CN102515762A - Sodium niobate barium-bismuth-potassium titanate lead-free piezoelectric ceramic composition - Google Patents
Sodium niobate barium-bismuth-potassium titanate lead-free piezoelectric ceramic composition Download PDFInfo
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- CN102515762A CN102515762A CN201110435330XA CN201110435330A CN102515762A CN 102515762 A CN102515762 A CN 102515762A CN 201110435330X A CN201110435330X A CN 201110435330XA CN 201110435330 A CN201110435330 A CN 201110435330A CN 102515762 A CN102515762 A CN 102515762A
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Abstract
The invention provides a novel sodium niobate barium-bismuth-potassium titanate lead-free piezoelectric ceramic composition. The composition comprises perovskite antiferroelectric NaNbO3 and strong ferroelectric Ba1-y(Bi0.5K0.5)yTiO3. A general formula of the composition is (1-x)NaNbO3-xBa1-y(Bi0.5K0.5)yTiO3, wherein x and y in the formula satisfy the following equations: 0.025<=x<=0.25 and 0<y<1. The lead-free piezoelectric ceramic composition can further comprise one or more oxides and have a general formula of (1-x)NaNbO3-xBa1-y(Bi0.5K0.5)yTiO3 ((100-a)mol%) + MalphaObeta (amol%), wherein MalphaObeta is one or more oxides, the content a of MalphaObeta is 0 to 3%, expressed in molar ratio, of the main components of (1-x) of NaNbO3 xBa1-y(Bi0.5K0.5) yTiO3, M is monovalence to sexavalence elements which can form solid oxides with oxygen, and alpha and beta respectively represent corresponding atomic numbers of the element M and oxygen in a relevant oxide. The sodium niobate barium-bismuth-potassium titanate piezoelectric ceramic composition has an optimal value d33 of more than 130pC/N, kp of more than 20% and Qm of more than 1200 and has good compactness; a process for the composition is stable; the composition is prepared by using a conventional preparation process for piezoelectric ceramics and has practicability.
Description
Technical field
The invention belongs to calcium titanium ore structure piezoelectric ceramics field, relate to a kind of novel polynary system columbate leadless piezoelectric ceramic composition, particularly relate to a kind of sodium columbate barium titanate bismuth potassium series lead-free piezoelectric ceramic compsn.
Background technology
From the piezoelectricity of middle 1940s discovery barium titanate ceramics, particularly have Pb-based lanthanumdoped zirconate titanates Pb (Ti, Zr) O of excellent piezoelectric property and high-curie temperature
3After pottery was succeeded in developing, constitutional features was ABO
3The research and development of the lead-based perovskite piezoelectric ceramics of type are very active, and piezoelectric ceramics and piezoelectric ceramic devices 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, add the 3rd constituent element [as with lead magnoniobate (Pb (Mg
1/3Nb
2/3) O
3), the plumbous Pb (Mn of antimony mangaic acid
1/3Sb
2/3) O
3Be representative] the lead base ternary system piezoelectric ceramic have good piezoelectricity ferro performance, high Tc.The piezoelectric ceramics overwhelming majority who uses in the industrial production is this perovskite-like lead base piezoelectric ceramics.
But, in the lead base piezoceramic material, PbO or Pb
3O
4Content account for 70% of raw material total amount.Lead contamination has become one of human public hazards.The lead base piezoelectric ceramics 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, exploitation piezoelectric ceramics system lead-free, superior performance receives the particularly pay attention to day by day of America and Europe, Japan, Korea S and China of countries in the world.
The leadless piezoelectric ceramics system of broad research has four types at present: bismuth laminated leadless piezoelectric ceramic, BaTiO
3Based leadless piezoelectric ceramics, Bi
0.5Na
0.5TiO
3Based leadless piezoelectric ceramics and K
0.5Na
0.5NbO
3Alkali Metals Niobate Lead Free Piezoelectric Ceramics.The bismuth laminated leadless piezoelectric ceramic Tc is high, and anisotropy is big, but piezoelectric activity is extremely low; BaTiO
3The base piezoelectric ceramic Tc is merely 120 ℃, has ferroelectric four directions-ferroelectric quadrature phase boundary near the room temperature, and the temperature stability of electric property is relatively poor, and mechanical quality factor is little; Bi
0.5Na
0.5TiO
3It is strong and be easy to the characteristics that modification improves piezoelectric property that based leadless piezoelectric ceramics has piezoelectricity; But near second phase transformation 210 ℃ causes the umpolarization temperature to be lower than 210 ℃; Often follow the serious reduction of umpolarization temperature when modification improves piezoelectric property, mechanical quality factor is little; K
0.5Na
0.5NbO
3Alkali Metals Niobate Lead Free Piezoelectric Ceramics is through introducing ABO
3Type compound or similar ionic replacement modification make ferroelectric four directions-ferroelectric quadrature phase transformation shift to room temperature and improve piezoelectric property, but the ferroelectric four directions of room temperature-ferroelectric quadrature two-phase coexistent makes the temperature stability of electric property relatively poor, and mechanical quality factor is little.
Sodium columbate NaNbO
3Be orthohormbic structure uhligite antiferroelectric, be considered to the most complicated perovskite structural material.Along with the reduction of temperature, paraelectric phase-antiferroelectric phase-ferroelectric equal six structural phase transitions (Phys. Rev. B, 76,024110-1-8 (2007)) take place successively.At NaNbO
3The middle ABO that introduces
3The type compound can form NaNbO
3-CaTiO
3(Phys. Rev. B 77,052104 (2008)), NaNbO
3-SrTiO
3(Chem. Mater., 17,1880-1886 (2005)), NaNbO
3-BaSnO
3(Solid State Sci. 6,333-337 (2004)), NaNbO
3-CaSnO
3NaNbO such as (J. Alloys Compd., 465,222-226 (2008))
3Matrix system, these systems have significant improved relaxation behavior and are furtherd investigate as dielectric materials, but do not demonstrate piezoelectric property.In addition, at NaNbO
3Middle niobate ferroelectric such as the KNbO of introducing
3(J. Am.Ceram. Soc., 82,797 – 818 (1999)), LiNbO
3(J. Appl. Phys., 48,3014-3017 (1977)) can obtain piezoelectrics.In addition, with respect to above-mentioned four types of leadless piezoelectric ceramicss, about NaNbO
3The research of base non-plumbum ferroelectric piezoceramic material is few.
Summary of the invention
The object of the present invention is to provide a kind of sodium columbate barium titanate bismuth potassium series lead-free piezoelectric ceramic compsn, to solve the problems referred to above on the prior art.Compsn provided by the present invention has overcome the inherent defective of existing lead base piezoelectric ceramics system own, and has improved existing leadless piezoelectric ceramics performance.Such lead-free piezoelectric ceramic composition adopts the traditional ceramics prepared, has good piezoelectricity ferro performance, and mechanical quality factor is high, and dielectric loss is little, and technology stability is good, has practicality.
Sodium columbate barium titanate bismuth potassium series lead-free piezoelectric ceramic compsn provided by the invention comprises uhligite antiferroelectric NaNbO
3With strong ferroelectrics Ba
1-y(Bi
0.5K
0.5)
yTiO
3According to antiferroelectric NaNbO
3And strong ferroelectrics Ba
1-y(Bi
0.5K
0.5)
yTiO
3Inherent characteristics own, being expected to form good piezoelectrics principle with antiferroelectric and ferroelectrics solid solution is guidance, the present invention is to antiferroelectric NaNbO
3The strong ferroelectrics Ba of middle introducing
1-y(Bi
0.5K
0.5)
yTiO
3, solid solution has formed a kind of novel calcium titanium ore structure lead-free piezoceramic material.
Ceramic composition provided by the present invention can be used general formula (1-x) NaNbO
3-xBa
1-y(Bi
0.5K
0.5)
yTiO
3Represent that x, y represent the atomicity that respective element is shared, i.e. atomic percent, 0.025≤x in the formula≤0.25,0<y<1.
In addition, can also further contain one or more oxide compounds in the sodium columbate barium titanate bismuth potassium series lead-free piezoelectric ceramic compsn of the present invention, then the general formula of compsn is (1-x) NaNbO
3-xBa
1-y(Bi
0.5K
0.5)
yTiO
3((100-a) mol%)+M
αO
β(amol%), M in formula
αO
βExpression oxide compound, α and β are represented the atomicity of corresponding element M and oxygen in the relevant oxide compound respectively, and amol% accounts for the overall mol ratio of compsn, wherein 0≤a≤3 for this oxide compound.M is+1 to+6 valency and the element that can form solid-oxide with oxygen, and it includes but not limited to the element of at least a Na of being selected from, 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 or Ag.Preferred M is Mn.
The piezoceramic material that the present invention proposes can also be added oxide compound (being base-material+hotchpotch) to be made up of the base-material that the front general formula is represented, makes some performance optimizations.Can be expressed as (1-x) NaNbO with general formula
3-xBa
1-y(Bi
0.5K
0.5)
yTiO
3((100-a) mol%)+M
αO
β(amol%), M in formula
αO
βThe expression hotchpotch, the shared proportion of hotchpotch is 0-3mol%.M
αO
βBe one or more doping oxides; M is+1 to+6 valency and the element that can form solid-oxide with oxygen; Like 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, Bi, Ag etc., α and β represent the atomicity of corresponding element M and oxygen in the relevant oxide compound respectively.
Sodium columbate barium titanate bismuth potassium series lead-free piezoelectric ceramic compsn of the present invention has good piezoelectricity ferro performance, through material properties test, and piezoelectric constant
d 33Can reach more than the 130pC/N,
k pCan reach more than 20%,
Q mCan reach more than 1200, dielectric loss is lower than 2.50%.The advantage of compsn provided by the invention is: not leaded; Piezoelectric property is good; Ferroelectricity is strong; Mechanical quality factor is big; Dielectric loss is little; Stable preparation process adopts the conventional piezoelectric ceramics processing to obtain; Sintering temperature is low, is about 1060-1220 ℃.Through further containing oxide compound, can modulate some performance perameters of this lead-free piezoelectric ceramic composition.
Description of drawings
Fig. 1 is the 0.95NaNbO that the present invention records
3-0.05Ba
0.6(Bi
0.5K
0.5)
0.4TiO
3(99mol%)+MnO
2(1mol%) leadless piezoelectric ceramics ferroelectric hysteresis loop at room temperature.
Fig. 2 is the 0.95NaNbO that the present invention records
3-0.05Ba
0.6(Bi
0.5K
0.5)
0.4TiO
3(99mol%)+MnO
2(1mol%) at the specific inductivity (ε of 1kHz
r)-temperature (T) curve.
Embodiment
Below will describe the present invention through embodiment, these embodiment are property illustrative purposes presented for purpose of illustration just, and is not to be used to limit the present invention.
Preparing general formula according to the invention is (1-x) NaNbO
3-xBa
1-y(Bi
0.5K
0.5)
yTiO
3Leadless piezoelectric ceramics can adopt technical pure, CP or analytically pure Na
2CO
3, K
2CO
3, BaCO
3, Bi
2O
3, TiO
2, Nb
2O
5Be raw material, make according to conventional preparation method.For example; A kind of method wherein is the stoichiometric ratio raw materials weighing according to general formula, after abundant milling mixing, in the alumina crucible of packing into; Carry out pre-burning at 800-900 ℃; Soaking time is 6 hours, and levigate through ball milling again, thorough mixing, adding additives, moulding, plastic removal are at last at 1060-1120 ℃ of following sintering 2-6 hour.Ceramic plate behind the sintering is by last silver electrode, and in 60-100 ℃ silicone oil, polarization is 30-40 minute under the voltage of 3-6kV/mm.
Preparing general formula according to the invention is (1-x) NaNbO
3-xBa
1-y(Bi
0.5K
0.5)
yTiO
3((100-a) mol%)+M
αO
βA kind of method of leadless piezoelectric ceramics (amol%) is to adopt technical pure, CP or analytically pure Na
2CO
3, K
2CO
3, BaCO
3, Bi
2O
3, TiO
2, Nb
2O
5Be raw material, by the stoichiometric ratio raw materials weighing of its general formula, after abundant milling mixing, in the alumina crucible of packing into, carry out pre-burning at 800-900 ℃, soaking time is 6 hours.Add in the pre-burning synthetic powder that appropriate amount of industrial is pure, CP or analytical pure M
αO
βProperty-modifying additive, levigate through ball milling again, thorough mixing, adding additives, moulding, plastic removal are at last at 1060-1120 ℃ of following sintering 2-6 hour.Ceramic plate behind the sintering is by last silver electrode, and in 60-100 ℃ silicone oil, polarization is 30-40 minute under the voltage of 3-6kV/mm.
The prescription and the performance index of the leadless piezoelectric ceramics of preparation are following according to the method described above:
Embodiment 1:
Prescription: 0.825NaNbO
3-0.175Ba
0.6(Bi
0.5K
0.5)
0.4TiO
3
Performance:
d 33(pC/N)
ε r k p(%)
Q m tanδ(%)
108 1079 17.4 326 2.53
Embodiment 2:
Prescription: 0.825NaNbO
3-0.175Ba
0.6(Bi
0.5K
0.5)
0.4TiO
3(99mol%)+MnO
2(1mol%)
Performance:
d 33(pC/N)
ε r k p(%)
Q m tanδ(%)
131 1470 17.5 391 2.13
Embodiment 3:
Prescription: 0.825NaNbO
3-0.175Ba
0.6(Bi
0.5K
0.5)
0.4TiO
3(99.5mol%)+MnO
2(0.5mol%)
Performance:
d 33(pC/N)
ε r k p(%)
Q m tanδ(%)
128 1337 18.4 260 1.60
Embodiment 4:
Prescription: 0.95NaNbO
3-0.05Ba
0.6(Bi
0.5K
0.5)
0.4TiO
3(99mol%)+MnO
2(1mol%)
Performance:
d 33(pC/N)
ε r k p(%)
Q m tanδ(%)
54 302 17.1 1862 1.87
Embodiment 5:
Prescription: 0.925NaNbO
3-0.075Ba
0.6(Bi
0.5K
0.5)
0.4TiO
3(99mol%)+MnO
2(1mol%)
Performance:
d 33(pC/N)
ε r k p(%)
Q m tanδ(%)
60 440 16.8 1211 2.27
Embodiment 6:
Prescription: 0.90NaNbO
3-0.10Ba
0.6(Bi
0.5K
0.5)
0.4TiO
3(99mol%)+MnO
2(1mol%)
Performance:
d 33(pC/N)
ε r k p(%)
Q m tanδ(%)
105 952 26.5 384 0.84
Embodiment 7:
Prescription: 0.85NaNbO
3-0.15Ba
0.6(Bi
0.5K
0.5)
0.4TiO
3(99mol%)+MnO
2(1mol%)
Performance:
d 33(pC/N)
ε r k p(%)
Q m tanδ(%)
96 1134 21.8 682 1.47
Embodiment 8:
Prescription: 0.85NaNbO
3-0.15Ba
0.5(Bi
0.5K
0.5)
0.5TiO
3(99mol%)+MnO
2(1mol%)
Performance:
d 33(pC/N)
ε r k p(%)
Q m tanδ(%)
99 1180 22.3 608 1.87
Claims (3)
1. sodium columbate barium titanate bismuth potassium series lead-free piezoelectric ceramic material compositions is characterized in that comprising in the said composition uhligite antiferroelectric NaNbO
3With strong ferroelectrics Ba
1-y(Bi
0.5K
0.5)
yTiO
3, wherein said composition is by general formula (1-x) NaNbO
3-xBa
1-y(Bi
0.5K
0.5)
yTiO
3Represent 0.025≤x in the formula≤0.25,0<y<1.
2. lead-free piezoceramic material compsn as claimed in claim 1 is characterized in that said compsn also contains one or more oxide compounds, and the general formula of compsn is (1-x) NaNbO
3-xBa
1-y(Bi
0.5K
0.5)
yTiO
3((100-a) mol%)+M
αO
β(amol%), M in formula
αO
βRepresent one or more oxide compounds; α and β represent the atomicity of corresponding element M and oxygen in the relevant oxide compound respectively; Amol% accounts for the overall mol ratio of compsn for this oxide compound; 0≤a≤3 wherein; M is for+1 to+6 valency and can form the element of solid-oxide with oxygen, and it is selected from least a among 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, Bi or the Ag.
3. lead-free piezoceramic material compsn as claimed in claim 2 is characterized in that said M is Mn.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011805A (en) * | 2012-12-24 | 2013-04-03 | 陕西科技大学 | BaTiO3 based leadless X8R type ceramic capacitor dielectric material and preparation method thereof |
| WO2014034692A1 (en) * | 2012-08-27 | 2014-03-06 | Canon Kabushiki Kaisha | Piezoelectric material and piezoelectric element using the same, and electronic apparatus using the piezoelectronic element |
| JP2014062032A (en) * | 2012-08-27 | 2014-04-10 | Canon Inc | Piezoelectric material, piezoelectric element, and electronic apparatus |
| CN113735581A (en) * | 2021-09-16 | 2021-12-03 | 湖南省美程陶瓷科技有限公司 | Lead-free piezoelectric ceramic material and preparation method thereof |
| CN115959900A (en) * | 2021-10-08 | 2023-04-14 | 四川大学 | Lead-free piezoceramic material containing iron, titanium, scandium, bismuth, manganese, barium and neodymium and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376594A (en) * | 2007-08-30 | 2009-03-04 | 香港理工大学 | Niobium niobium antimony sodiate potassium leadless piezoelectric ceramic composition |
| CN101462875A (en) * | 2009-01-15 | 2009-06-24 | 西安科技大学 | Bismuth sodium titanate based leadless piezoelectric ceramic and preparation technique thereof |
-
2011
- 2011-12-22 CN CN201110435330XA patent/CN102515762A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376594A (en) * | 2007-08-30 | 2009-03-04 | 香港理工大学 | Niobium niobium antimony sodiate potassium leadless piezoelectric ceramic composition |
| CN101462875A (en) * | 2009-01-15 | 2009-06-24 | 西安科技大学 | Bismuth sodium titanate based leadless piezoelectric ceramic and preparation technique thereof |
Cited By (12)
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|---|---|---|---|---|
| WO2014034692A1 (en) * | 2012-08-27 | 2014-03-06 | Canon Kabushiki Kaisha | Piezoelectric material and piezoelectric element using the same, and electronic apparatus using the piezoelectronic element |
| JP2014062032A (en) * | 2012-08-27 | 2014-04-10 | Canon Inc | Piezoelectric material, piezoelectric element, and electronic apparatus |
| JP2014062034A (en) * | 2012-08-27 | 2014-04-10 | Canon Inc | Piezoelectric material, piezoelectric element, and electronic apparatus |
| CN104584249A (en) * | 2012-08-27 | 2015-04-29 | 佳能株式会社 | Piezoelectric material and piezoelectric element using the same, and electronic apparatus using the piezoelectric element |
| TWI500191B (en) * | 2012-08-27 | 2015-09-11 | Canon Kk | Piezoelectric material and piezoelectric element using the same, and electronic apparatus using the piezoelectronic element |
| KR101728255B1 (en) * | 2012-08-27 | 2017-04-18 | 캐논 가부시끼가이샤 | Piezoelectric material and piezoelectric element using the same, and electronic apparatus using the piezoelectronic element |
| US9660174B2 (en) | 2012-08-27 | 2017-05-23 | Canon Kabushiki Kaisha | Piezoelectric material and piezoelectric element using the same, and electronic apparatus using the piezoelectronic element |
| CN104584249B (en) * | 2012-08-27 | 2017-10-27 | 佳能株式会社 | Piezoelectric and the piezoelectric element using the piezoelectric and the electronic installation using the piezoelectric element |
| CN103011805A (en) * | 2012-12-24 | 2013-04-03 | 陕西科技大学 | BaTiO3 based leadless X8R type ceramic capacitor dielectric material and preparation method thereof |
| CN113735581A (en) * | 2021-09-16 | 2021-12-03 | 湖南省美程陶瓷科技有限公司 | Lead-free piezoelectric ceramic material and preparation method thereof |
| CN113735581B (en) * | 2021-09-16 | 2022-07-15 | 湖南省美程陶瓷科技有限公司 | Lead-free piezoelectric ceramic material and preparation method thereof |
| CN115959900A (en) * | 2021-10-08 | 2023-04-14 | 四川大学 | Lead-free piezoceramic material containing iron, titanium, scandium, bismuth, manganese, barium and neodymium and preparation method thereof |
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Application publication date: 20120627 |