CN1224589C - Bismuth-sodium-potassium-lithium titanate lead-free piezoelectric ceramics - Google Patents
Bismuth-sodium-potassium-lithium titanate lead-free piezoelectric ceramics Download PDFInfo
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- CN1224589C CN1224589C CN 02128112 CN02128112A CN1224589C CN 1224589 C CN1224589 C CN 1224589C CN 02128112 CN02128112 CN 02128112 CN 02128112 A CN02128112 A CN 02128112A CN 1224589 C CN1224589 C CN 1224589C
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Abstract
The present invention relates to bismuth sodium potassium litium titanate leadless piezoelectric ceramics which belong to the field of environmental consistency piezoelectric ceramics with perovskite structures. The leadless piezoelectric ceramics provided by the present invention can be expressed by the general formula of (Bi<1-z>(Na<1-x-y>KxLi<y>)<z>)TiO3+aM<alpha>O<beta> (wt%), wherein x is more than 0 and less than 1, y is more than 0 and less than 1, x plus y is more than 0 and less than 1, and z is from 0.3 to 0.7; M<alpha>O<beta> is one kind or a plurality of kinds of doped oxide, the content a of M<alpha>O<beta> accounts for 0 to 10 wt% of the main components ((Bi<1-z>(Na<1-x-y>KxLi<y>)<z>)TiO3), M is +1 to +6 valent elements which can form solid-state oxide with oxygen, and alpha and beta respectively express atomic numbers of a corresponding element M and oxygen in relevant oxide. D33 of the piezoelectric ceramic can reach more than 150 pC/N, and k<p> can reach more than 26.0%. The present invention has the advantages of stable technology and practical application value, and can be prepared from industrial raw materials by adopting the traditional piezoelectric ceramic preparing technology.
Description
One, technical field
The present invention relates to a kind of novel lead-free piezoelectric ceramics, belong to perovskite structure environment compatibility piezoelectric ceramics field.
Two, background technology
From middle 1940s, after the piezoelectricity of discovery barium titanate ceramics, the research and development of piezoelectric ceramics are very active, and the components and parts that piezoelectric ceramics and piezoelectric ceramics are made have been widely used in particularly information industry field of industry.With Pb-based lanthanumdoped zirconate titanates (Pb (Ti, Zr) O
3) for the lead base two component system of representative with Pb-based lanthanumdoped zirconate titanates (Pb (Ti, Zr) O
3) be base-material, add the 3rd constituent element [as with lead magnoniobate (Pb (Mg
1/3Nb
2/3) O
3) for representative] and the lead base ternary system piezoelectric ceramic have good piezoelectricity ferro performance, high Curie temperature.At present, the piezoelectric ceramics overwhelming majority who uses in the industrial production is such lead base piezoelectric ceramics.
But, because in the lead base piezoceramic material, PbO or Pb
3O
4Content account for 70% of raw material total amount.PbO or Pb
3O
4At high temperature volatile, thus make plumbous series piezoelectric ceramic produce, use and discarded last handling process in cause serious harm for the mankind and ecotope, be unfavorable for the Sustainable development of human society.In recent years, seek piezoelectric ceramics system lead-free, superior performance and be subjected to the attention of countries in the world.For example: patent CN85100426, JP11-217262, JP2000-22235, JP2000-272962 provide ABO
3The composition formula of structure is [Bi
0.5(Na
1-xK
x)
0.5] TiO
3The piezoelectric ceramics compound, its A position is Bi, Na, K; The B position is Ti.It is [Bi that patent JP2000-44335 has also provided composition formula
0.5(Na
1-xLi
x)
0.5] TiO
3The piezoelectric ceramics compound, its A position is Bi, Na, Li; The B position is Ti.But the performance of these leadless piezoelectric ceramicss also has some gaps apart from practical application.
Three, summary of the invention
Purpose of the present invention is exactly in order to overcome the inherent defective of existing lead base piezoelectric ceramics system own, has proposed a kind of new non-lead base, has had good piezoelectricity ferro performance and can practical piezoelectric ceramics.
For realizing purpose of the present invention, the present invention is directed to ABO
3(the Bi of structure
0.5Na
0.5) TiO
3Piezoelectric ceramic body, the material that has proposed a kind of composition can be used general formula [Bi
1-z(Na
1-x-yK
xLi
y)
z] TiO
3The perovskite typed leadless piezoelectric ceramics of expression, its A position are the compound ion that Bi, Na, K and Li form, and the x in the formula, y, z represent the atomicity of component material, and the scope of its numerical value is: 0＜x＜1,0＜y＜1,0＜(x+y)＜1,0.3≤z≤0.7.
The present invention adds one or more other metal oxides as property-modifying additive in the base-material of being represented by the general formula that proposes previously, promptly base-material+hotchpotch is formed piezoelectric ceramics, can obtain this class leadless piezoelectric ceramics of different performance.Leadless piezoelectric ceramics behind the interpolation hotchpotch can be expressed as [Bi with general formula
1-z(Na
1-x-yK
xLi
y)
z] TiO
3+ M
αO
β, the x in the formula, y, z represent the atomicity of component material, its numerical range is: 0＜x＜1,0＜y＜1,0＜(x+y)＜1,0.3≤z≤0.7; M
αO
βRepresent the doping oxide that one or more are elementary composition, M representative+1-+6 valency and can form the element of oxide compound with oxygen, be selected from Na, K, Li, Al, Cu, Fe, Ce, Pr, Nd, Sm, Gd, Dy, Er, Yb, Y, Sc, Mn, Ca, Ba, Sr, Mg and Si etc., α and β represent the atomicity of corresponding element M and oxygen in the relevant oxide compound respectively.The ratio of hotchpotch in the piezoelectric ceramics raw material is the 0-10Wt% of raw material gross weight; Base-material accounts for 90-100Wt%.
The perovskite typed leadless piezoelectric ceramics that the present invention proposes has good piezoelectricity ferro performance, and line smoothing does not have clutter as can be seen from the tuning curve figure of Fig. 1 piezoelectric ceramics system sample.In its material property parameter, percentage coupling K
pReach more than 150 piezoelectric constant d
33Be more than 26.Advantage of the present invention is: 1. material system is a leadless piezoelectric ceramics;
2. piezoelectricity ferro excellent property; 3. process stabilizing; 4. can adopt traditional industry with starting material and the preparation of piezoelectric ceramics technology of preparing, be applicable to scale production.
Four, description of drawings
Fig. 1 is the tuning curve figure of polynary lead-free piezoelectric ceramics system sample.
Five, embodiment
Prepare piezoelectric ceramics of the present invention and can adopt technical pure or chemical pure Bi
2O
3, Na
2CO
3, K
2CO
3, Li
2CO
3, TiO
2Be raw material, can select the associated metal oxide compound as hotchpotch M according to different needs
αO
βPreparation process is: press general formula [Bi
1-z(Na
1-x-yK
xLi
y)
z] TiO
3Or proportionally (Wt%) adds M
αO
βAfter the stoichiometric ratio raw materials weighing, behind abundant ball milling mixing, in the alumina crucible of packing into, under 800-900 ℃ of temperature, carry out pre-burning, soaking time is 4-6 hour.Pre-burning synthetic powder is levigate through ball-milling technology again, adding additives, moulding, plastic removal, then at 1100-1200 ℃ of sintering temperature 2-3 hour.Ceramic plate behind the sintering is by last silver electrode, and in 100-120 ℃ silicone oil, polarization is 10-15 minute under the voltage of 3-4kV/mm.At last, by the IRE standard piezoelectric ceramics of making is measured performance perameters such as piezoelectricity.
Embodiment:
Be the prescription of several leadless piezoelectric ceramics embodiment and the piezoelectric property parameters that records below:
One, adopts [Bi
0.5(Na
0.7K
0.25Li
0.05)
0.5] TiO
3Form leadless piezoelectric ceramics, the performance of piezoelectric ceramics for preparing is:
d
33(pC/N) ε
33/ ε
0k
p(%) Poisson's ratio
150 1280 22.1 0.285
Two, adopt [Bi
0.5(Na
0.6K
0.35Li
0.05)
0.5] TiO
3Form leadless piezoelectric ceramics, the performance of piezoelectric ceramics for preparing is:
d
33(pC/N) ε
33/ ε
0k
p(%) Poisson's ratio
120 1750 26.4 0.174
Three, adopt [Bi
0.5(Na
0.65K
0.25Li
0.1)
0.5] TiO
3(99.5Wt%); Add Li
2O (0.5Wt%) forms leadless piezoelectric ceramics, and the performance of piezoelectric ceramics for preparing is:
d
33(pC/N) ε
33/ ε
0k
p(%) Poisson's ratio
100 1110 17.3 0.295
Four, adopt Bi
0.5(Na
0.7K
0.25Li
0.05) TiO
3(98Wt%); Add CeO
2(2Wt%) form leadless piezoelectric ceramics, the performance of piezoelectric ceramics for preparing is:
d
33(pC/N) ε
33/ ε
0k
p(%) Poisson's ratio
150 1280 22.1 0.285
Five, adopt [Bi
0.5(Na
0.06K
0.35Li
0.05)
0.5] TiO
3(94Wt%); Add Er
2O
3(3Wt%) and Yb
2O
3(3Wt%) form leadless piezoelectric ceramics, the performance of piezoelectric ceramics for preparing is:
d
33(pC/N) ε
33/ ε
0k
p(%) Poisson's ratio
120 1750 26.4 0.174
Six, adopt [Bi
0.5(Na
0.65K
0.25Li
0.1)
0.5] TiO
3(95.5Wt%); Add Li
2O (0.5Wt%), Dy
2O
3(2Wt%) and Yb
2O
3(2Wt%) form leadless piezoelectric ceramics, the performance of piezoelectric ceramics for preparing is:
d
33(pC/N) ε
33/ ε
0k
p(%) Poisson's ratio
110 1110 17.4 0.295
Seven, adopt [Bi
0.5(Na
0.6K
0.3Li
0.1)
0.5] TiO
3(98Wt%); Add CaO (2Wt%) and form leadless piezoelectric ceramics, the performance of piezoelectric ceramics for preparing is:
d
33(pC/N) ε
33/ ε
0k
p(%) Poisson's ratio
118 1200 21.5 0.273
Claims (2)
1. a perovskite structure leadless piezoelectric ceramics is characterized in that it being with general formula [Bi
1-z(Na
1-x-yK
xLi
y)
z] TiO
3+ M
αO
βThe material of expression is formed, in the formula: 0＜x＜1,0＜y＜1,0＜(x+y)＜1,0.3≤z≤0.7; M
αO
βOne or more doping oxides that be to add, M are+1-+6 valency and can form the element of oxide compound, and the content of doping oxide is 0-10% weight, the content of all the other materials is 90-100% weight.
2. piezoelectric ceramics as claimed in claim 1 is characterized in that said M is selected from element Na, K, Li, Al, Cu, Fe, Ce, Pr, Nd, Sm, Gd, Dy, Er, Yb, Y, Sc, Mn, Ca, Ba, Sr, Mg and Si.
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|---|---|---|---|
| CN 02128112 CN1224589C (en) | 2002-12-27 | 2002-12-27 | Bismuth-sodium-potassium-lithium titanate lead-free piezoelectric ceramics |
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|---|---|---|---|
| CN 02128112 CN1224589C (en) | 2002-12-27 | 2002-12-27 | Bismuth-sodium-potassium-lithium titanate lead-free piezoelectric ceramics |
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|---|---|
| CN1511800A CN1511800A (en) | 2004-07-14 |
| CN1224589C true CN1224589C (en) | 2005-10-26 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100371294C (en) * | 2005-02-01 | 2008-02-27 | 四川大学 | Bi.Na.K.Li Ag titanate series lead-free piezoelectric ceramics |
| CN100357221C (en) * | 2005-02-01 | 2007-12-26 | 四川大学 | Bi.Na.Ag Ba titanate series lead-free piezoelectric ceramics |
| JP5273140B2 (en) * | 2008-03-26 | 2013-08-28 | Ｔｄｋ株式会社 | Piezoelectric ceramic and piezoelectric ceramic composition |
| DE102010045597B4 (en) * | 2010-09-16 | 2021-11-04 | Tdk Electronics Ag | Ceramic material, piezoelectric actuator containing the ceramic material and method for producing the ceramic material |
| US8734670B2 (en) | 2010-09-30 | 2014-05-27 | Hewlett-Packard Development Company, L.P. | Lead-free piezoelectric materials with enhanced fatigue resistance |
| CN102173788A (en) * | 2011-01-27 | 2011-09-07 | 西北工业大学 | Sodium bismuth titanate-based high-strain lead-free piezoelectric ceramic and preparation method thereof |
| CN105601270B (en) * | 2015-12-28 | 2018-06-15 | 北京有色金属研究总院 | A kind of water base preparation method of scandium doping with bismuth titanate sodium piezoelectric membrane |
| CN106495684A (en) * | 2016-10-08 | 2017-03-15 | 常州创索新材料科技有限公司 | A kind of preparation method of lead-free piezoceramic material |
| CN109734442A (en) * | 2019-03-21 | 2019-05-10 | 河南城建学院 | A kind of high performance piezoelectric ceramic material and preparation method |
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