed oxide method (mix all initial compounds, and then be sintered into uniform KNN mixed crystal) by the niobite method.
Temperature during calcining preferably remains 650 ℃-950 ℃.Except that independent calcining step, also can provide a plurality of one calcining steps.
For the incinerating lead-free piezoceramic material is reprocessed into the electroceramics member, particularly piezoelectric activated device, thermistor or electric capacity can adopt known method.A kind ofly may be the powder of shaping gained in pressing process and then sinter closely knit pottery into.
The preferred temperature of sintering process is 950 ℃-1250 ℃.
Another object of the present invention provides a kind of lead-free piezoelectric ceramic composition based on potassium-sodium-niobate mixed crystal by the inventive method preparation.
Another purpose of the present invention provides a kind of piezoelectric member, it is characterized in that, this member contains of the present invention or by the lead-free piezoelectric ceramic composition based on potassium-sodium-niobate mixed crystal of the present invention preparation.
An also purpose of the present invention be of the present invention or by the present invention's preparation based on the application in preparing the piezoelectric activated device of automobile injection system particularly of the lead-free piezoelectric ceramic composition of potassium-sodium-niobate mixed crystal.
Embodiment
The preparation rules:
In mixing vessel, be added with and amount to the alkali metal cation composition listed in the table containing of 10g-100g and possible tantalum composition (Na
xK
yLi
z(Nb
1-wTa
w) O
3) be carbonate, niobium oxides, also may be the tantalum oxide form and/or be through the potassium-sodium-lithium compound of the base metal niobate form of pre-reaction and the powder or the solution in water and/or pure medium (Virahol) of niobium compound, and always with pulverous or be the given component i i of the solution form in water and/or pure medium) and possible component i ii) mix mutually and homogeneity.Then calcine this mixture down, then at the given sintering temperature 180min of table at 750 ℃.Perhaps this component i i) and possible component i ii) also can after calcining, just add.Corresponding reinforced order of addition(of ingredients) of having pointed out each experiment in tabulating down.The electric charge constant d that provides
33 *The displacement sensor with optics control with Haidenhain company is measured under 2kV/mm.
Table 1: component i i) to the piezoelectric charge constant d of material
33With the burning Temperature Influence
| Numbering | ??K??x | ??Na??y | ??Li??z | ??x+y+z | ??Ta??w | Component i i) | Mol% component i i) (by the mole number of KNN basic components) | Calcine front/rear adding | Sintering temperature (℃) | ??d 33 *??2kV/mm??(pm/V) |
| ?? *1 | ??0.5 | ??0.5 | ??0 | ??1 | ??0 | ??Fe 2O 3 | ??0 | ?- | ??1050 | ??n.b. |
| ?? *2 | ??0.5 | ??0.5 | ??0 | ??1 | ??0.1 | ??Fe 2O 3 | ??0 | ?- | ??1050 | ??120 |
| ?? *3 | ??0.47 | ??0.47 | ??0.06 | ??1 | ??0 | ??Fe 2O 3 | ??0 | ?- | ??1050 | ??n.b. |
| ??4 | ??0.44 | ??0.52 | ??0.04 | ??1 | ??0.12 | ??Fe 2O 3 | ??0.15 | After | ??1050 | ??350 |
| ??5 | ??0.44 | ??0.52 | ??0.04 | ??1 | ??0.12 | Iron acetate | ??0.15 | After | ??1050 | ??280 |
| ??6 | ??0.5 | ??0.5 | ??0 | ??1 | ??0 | ??Fe 2O 3 | ??0.3 | After | ??1050 | ??180 |
| ??7 | ??0.44 | ??0.52 | ??0.04 | ??1 | ??0.12 | Iron acetate | ??0.3 | Before | ??1050 | ??280 |
| ??8 | ??0.47 | ??0.47 | ??0.06 | ??1 | ??0 | ??Fe 2O 3 | ??0.3 | Before | ??1100 | ??235 |
| ??9 | ??0.47 | ??0.47 | ??0.06 | ??1 | ??0 | ??Fe 2O 3 | ??0.3 | After | ??1100 | ??225 |
| ??10 | ??0.47 | ??0.47 | ??0.06 | ??1 | ??0 | ??Fe 2O 3 | ??0.3 | After | ??1120 | ??320 |
| ??11 | ??0.5 | ??0.5 | ??0 | ??1 | ??0.005 | Iron acetate | ??0.5 | Before | ??1100 | ??280 |
| ??12 | ??0.44 | ??0.52 | ??0.04 | ??1 | ??0.12 | Iron acetate | ??0.8 | Before | ??1050 | ??240 |
| ??13 | ??0.44 | ??0.52 | ??0.04 | ??1 | ??0.12 | Iron acetate | ??1.5 | Before | ??1100 | ??350 |
| ??14 | ??0.63 | ??0.28 | ??0.1 | ??1.01 | ??0 | ??Fe 2O 3 | ??1.9 | After | ??1100 | ??300 |
| ??15 | ??0.44 | ??0.52 | ??0.04 | ??1 | ??0.12 | Iron acetate | ??2 | After | ??1050 | ??350 |
| ??16 | ??0.3 | ??0.65 | ??0.05 | ??1 | ??0 | ??Fe 2O 3 | ??2.37 | Before | ??1100 | ??270 |
| ??17 | ??0.43 | ??0.5 | ??0.07 | ??1 | ??0.2 | ??Fe 2O 3 | ??3.3 | Before | ??1050 | ??300 |
| ??18 | ??0.43 | ??0.55 | ??0.02 | ??1 | ??0 | ??Fe 2O 3 | ??3.48 | Before | ??1100 | ??230 |
| ??19 | ??0.44 | ??0.52 | ??0.04 | ??1 | ??0.12 | Iron acetate | ??6 | Before | ??1100 | ??350 |
| ??20 | ??0.47 | ??0.47 | ??0.06 | ??1 | ??0 | ??Fe 2O 3 | ??6 | After | ??1100 | ??270 |
*Experiment numbers 1,2, the non-piezoelectric ceramics based on KNN of the present invention of 3 expressions, it is as a comparison by above-mentioned rules preparation and mensuration.
N.b.: short circuit
Experimental result by table 1 is obviously found out, does not add the used component i i of the present invention) the piezoelectric ceramics based on KNN under lower sintering temperature, do not have satisfied electric charge constant d
33 *On the contrary, be added with ferrous components ii) pottery of the present invention in addition under lower sintering temperature, also have excellent result, simultaneously used with it iron cpd (oxide compound or acetate) is irrelevant.
In the subsequent experimental of being undertaken, checked optional ingredients influence iii) by above-mentioned given preparation procedure.In all experiments in table 2, all ii) and iii) at the calcining prefix.As component i) use the KNN basic ingredient contain the alkalimetal ion that table 2 gives.Component i) do not contain the Ta composition in.
Table 2: component i i) and iii) to the piezoelectric charge constant d of material
33Influence with sintering temperature
| Numbering | ??K??x | ??Na??y | ??Li??z | ??x+y+??z | Component i i) | Mol% component i i) 1 | Component i is A-B ii) | Mol compares A/B | ??mol??％??A-B 1 | Sintering temperature (℃) | ??d 33 *??2kV/mm??(pm/V) |
| ?? *21 | ??0.493 | ??0.523 | ??0 | ??1.016 | ??Fe 2O 3 | ??0 | ??Bi 2O 3+Fe 2O 3 | ??- | ??0.00 | ??1050 | ??n.b. |
| ??22 | ??0.496 | ??0.526 | ??0 | ??1.022 | ??Fe 2O 3 | ??0.01 | ??Bi 2O 3+Fe 2O 3 | ??1.25 | ??0.05 | ??1050 | ??230 |
| ??23 | ??0.5 | ??0.5 | ??0 | ??1 | ??Fe 2O 3 | ??0.05 | ??Bi 2O 3+Fe 2O 3 | ??1.33 | ??0.20 | ??1050 | ??200. |
| ??24 | ??0.47 | ??0.47 | ??0.06 | ??1 | ??Fe 2O 3 | ??0.05 | ??Bi 2O 3+Fe 2O 3 | ??1.33 | ??0.20 | ??1100 | ??330 |
| ??25 | ??0.47 | ??0.47 | ??0.06 | ??1 | ??Fe 2O 3 | ??0.05 | ??Bi 2O 3+Fe 2O 3 | ??1.20 | ??0.30 | ??1100 | ??330 |
| ??26 | ??0.5 | ??0.5 | ??0 | ??1 | ??Fe 2O 3 | ??0.03 | ??La 2O 3+Fe 2O 3 | ??1.00 | ??0.10 | ??1100 | ??206 |
| ??27 | ??0.5 | ??0.5 | ??0 | ??1 | ??Fe 2O 3 | ??2.05 | ??La 2O 3+Fe 2O 3 | ??1.00 | ??0.25 | ??1050 | ??350 |
| ??28 | ??0.5 | ??0.5 | ??0 | ??1 | ??Fe 2O 3 | ??2.11 | ??La 2O 3+Fe 2O 3 | ??1.00 | ??0.19 | ??1050 | ??160 |
*The non-piezoelectric ceramics based on KNN of the present invention of experiment numbers 21 expressions, it is as a comparison by above-mentioned rules preparation and mensuration.
1By the KNN basic ingredient
N.b.: short circuit
Experimental result by table 2 is obviously found out, does not add the used component i i of the present invention) and piezoelectric ceramics iii) based on KNN under lower sintering temperature, do not have satisfied electric charge constant d
33 *On the contrary, be added with ferrous components ii) with optional ingredients iii) pottery of the present invention in addition under lower sintering temperature, also have excellent result.
Claims (11)
1. based on the lead-free piezoelectric ceramic composition of potassium-sodium-niobate mixed crystal, it is characterized in that said composition can be prepared by following ingredients:
i)Na
xK
yLi
z(Nb
1-wTa
w)O
3
Ii) at least a ferrous components and
Iii) randomly at least a other composition AB,
Wherein, 0＜x, y, z≤1,0.9≤x+y+z≤1.1,0≤w≤0.3, A is the compound of trivalent metal cation, described positively charged ion is selected from Bi, La, Sc, Y, Ce, Pr, Nd, Sm, Eu, Gd, Er, Yb, In, Tl or these cationic combinations, and B is divalence and/or ferric iron compound.
2. the piezoelectricity composition of claim 1 is characterized in that, the content of ferrous components is by used KNN mixed crystal component i in the said composition) molar weight count 〉=0.1 mole of %-≤15 mole %.
3. claim 1 or 2 piezoelectricity composition is characterized in that, described ferrous components ii) with metal, oxide compound, halogenide, carbonate, nitrate, oxyhydroxide, Citrate trianion and/or complex form with Powdered and use as salts solution.
4. the piezoelectricity composition that one of requires at least of aforesaid right is characterized in that said composition can contain other component i ii), and its content is by used KNN mixed crystal component i) molar weight count 〉=0.01 mole of %-＜10 mole %.
5. the piezoelectricity composition that one of requires at least of aforesaid right is characterized in that, described other component i ii) adds with the form through the mixing cpd AB of the stoichiometric quantity of pre-reaction, particularly adds with the mixed oxide forms through pre-reaction.
6. the piezoelectricity composition that one of requires at least of aforesaid right is characterized in that described other component i ii) adds with the stoichiometric quantity form of mixtures of single compd A and B, particularly adds with the single oxide form without pre-reaction.
7. the piezoelectricity composition that one of requires at least of aforesaid right is characterized in that said composition does not contain other ceramics component and/or oxide components.
8. preparation is based on the method for the lead-free piezoelectric ceramic composition of potassium-sodium-niobate mixed crystal, wherein following ingredients mixed mutually and is sintered into calcined body:
i)Na
xK
yLi
z(Nb
1-wTa
w)O
3
Ii) at least a ferrous components and
Iii) randomly at least a other composition AB,
Wherein, 0＜x, y, z≤1,0.9≤x+y+z≤1.1,0≤w≤0.3, A is the compound of trivalent metal cation, described positively charged ion is selected from Bi, La, Sc, Y, Ce, Pr, Nd, Sm, Eu, Gd, Er, Yb, In, Tl or these cationic combinations, and B is divalence and/or ferric iron compound.
9. the method for claim 8 is characterized in that, described component i i) before calcining, be added in the mixture with ionic species or with metallic forms, or after calcining with ionic species or be added to form of pure metal in the high energy fine grainding body of described calcined material.
10. claim 8 or 9 method is characterized in that described component i add-on ii) is by used KNN mixed crystal component i) molar weight count 〉=0.01 mole of %-＜10 mole %.
11. piezoelectric member, it is characterized in that, this member contain by claim 1-7 one of at least based on the lead-free piezoelectric ceramic composition of potassium-sodium-niobate mixed crystal or by the lead-free piezoelectric ceramic composition based on potassium-sodium-niobate mixed crystal of claim 8,9 and/or 10 method preparation.
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| DE102007016854.5A DE102007016854B4 (en) | 2007-04-10 | 2007-04-10 | Piezoelectric, lead-free ceramic composition, process for their preparation and a piezoelectric component comprising this material |
| DE102007016854.5 | 2007-04-10 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173799A (en) * | 2011-02-28 | 2011-09-07 | 上海海事大学 | Method and equipment for synthesizing lithium tantalite doped potassium sodium niobate ceramic |
| CN112510171A (en) * | 2019-09-13 | 2021-03-16 | 株式会社东芝 | Composite oxide, active material composite material, electrode, battery pack, and vehicle |
| CN115028450A (en) * | 2022-06-09 | 2022-09-09 | 清华大学 | Sodium niobate-based ceramic material and preparation method thereof |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007046450A1 (en) * | 2007-09-28 | 2009-04-02 | Siemens Ag | Lead-free piezoceramic material of the potassium-sodium niobate system with iron-lanthanum doping, method for producing a component with the piezoceramic material and use of the component |
| DE102008008902B3 (en) * | 2008-02-13 | 2009-06-04 | Siemens Aktiengesellschaft | Method for producing a lead-free piezoceramic material of the potassium-sodium niobate system with the aid of niobium hydroxide and use of a component with the material |
| GB2469285A (en) | 2009-04-06 | 2010-10-13 | Ntnu Technology Transfer As | Ferroelectric niobate materials formed by spray pyrolysis |
| CN109336599B (en) * | 2018-12-18 | 2021-08-31 | 宁波大学 | Lead-free ferroelectric up-conversion luminescent material and preparation method thereof |
| WO2020184242A1 (en) * | 2019-03-13 | 2020-09-17 | 京セラ株式会社 | Piezoelectric porcelain composition |
| CN111174950B (en) * | 2020-01-04 | 2022-04-19 | 湖北大学 | Potassium-sodium niobate nanorod array growth operation method and manufacturing method of sensing device thereof |
| CN113149647A (en) * | 2021-06-06 | 2021-07-23 | 福州大学 | Ytterbium and up-conversion rare earth luminescent ion double-doped potassium-sodium niobate thick film |
| CN115572165B (en) * | 2021-06-21 | 2023-08-29 | 四川大学 | Bismuth potassium sodium copper iron niobate leadless piezoelectric ceramic with high mechanical quality factor |
| CN116332644B (en) * | 2023-03-17 | 2024-03-22 | 西安建筑科技大学 | K (K) 0.5 Na 0.5 Nb 0.7 Ta 0.3 O 3 Lead-free piezoelectric ceramic material, preparation method and application |
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| TWI228728B (en) * | 2001-05-29 | 2005-03-01 | Murata Manufacturing Co | Piezoelectric ceramic composition, piezoelectric ceramic element and method for producing piezoelectric ceramic composition |
| EP1457471B1 (en) * | 2003-03-14 | 2014-02-26 | Denso Corporation | Crystal oriented ceramics and production method of same |
| BRPI0409353B1 (en) * | 2003-05-29 | 2017-10-31 | Ngk Spark Plug Co., Ltd. | The piezoelectric ceramic and piezoelectric element comprising the composition |
| JP4513948B2 (en) | 2003-12-22 | 2010-07-28 | Ｔｄｋ株式会社 | Piezoelectric ceramic and manufacturing method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173799A (en) * | 2011-02-28 | 2011-09-07 | 上海海事大学 | Method and equipment for synthesizing lithium tantalite doped potassium sodium niobate ceramic |
| CN112510171A (en) * | 2019-09-13 | 2021-03-16 | 株式会社东芝 | Composite oxide, active material composite material, electrode, battery pack, and vehicle |
| CN115028450A (en) * | 2022-06-09 | 2022-09-09 | 清华大学 | Sodium niobate-based ceramic material and preparation method thereof |
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| Publication number | Publication date |
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| DE102007016854B4 (en) | 2017-02-16 |
| DE102007016854A1 (en) | 2008-10-16 |
| WO2008122458A1 (en) | 2008-10-16 |
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