CN100357221C - Bi.Na.Ag Ba titanate series lead-free piezoelectric ceramics - Google Patents

Bi.Na.Ag Ba titanate series lead-free piezoelectric ceramics Download PDF

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CN100357221C
CN100357221C CNB200510020295XA CN200510020295A CN100357221C CN 100357221 C CN100357221 C CN 100357221C CN B200510020295X A CNB200510020295X A CN B200510020295XA CN 200510020295 A CN200510020295 A CN 200510020295A CN 100357221 C CN100357221 C CN 100357221C
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piezoelectric ceramics
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CN1814569A (en
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肖定全
吴浪
赁敦敏
朱建国
余萍
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Sichuan University
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Abstract

The present invention relates to bismuth sodium silver barium titanate series piezoelectric ceramics with ABO3 structures, which belongs to the field of environmental consistency piezoelectric ceramics with perovskite structures. The piezoelectric ceramic composition provided by the present invention can be expressed by the general formula of (Bi<0.5>(Na<1-x>Ag<x>)<0.5>)<1-y>Ba<y>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, and x plus y is more than 0 and less than 1; M<alpha>O<beta> is one or a plurality of kinds of doped oxide, the content a of M<alpha>O<beta> accounts for 0 to 5% of the weight of the main components (Bi<w>(Na<1-x-y-z>K<x>Li<y>Ag<z>)<1-w>TiO3), and M is +1 to +6 valent elements, such as 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, Bi, etc., which can form solid-state oxide with oxygen; alpha and beta respectively express atomic number of a corresponding element M and oxygen in relevant oxide. The calcination temperature is controlled to 800 to 1000 DEG C, and heat preservation is carried out for 1 to 4 hours; the sintering temperature is controlled to 1100 to 1200 DEG C, and heat preservation is carried out for 1 to 4 hours. The piezoelectric constant d33 of the obtained piezoelectric ceramic materials can reach more than 160 pC/N, the electromechanical coupling coefficient kp reaches more than 31.0%, and dielectric loss tgdelta is below 0.03. The series piezoelectric ceramic materials have stable preparing technology and practicability, and are prepared from industrial raw materials by the traditional piezoelectric ceramic preparing technique.

Description

Bismuth-sodium titanate silver barium series lead-free piezoelectric ceramic
One, technical field
The present invention relates to a class novel lead-free piezoelectric ceramics, belong to perovskite structure environment compatibility piezoelectric ceramics field.
Two, background technology
From middle 1940s; after finding the piezoelectricity of barium titanate ceramics, the research and development of piezoelectric ceramics are very active, at present; piezoelectric ceramics has been widely used in particularly information industry field of industry, and the components and parts of being made by piezoelectric ceramics have been penetrated in the middle of the daily life.
But, 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.In recent years, seek piezoelectric ceramics system lead-free, superior performance and be subjected to the attention of countries in the world.
Bismuth-sodium titanate (Bi 0.5Na 0.5TiO 3, be called for short BNT) and be a kind of leadless environment-friendly type piezoelectricity ferro stupalith with perovskite structure, have very big residual polarization (Pr=38 μ C/cm 2), but because coercive electric field very high (Ec=73kV/mm), therefore the very difficulty that polarizes during making need reduce its coercive field by doping vario-property, makes it to be beneficial to polarization to improve its performance.At present, best, the most promising component of the performance of Gong Rening is Bi 0.5Na 0.5TiO 3-BaTiO 3(being called for short BNBT), its piezoelectric constant d 33Can reach 125 pC/N.Having a small amount of in the existing document is the report that matrix carries out the doped and substituted modification with BNBT.It is [Bi that patent CN1511800A has provided composition formula 1-z(Na 1-x-yK xLi y) z] TiO 3The piezoelectric ceramic composition of system; Patent CN1456531A provides the piezoelectric ceramic composition of Co+ doping with bismuth titanate sodium-barium titanate system; It is (1-x) Bi that patent JP11-180769 has provided composition formula 0.5Na 0.5TiO 3-xBaTiO 3, the La of interpolation 0.5-1.5wt% 2O 3, Y 2O 3, Yb 2O 3, Sm 2O 3, Nd 2O 3, CeO 2Deng the piezoelectric ceramics that can obtain different performance behind the oxide compound.
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, and to composition formula Bi 0.5Na 0.5TiO 3-BaTiO 3The leadless piezoelectric ceramics of (be called for short BNBT) by with the Ag element Na element of A position among the BNBT being carried out the part replacement, has proposed new non-lead base of a class and the piezoelectric ceramic composition with good piezoelectricity ferro performance.
For realizing purpose of the present invention, the present invention proposes a class ABO 3The bismuth-sodium titanate silver barium series lead-free piezoelectric ceramic of structure is at composition formula Bi 0.5Na 0.5TiO 3-BaTiO 3, in the A position, partly replacing Na with Ag, i.e. the compound ion formed of Bi and Na, Ag and Ba forms a kind of novel lead-free piezoelectric ceramic composition of perovskite structure.
The lead-free piezoelectric ceramic composition that the present invention proposes can be used general formula [Bi 0.5(Na 1-xAg x) 0.5] 1-yBa yTiO 3Represent that x, y represent the atomicity of component material in the formula, the numerical range of x, y is: 0＜x＜1,0＜y＜1,0＜(x+y)＜1.
The present invention adds one or more oxide Ms in the represented base-material of above-mentioned general formula αO βAs property-modifying additive, to obtain this class lead-free piezoelectric ceramic composition of different performance, this class lead-free piezoelectric ceramic composition can be used general formula [Bi 0.5(Na 1-xAg x) 0.5] 1-yBa yTiO 3+ a M αO β(%) expression, in the formula: x, y represent the atomicity of component material, its numerical range is: 0＜x＜1,0＜y＜1,0＜(x+y)＜1; A is an additive level, and its numerical value is the 0-5wt% of body material; M is for+1-+6 valency and can form the element of solid-oxide with oxygen, as Na, K, Li, Al, Cu, Fe, Ce, Pr, Nd, Sm, Gd, Dy, Er, Yb, Y, Sc, Mn, Ca, Ba, Sr, Mg or Si etc.; α and β represent the atomicity of corresponding element M and oxygen in the relevant oxide compound respectively.
Advantage of the present invention has: 1. material system is a leadless piezoelectric ceramics; 2. be beneficial to polarization, piezoelectricity ferro excellent property, d 33Can reach 168 (pC/N) even higher; 3. need not to seal sintering, technology stability is good; 4. density is good; 5. calcining temperature and sintering temperature are lower, in 800～1200 ℃ of temperature ranges; Have more environment compatibility.
Four, embodiment
Prepare leadless piezoelectric ceramics of the present invention and can adopt technical pure or chemical pure bismuth oxide (Bi 2O 3), anhydrous sodium carbonate (Na 2CO 3), barium carbonate (BaCO 3), titanium dioxide (TiO 2), silver suboxide (Ag 2O), can also select the associated metal oxide compound as hotchpotch M according to different needs as raw material αO βPreparation process is: press general formula [Bi 0.5(Na 1-xAg x) 0.5] 1-yBa yTiO 3Or according to general formula [Bi 0.5(Na 1-xAg x) 0.5] 1-yBa yTiO 3+ aM αO β(wt%) press stoichiometry weight ratio raw materials weighing when, behind abundant ball milling mixing, in the alumina crucible of packing into, under 800～1000 ℃ of temperature, calcine soaking time 2～4 hours.Calcining synthetic powder is levigate through ball-milling technology again, and adding additives, moulding, plastic removal are then 1100～1200 ℃ of sintering temperatures 2～4 hours.Ceramic plate behind the sintering, was polarized under the voltage of 3～4kV 15～30 minutes in 60～120 ℃ silicone oil by last silver electrode.At last by the performance perameters such as leadless piezoelectric ceramics test piezoelectricity of IRE standard to making.
Further specify the present invention below in conjunction with embodiment.
Preparation process and condition that embodiment adopts are:
According to molecular formula proportioning, raw materials weighing,,, behind abundant ball milling mixing, in the alumina crucible of packing into, compress gently as medium with dehydrated alcohol, in air, calcine soaking time 2～4 hours under 800～1000 ℃ of temperature.Calcining synthetic powder is levigate through ball-milling technology again, adds 10wt% binding agent (concentration is the polyvinyl alcohol water solution of 10wt%) in dried powder, at the forming under the pressure of 10～20Mpa.Base substrate after the moulding is carried out plastic removal at 500～800 ℃, then 1100～1200 ℃ of sintering temperatures 2～4 hours.Ceramic plate behind the sintering, was polarized under the voltage of 3～4kV 15～30 minutes in 60～120 ℃ silicone oil by last silver electrode.
The test condition that the leadless piezoelectric ceramics for preparing is adopted is:
Test specific inductivity and dielectric loss: under the 1KHz electric field frequency, use HP 4278A type electric impedance analyzer to record the sample capacitor C pAnd dielectric loss, then by formula ε r=4 * C p* t/ π * ε 0* d 2Calculate relative permittivity.
Test piezoelectric constant d 33: with the ZJ-3A type quasistatic d of Acoustical Inst., Chinese Academy of Sciences's development 33Survey meter records.
Test machine electric coupling coefficient k p: record by resonance-antiresonance method (using HP4194A type electric impedance analyzer).
Embodiment 1:
According to molecular formula [Bi 0.5(Na 0.96Ag 0.04) 0.5] 0.94Ba 0.06TiO 3Proportioning raw material, preparation process condition are as previously mentioned.
Recording performance perameter is:
d 33(pC/N) tg δ ε 33/ ε 0k p(%) Qm Q MPoisson's ratio
163 0.0269 857.6 32.6 118.9 0.271
Embodiment 2:
According to molecular formula [Bi 0.5(Na 0.94Ag 0.06) 0.5] 0.94Ba 0.06TiO 3Proportioning raw material, preparation process condition are as previously mentioned.
Recording performance perameter is:
d 33(pC/N) tg δ ε 33/ ε 0k p(%) Qm Q MPoisson's ratio
168 0.0296 918.8 31.0 120.5 0.270
Embodiment 3:
According to molecular formula [Bi 0.5(Na 0.98Ag 0.02) 0.5] 0.94Ba 0.06TiO 3Proportioning raw material, preparation process condition are as previously mentioned.
Recording performance perameter is:
d 33(pC/N) tg δ ε 33/ ε 0k p(%) Qm Q MPoisson's ratio
159 0.0252 813.6 32.6 122.8 0.269
Embodiment 4:
According to molecular formula [Bi 0.5(Na 0.96Ag 0.04) 0.5] 0.92Ba 0.08TiO 3Proportioning raw material, preparation process condition are as previously mentioned.
Recording performance perameter is:
d 33(pC/N) tg δ ε 33/ ε 0k p(%) Qm Q MPoisson's ratio
159 0.0282 1127.3 16.5 96.9 0.276
Embodiment 5:
According to molecular formula [Bi 0.5(Na 0.96Ag 0.04) 0.5] 0.90Ba 0.10TiO 3Proportioning raw material, preparation process condition are as previously mentioned.
Recording performance perameter is:
d 33(pC/N) tg δ ε 33/ ε 0k p(%) Qm Q MPoisson's ratio
137 0.0266 878.1 16.2 99.2 0.269
Embodiment 6:
By molecular formula [Bi 0.5(Na 0.94Ag 0.06) 0.5] 0.94Ba 0.06TiO 3+ 0.15% (wt) MnO 2Raw materials weighing.Preparation process condition as previously mentioned.
Recording performance perameter is:
d 33(pC/N) tg δ ε 33/ ε 0k p(%) Qm Q MPoisson's ratio
160 0.0200 803.9 33.5 162.2 0.267
Embodiment 7:
By molecular formula [Bi 0.5(Na 0.94Ag 0.06) 0.5] 0.94Ba 0.06TiO 3+ 0.10% (wt) Y 2O 3Raw materials weighing.Preparation process condition as previously mentioned.
Recording performance perameter is:
d 33(pC/N) tg δ ε 33/ ε 0k p(%) Qm Q MPoisson's ratio
165 0.0218 829.2 33.4 146.7 0.267
Embodiment 8:
By molecular formula [Bi 0.5(Na 0.94Ag 0.06) 0.5] 0.94Ba 0.06TiO 3+ 0.25% (wt) MgO raw materials weighing.Preparation process condition as previously mentioned.
Recording performance perameter is:
d 33(pC/N) tg δ ε 33/ ε 0k p(%) Qm Q MPoisson's ratio
149 0.0177 788.9 31.2 180.9 0.269

Claims (4)

1. ABO 3The bismuth-sodium titanate silver barium system piezoelectric ceramics of structure, composition formula is Bi 0.5Na 0.5TiO 3-BaTiO 3, it is characterized in that partly replacing Na with Ag in the A position forms compound ion, is expressed as [Bi with general formula 0.5(Na 1-xAg x) 0.5] 1-yBa yTiO 3, 0＜x in the formula≤0.06,0＜y≤0.1,0＜(x+y)≤0.16.
2. piezoelectric ceramics as claimed in claim 1 is characterized in that adding oxide M in this piezoceramic material αO β, be expressed as [Bi with general formula 0.5(Na 1-xAg x) 0.5] 1-yBa yTiO 3+ a M αO β(wt%), 0＜x in the formula≤0.06,0＜y≤0.1,0＜(x+y)≤0.16; Additive level a is the 0-5wt% of body material; M is for+1-+6 valency and can form element Na, K, Li, Al, Cu, Fe, Ce, Pr, Nd, Sm, Gd, Dy, Er, Yb, Y, Sc, Mn, Ca, Ba, Sr, Mg or the Si of solid-oxide with oxygen; α and β represent the atomicity of corresponding element M and oxygen in the relevant oxide compound respectively.
3. piezoelectric ceramics as claimed in claim 1 is characterized in that by composition formula [Bi 0.5(Na 0.96Ag 0.04) 0.5] 0.94Ba 0.06TiO 3Or [Bi 0.5(Na 0.94Ag 0.06) 0.5] 0.94Ba 0.06TiO 3Or [Bi 0.5(Na 0.98Ag 0.02) 0.5] 0.94Ba 0.06TiO 3Or [Bi 0.5(Na 0.96Ag 0.04) 0.5] 0.92Ba 0.08TiO 3Or [Bi 0.5(Na 0.96Ag 0.04) 0.5] 0.90Ba 0.10TiO 3The material of expression constitutes.
4. piezoelectric ceramics as claimed in claim 2 is characterized in that by composition formula [Bi 0.5(Na 0.94Ag 0.06) 0.5] 0.94Ba 0.06TiO 3+ 0.15% (et) MnO 2Or [Bi 0.5(Na 0.94Ag 0.06) 0.5] 0.94Ba 0.06TiO 3+ 0.10% (wt) Y 2O 3Or [Bi 0.5(Na 0.94Ag 0.06) 0.5] 0.94Ba 0.06TiO 3The material that+0.25% (wt) MgO represents constitutes.
CNB200510020295XA 2005-02-01 2005-02-01 Bi.Na.Ag Ba titanate series lead-free piezoelectric ceramics Expired - Fee Related CN100357221C (en)

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CN103803966B (en) * 2013-12-19 2015-08-19 桂林电子科技大学 A kind of high-temp leadless piezoelectric ceramics with nearly zero-temperature coefficient and preparation method thereof
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CN106866135B (en) * 2017-03-13 2019-12-06 中国地质大学（北京） Preparation method of lead-free high-Curie temperature BaTiO 3-based positive temperature coefficient thermal sensitive ceramic
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Patent Citations (4)

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JPH11180769A (en) * 1997-12-19 1999-07-06 Nissan Motor Co Ltd Piezoelectric ceramic material and its production
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