CN1260171C - 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 PDFInfo
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- CN1260171C CN1260171C CN200310110880.XA CN200310110880A CN1260171C CN 1260171 C CN1260171 C CN 1260171C CN 200310110880 A CN200310110880 A CN 200310110880A CN 1260171 C CN1260171 C CN 1260171C
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- 239000000919 ceramic Substances 0.000 title claims abstract description 52
- 229910002113 barium titanate Inorganic materials 0.000 title claims description 5
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims description 4
- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 title claims description 3
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 title claims description 3
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 title claims description 3
- 239000011734 sodium Substances 0.000 claims abstract description 47
- 239000011575 calcium Substances 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052788 barium Inorganic materials 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 3
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 3
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052738 indium Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 14
- -1 compound ion Chemical class 0.000 claims description 10
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 16
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 229910010252 TiO3 Inorganic materials 0.000 abstract 4
- MUSRXJYSDKILRA-UHFFFAOYSA-N [Ca].[Sr].[Ba].[Na].[Bi] Chemical compound [Ca].[Sr].[Ba].[Na].[Bi] MUSRXJYSDKILRA-UHFFFAOYSA-N 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000470 constituent Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910020215 Pb(Mg1/3Nb2/3)O3PbTiO3 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
The present invention relates to bismuth sodium barium strontium calcium titanate leadless piezoelectric ceramics, particularly to a novel multicomponent leadless piezoelectric ceramic composition, which belongs 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 (1-z)Bi<1-w>Na<w>TiO3+z(Ba<1-x-y>Sr<x>Ca<y>)TiO3 +aM<alpha>O<beta> (wt%), wherein x is greater than 0 and less than 1, y is greater than 0 and less than 1, z is greater than 0 and less than 1, x plus y is greater than 0 and less than 1, and w 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 ((1-z)Bi<1-w>Na<w>TiO3+z(Ba<1-x-y>Sr<x>Ca<y>)TiO3), M is +1 to +6 valent elements, such 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., which can from solid-state oxide with oxygen, and alpha and beta respectively express atomic numbers of corresponding elements M and oxygen in relevant oxide. D33 of the piezoelectric ceramic composition can reach more than 160 pC/N, and k<p> can reach more than 30.0%. The present invention has the advantages of stable technology and practicability, 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 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 Bi that document 3 (phys.stat.sol. (a) 157,499 (1996)) has provided composition formula
0.5Na
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 the shared atomicity (being atomic percent) in each constituent element of respective element material in the compound ion.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 3-4kV/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 (3)
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.
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|---|---|---|---|
| CN200310110880.XA CN1260171C (en) | 2003-11-07 | 2003-11-07 | Bismuth sodium titanate barium titanate strontium titanate calcium titanate based lead-free piezoelectric ceramics |
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|---|---|---|---|
| CN200310110880.XA CN1260171C (en) | 2003-11-07 | 2003-11-07 | Bismuth sodium titanate barium titanate strontium titanate calcium titanate based lead-free piezoelectric ceramics |
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|---|---|
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| CN1260171C true CN1260171C (en) | 2006-06-21 |
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| 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 |
| 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 |
| CN107851514B (en) * | 2015-05-27 | 2020-08-21 | 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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