CN1541979A - Bismuth sodium titanate barium titanate strontium titanate calcium titanate based lead-free piezoelectric ceramics - Google Patents

Bismuth sodium titanate barium titanate strontium titanate calcium titanate based lead-free piezoelectric ceramics Download PDF

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CN1541979A
CN1541979A CNA200310110880XA CN200310110880A CN1541979A CN 1541979 A CN1541979 A CN 1541979A CN A200310110880X A CNA200310110880X A CN A200310110880XA CN 200310110880 A CN200310110880 A CN 200310110880A CN 1541979 A CN1541979 A CN 1541979A
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titanate
piezoelectric ceramics
piezoelectric ceramic
lead
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CN1260171C (en
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肖定全
赁敦敏
朱建国
余萍
李灵芝
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Sichuan University
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Sichuan University
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Abstract

The lead-free bismuth sodium barium strontium calcium titanate piezoelectric ceramic is one polycomponent perovskite type environment consistency piezoelectric ceramic composition. The composition has the general expression of (1-z)Bi1-wNawTiO3+z+z(Ba1-x-ySrxCay)TiO3 +aMalphaObeta, where x is 0-1, y 0-1, z 0-1, (x+y) 0-1, w 0.3-0.7; MalphaObeta is doping oxide(s) in the content an of 0-10 %; M is +1~+6 valent element capable of forming solid oxide, such as Na, K, Li, Ni, Zn, etc. with alpha and beta being atom number. The piezoelectric ceramic composition has d33 up to 160 pC/N, kp up to 30.0 % and stable technological process, may be produced via traditional piezoelectric ceramic preparation process and industrial material, and is practical.

Description

The bismuth sodium titanate barium titanate strontium titanate calcium titanate based leadless piezoelectric ceramics
One, technical field
The present invention relates to a kind of novel polynary lead-free piezoelectric ceramics composition, belong to perovskite structure environment compatibility piezoelectric ceramics field.
Two, background technology
Find the piezoelectricity of barium titanate ceramics from middle 1940s after, constitutional features is AB O 3The research and development of the piezoelectric ceramics of type are very active, and the components and parts of piezoelectric ceramics and making have been widely used in particularly information industry field of industry.With Pb-based lanthanumdoped zirconate titanates (Pb (Ti, Zr) O 3) being the lead base two component system of representative, the A position is Pb; The B position is Ti, Zr and with PMN-PT [Pb (Mg 1/3Nb 2/3) O 3-PbTiO 3] be base-material, add the 3rd constituent element, as with lead magnoniobate (Pb (Mg 1/3Nb 2/3) O 3) being representative, the A position is Pb, the B position is Mg 1/3Nb 2/3All have good piezoelectricity ferro performance and high Curie temperature with the lead base ternary system piezoelectric ceramic of Ti.The piezoelectric ceramics overwhelming majority who uses in the industrial production is such lead base piezoelectric ceramics.
But, PbO in the lead base piezoceramic material or Pb 3O 4Content accounts for 70% of raw material total amount.PbO or Pb 3O 4At high temperature volatile, cause severe contamination and harm for the mankind and ecotope thereby make in the treating processes of lead base piezoelectric ceramics after producing, use and discarding.In recent years, seek piezoelectric ceramics system lead-free, superior performance and be subjected to the pay attention to day by day of countries in the world.
Common leadless piezoelectric ceramics system has four classes: BaTiO at present 3Based leadless piezoelectric ceramics, bismuth laminated leadless piezoelectric ceramic, base metal niobate leadless piezoelectric ceramics and Bi 0.5Na 0.5TiO 3Based leadless piezoelectric ceramics.More than the characteristics of four class leadless piezoelectric ceramicss be: BaTiO3 base piezoelectric ceramic Curie temperature is 120 ℃ only, and piezoelectric property is medium; The Curie temperature height of bismuth laminated leadless piezoelectric ceramic, but piezoelectric activity is low; The base metal niobate leadless piezoelectric ceramics then is difficult to sinter into fine and close pottery; Bi 0.5Na 0.5TiO 3Based leadless piezoelectric ceramics has the Curie temperature height, easily add other constituent element modification becomes the research focus of non-lead base piezoelectric ceramics to improve characteristics such as piezoelectric property.
Bi 0.5Na 0.5TiO 3Be that the A position is by compound ion Bi 0.5Na 0.5The ABO that constitutes 3The perovskite typed ferroelectrics, A position compound ion Bi 0.5Na 0.5By Bi 3+(A1 position) and Na +(A2 position) constitutes.Simple Bi 0.5Na 0.5TiO 3The pottery coercive field is (73Kv/cm) greatly, and the polarization difficulty is difficult to practicability, must be to Bi 0.5Na 0.5TiO 3It is low to obtain coercive field to carry out modification, the leadless piezoelectric ceramics system that the piezoelectricity ferro performance is good.At present common to Bi 0.5Na 0.5TiO 3Adding method that other constituent element carries out modification has merely with+divalent alkaline-earth metal ions and partly replaces A position ion Bi 0.5Na 0.5Or merely+1 the alkalimetal ion of valency partly replaces the Na of A2 position +Document 1 (JAPANESE JOURNAL OF APPLIED PHYSICS, Vol30,9B, 1991,9, p2236-2239), to have provided composition formula be (1-x) Bi to document 2 (Journal of Inorganic Materials, Vol 15, No5,2000,12) 0.5Na 0.5TiO 3-xBaTiO 3The leadless piezoelectric ceramics system, d 33=125pC/N, k p=29%; It is Bi0.5Na that document 3 (phys.stat.sol. (a) 157,499 (1996)) has provided composition formula 0.5TiO 3-Bi 0.5K 0.5TiO 3The leadless piezoelectric ceramics system, d 33=96pC/N, k p=21%; It is Bi that document 4 (Ferroelectrics.1997, Vol 196, p 175-178) and document 5 (Key Engineering Materials Vols, 157-158 (1999) are p.57-64) have provided composition formula respectively 0.5Na 0.5TiO 3-1/2 (Bi 2O 3Sc 2O 3), Bi 0.5Na 0.5TiO 3-NaNbO 3The leadless piezoelectric ceramics system, d 33=71-92pC/N, k pBe about 15%; It is (Bi that document 6 (Ferroelectrics.1995, Vol 169, p 317-325) and 7 (Ferroelectrics.1990, Vol 106, p 375-380) have provided composition formula 1/2Na 1/2) 1-x(Sr 1/2Ca 1/2) xTiO 3, (Bi 1/2Na 1/2) 1-x(Sr aPb bCa c) xTiO 3The leadless piezoelectric ceramics system, d 33=82pC/N, k p=12-20.3%.It is (1-x) Bi that patent CN85100513, JP2001-48642 provide composition formula 0.5Na 0.5TiO 3-xBaTiO 3Piezoelectric ceramic composition, k p=20.2%, ε 33/ ε 0=290, d 33=159pC/N; It is [Bi that patent JP11-217262, JP2000-22235 provide composition formula 0.5(Na 1-xK x) 0.5] TiO 3Piezoelectric ceramic composition, k p=21.1%, ε 33/ ε 0=611.It is Bi that patent DE19530592C2 has provided composition formula 0.5Na 0.5TiO 3-BaTiO 3-CaTiO 3Piezoelectric ceramic composition, said composition has thickness and big characteristics of electromechanical coupling factor anisotropy radially, k p=16%; It is [Bi that patent JP2000-44335 has provided composition formula 0.5(Na 1-xLi x) 0.5] TiO 3Piezoelectric ceramic composition, k p=23.4%, ε 33/ ε 0=432.
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, to improve existing BaTiO 3Base lead-free battery performance, proposed a class novel form leadless piezoelectric ceramics by the polynary lead-free material.This piezoelectric ceramics adopts the traditional ceramics prepared, and technology stability is good, has good piezoelectricity ferro performance, has approached the product performance of lead base pottery, has practicality.
For realizing purpose of the present invention, the present invention is directed to ABO 3The perovskite typed piezoelectricity system (Bi of structure 0.5Na 0.5) TiO 3, a class A position compound ion Bi has been proposed 0.5Na 0.5The compound ion Ba that part is formed by alkaline-earth metal ions Ba, Sr, Ca 1-x-ySr xCa yReplace formed novel lead-free piezoceramic material, can use general formula (1-z) Bi (1-w)Na wTiO 3+ z (Ba 1-x-ySr xCa y) TiO 3Represent that the x in the formula, y, z and w represent that the respective element material is shared in each constituent element in the compound ion
Atomicity (being atomic percent).The atomicity summation of all elements on the A position should be 1, and the numerical value of x, y, z and w is in the formula: 0＜x＜1,0＜y＜1,0＜z＜1,0＜(x+y)＜1,0.3≤w≤0.7.
The piezoceramic material that the present invention proposes can also be added other metals by the base-material that the front general formula is represented as hotchpotch, and promptly base-material+hotchpotch is formed, and its performance is optimized more.Can be expressed as with general formula: (1-z) Bi (1-w)Na wTiO 3+ z (Ba 1-x-ySr xCa y) TiO 3+ M αO β(wt%), M in general formula αO βThe expression hotchpotch.The shared ratio of hotchpotch is 0-10wt%; The shared ratio of base-material is 90-100wt%.M αO βBe one or more doping oxides, M represents this class+1-+6 valency and can form the element of solid-oxide with oxygen, as Na, K, Li, Ni, Zn, Cr, Co, Nb, Ta, Al, Cu, Fe, Ce, Pr, Nd, Sm, Gd, Dy, Er, Yb, In, Y, Sc, La, Ho, Lu, Sn, Sb, Mn, Ca, Ba, Sr, Mg, Si etc.; α and β represent the atomicity of corresponding element M and oxygen in the relevant oxide compound respectively.
Polynary lead-free piezoelectric ceramics of the present invention has good piezoelectricity ferro performance, detects the piezoelectric constant d of this system piezoelectric ceramics through material property 33Can reach more than the 160pC/N percentage coupling k pCan reach more than 30.0%.Advantage of the present invention is: the leadless piezoelectric ceramics excellent property has had the performance level of Industrial products; Its process stabilizing can adopt conventional piezoelectric ceramics processing and industrial starting material to obtain, and sintering temperature is about 1175-1225 ℃, than low about 50-100 ℃ of lead base piezoelectric ceramics, has practicality.
Four, embodiment
Prepare leadless piezoelectric ceramics of the present invention and can adopt technical pure or chemical pure Bi 2O 3, Na 2CO 3, BaCO3, SrCO 3, CaCO 3, TiO 2, M αO βBe raw material, can select the associated metal oxide compound as required as hotchpotch M αO βConcrete preparation method is: press general formula (1-z) Bi (1-w)Na wTiO 3+ z (Ba 1-x-ySr xCa y) TiO 3The stoichiometric ratio raw materials weighing, behind abundant ball milling mixing, in the alumina crucible of packing into, carry out pre-burning at 800-900 ℃, soaking time is 2-6 hour; Add awt% property-modifying additive M in the pre-burning synthetic powder αO β, levigate through ball milling again, thorough mixing, adding additives, moulding, plastic removal are at last at 1075-1225 ℃ of following sintering 2-3 hour.Ceramic plate behind the sintering is by last silver electrode, and in 60-120 ℃ silicone oil, polarization is 10-20 minute under the voltage of 34kV/mm.
Preparation system (1-z) Bi (1-w)Na wTiO 3+ z (Ba 1-x-ySr xCa y) TiO 3(92-100wt%) or add hotchpotch M αO βThe prescription and the performance index of leadless piezoelectric ceramics (0-8wt%) are as follows:
Embodiment 1:
Prescription:
0.915Bi 0.5Na 0.5TiO 3+0.085(Ba 0.7Sr 0.18Ca 0.12)TiO 3
Performance:
d 33(pC/N) tg δ (%) ε 33/ ε 0k p(%) Qm Poisson's ratio
147 2.0 729 29.7 153 0.292
Embodiment 2:
Prescription:
0.935Bi 0.3Na 0.7TiO 3+0.065(Ba 0.62Sr 0.23Ca 0.15)TiO 3
Performance:
d 33(pC/N) tg δ (%) ε 33/ ε 0k p(%) Qm Poisson's ratio
105 1.2 502 27.0 258 0.292
Embodiment 3:
Prescription:
[0.9Bi 0.5Na 0.5TiO 3+0.1(Ba 0.6Sr 0.3Ca 0.1)TiO 3](95wt％)+Li 2O(5wt％)
Performance:
d 33(pC/N) tg δ (%) ε 33/ ε 0k p(%) Qm Poisson's ratio
162 2.5 984 25.4 126 0.295
Embodiment 4:
Prescription:
0.895Bi 0.4Na 0.6TiO 3+0.105(Ba 0.57Sr 0.14Ca 0.29)TiO 3
Performance:
d 33(pC/N) tg δ (%) ε 33/ ε 0k p(%) Qm Poisson's ratio
132 2.1 681 30.3 186 0.285
Embodiment 5:
Prescription:
[0.915Bi 0.5Na 0.5TiO 3+0.085(Ba 0.7Sr 0.18Ca 0.12)TiO 3](92wt％)+Nb 2O 5(6wt％)+Ta 2O 5(2wt％)
Performance:
d 33(pC/N) tg δ (%) ε 33/ ε 0k p(%) Qm Poisson's ratio
155 2.9 876 24.2 123 0.295
Embodiment 6:
Prescription:
[0.9Bi 0.5Na 0.5TiO 3+0.1(Ba 0.6Sr 0.3Ca 0.1)TiO 3](99wt％)+Na 2O(1wt％)
Performance:
d 33(pC/N) tg δ (%) ε 33/ ε 0k p(%) Qm Poisson's ratio
152 3.0 964 22.4 120 0.291
Embodiment 7:
Prescription:
[0.9Bi 0.5Na 0.5TiO 3+0.1(Ba 0.6Sr 0.3Ca 0.1)TiO 3](92wt％)+CeO 2(5wt％)+Nb 2O 5(3wt％)
Performance:
d 33(pC/N) tg δ (%) ε 33/ ε 0k p(%) Qm Poisson's ratio
158 2.9 979 21.4 127 0.294
Embodiment 8:
Prescription:
[0.895Bi 0.5Na 0.5TiO 3+0.105(Ba 0.57Sr 0.14Ca 0.29)TiO 3](92wt％)+La 2O 3(8wt％)
Performance:
d 33(pC/N) tg δ (%) ε 33/ ε 0k p(%) Qm Poisson's ratio
132 2.1 681 30.3 183 0.285
Embodiment 9:
Prescription:
[0.9Bi 0.5Na 0.5TiO 3+0.1(Ba 0.60Sr 0.30Ca 0.10)TiO 3](95wt％)+Fe 2O 3(5wt％)
Performance:
d 33(pC/N) tg δ (%) ε 33/ ε 0k p(%) Qm Poisson's ratio
148 3.9 961 20.0 147 0.290

Claims (6)

1. bismuth sodium titanate barium titanate strontium titanate calcium titanate based leadless piezoelectric ceramics is at ABO 3The A position is compound ion Bi in the structure 0.5Na 0.5, it is characterized in that A position compound ion Bi 0.5Na 0.5The compound ion Ba that part is formed by alkaline-earth metal ions Ba, Sr, Ca 1-x-ySr xCa yReplace and constitute lead-free piezoceramic material.
2. piezoelectric ceramics as claimed in claim 1 is characterized in that by general formula (1-z) Bi (1-w)Na wTiO 3+ z (Ba 1-x-ySr xCa y) TiO 3The material of expression constitutes, 0＜x in the formula＜1,0＜y＜1,0＜z＜1,0＜(x+y)＜1,0.3≤w≤0.7.
3. piezoelectric ceramics as claimed in claim 2 is characterized in that having added one or more doping oxides, and hotchpotch content is 0-10wt%, and the content of all the other base material is 90-100wt%, is expressed as (1-z) Bi with general formula (1-w)Na wTiO 3+ z (Ba 1-x-ySr xCa y) TiO 3+ M αO β(wt%), M αO βBe one or more doping oxides, M is for+1-+6 valency and can form element Na, K, Li, Ni, Zn, Cr, Co, Nb, Ta, Al, Cu, Fe, Ce, Pr, Nd, Sm, Gd, Dy, Er, Yb, In, Y, Sc, La, Ho, Lu, Sn, Sb, Mn, Ca, Ba, Sr, Mg or the Si of solid-oxide with oxygen.
4. as the piezoelectric ceramics of claim 1 or 2, it is characterized in that by composition formula 0.915Bi 0.5Na 0.5TiO 3+ 0.085 (Ba 0.7Sr 0.18Ca 0.12) TiO 3Or 0.935Bi 0.3Na 0.7TiO 3+ 0.065 (Ba 0.62Sr 0.23Ca 0.15) TiO 3Or 0.895Bi 0.4Na 0.6TiO 3+ 0.105 (Ba 0.57Sr 0.14Ca 0.29) TiO 3The material of expression constitutes.
5. piezoelectric ceramics as claimed in claim 3 is characterized in that by composition formula [0.9Bi 0.5Na 0.5TiO 3+ 0.1 (Ba 0.6Sr 0.3Ca 0.1) TiO 3] (95wt%)+Li 2O (5wt%) or [0.9Bi 0.5Na 0.5TiO 3+ 0.1 (Ba 0.6Sr 0.3Ca 0.1) TiO 3] (99wt%)+Na 2O (1wt%) or [0.895Bi 0.5Na 0.5TiO 3+ 0.105 (Ba 0.57Sr 0.14Ca 0.29) TiO 3] (92wt%)+La 2O 3(8wt%) or [0.9Bi 0.5Na 0.5TiO 3+ 0.1 (Ba 0.60Sr 0.30Ca 0.10) TiO 3] (95wt%)+Fe 2O 3(5wt%) material of expression constitutes.
6. piezoelectric ceramics as claimed in claim 3 is characterized in that by composition formula [0.915Bi 0.5Na 0.5TiO 3+ 0.085 (Ba 0.7Sr 0.18Ca 0.12) TiO 3] (92wt%)+Nb 2O 5(6wt%)+Ta 2O 5(2wt%) or [0.9Bi 0.5Na 0.5TiO 3+ 0.1 (Ba 0.6Sr 0.3Ca 0.1) TiO 3] (92wt%)+CeO 2(5wt%)+Nb 2O 5(3wt%) material of expression constitutes.
CN 200310110880 2003-11-07 2003-11-07 Bismuth sodium titanate barium titanate strontium titanate calcium titanate based lead-free piezoelectric ceramics Expired - Fee Related CN1260171C (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100522873C (en) * 2005-12-30 2009-08-05 中国科学院上海硅酸盐研究所 Bismuth layer structure relaxation ferroelectrical ceramic material and preparation process thereof
CN101891465A (en) * 2010-07-08 2010-11-24 桂林理工大学 Barium-strontium stannate titanate lead-free piezoelectric ceramics with high piezoelectric constant
CN101284731B (en) * 2008-05-21 2012-10-03 中国科学院上海硅酸盐研究所 Leadless positive temperature coefficient resistance material of high use temperature and stability and method for making same
CN103708829A (en) * 2013-12-19 2014-04-09 桂林电子科技大学 Abnormal piezoelectric anisotropy lead-free piezoelectric ceramic and texturing preparation method thereof
CN111875373A (en) * 2015-05-27 2020-11-03 爱普科斯公司 Dielectric composition based on bismuth sodium strontium titanate, dielectric element, electronic component and laminated electronic component thereof
CN113233890A (en) * 2021-05-13 2021-08-10 陕西科技大学 High-electrocaloric-effect sodium bismuth titanate-based ceramic material, preparation method, application and ceramic

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100522873C (en) * 2005-12-30 2009-08-05 中国科学院上海硅酸盐研究所 Bismuth layer structure relaxation ferroelectrical ceramic material and preparation process thereof
CN101284731B (en) * 2008-05-21 2012-10-03 中国科学院上海硅酸盐研究所 Leadless positive temperature coefficient resistance material of high use temperature and stability and method for making same
CN101891465A (en) * 2010-07-08 2010-11-24 桂林理工大学 Barium-strontium stannate titanate lead-free piezoelectric ceramics with high piezoelectric constant
CN103708829A (en) * 2013-12-19 2014-04-09 桂林电子科技大学 Abnormal piezoelectric anisotropy lead-free piezoelectric ceramic and texturing preparation method thereof
CN103708829B (en) * 2013-12-19 2016-04-06 桂林电子科技大学 A kind of unusual Piezoelectric Anisotropy leadless piezoelectric ceramics and texturing preparation method thereof
CN111875373A (en) * 2015-05-27 2020-11-03 爱普科斯公司 Dielectric composition based on bismuth sodium strontium titanate, dielectric element, electronic component and laminated electronic component thereof
CN111875373B (en) * 2015-05-27 2022-11-29 爱普科斯公司 Dielectric composition based on bismuth sodium strontium titanate, dielectric element, electronic component and laminated electronic component thereof
CN113233890A (en) * 2021-05-13 2021-08-10 陕西科技大学 High-electrocaloric-effect sodium bismuth titanate-based ceramic material, preparation method, application and ceramic

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