CN101948310A - Transition metal element-doped bismuth calcium niobate ceramic material and preparation method thereof - Google Patents
Transition metal element-doped bismuth calcium niobate ceramic material and preparation method thereof Download PDFInfo
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- CN101948310A CN101948310A CN 201010277247 CN201010277247A CN101948310A CN 101948310 A CN101948310 A CN 101948310A CN 201010277247 CN201010277247 CN 201010277247 CN 201010277247 A CN201010277247 A CN 201010277247A CN 101948310 A CN101948310 A CN 101948310A
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- transition metal
- metal element
- ceramic material
- niobic acid
- bismuth calcium
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Abstract
The invention belongs to the field of lead-free piezoelectric materials and particularly relates to a transition metal element-doped bismuth calcium niobate ceramic material and a preparation method thereof. The chemical components of the transition metal element-doped bismuth calcium niobate ceramic material conform to the chemical general formula: Cal-xAxBi2Nb2O9, wherein A is selected from transition metal element Fe, Mn or Co; and x is not less than 0.01 and not greater than 0.2. The preparation of the transition metal element-doped bismuth calcium niobate ceramic has the advantages of low cost and simple process and is suitable for large-batch industrial production. The piezoelectric performance of the transition metal element-doped bismuth calcium niobate ceramic is much higher than that of the undoped bismuth calcium niobate ceramic, and the transition metal element-doped bismuth calcium niobate ceramic can be widely applied to high-temperature fields such as aerospace and steelmaking.
Description
Technical field
The invention belongs to the leadless piezoelectric material material field, be specifically related to a kind of transition metal element doped niobic acid bismuth calcium ceramic material and preparation method thereof.
Background technology
Piezoelectric ceramics is widely used in fields such as Industry Control, environmental monitoring, communication, infosystem and medicine equipment as transmitter, stopper and frequency transformer.The piezoelectric of widespread use at present mainly is the PZT (PbZrO with perovskite structure
3-PbTiO
3) and PT (PbTiO
3) material.
Along with the day by day raising of people to environmental protection consciousness, a lot of countries and regions are more strict to the lead tolerance control of electron device, and proposed unleaded schedule, and this just needs exploitation can substitute PZT (PbZrO
3-PbTiO
3) and PT (PbTiO
3) lead-free piezoceramic material.Existing P ZT (PbZrO
3-PbTiO
3) and PT (PbTiO
3) Curie temperature of system is below 490 ℃, and near Curie temperature the time because umpolarization and can't using especially in some special industries, as industries such as aerospace, steel-making, need be used piezoceramic material under very high temperature, at this moment, PZT (PbZrO
3-PbTiO
3) and PT (PbTiO
3) pottery of system just is difficult to be competent at, and needs a kind of system of high curie point high-temperature stability to replace the lead base piezoceramic material.
Bismuth laminated stupalith has high Curie temperature, and it is by (Bi
2O
2)
2+The lattice layer of layer and perovskite structure alternately is formed by stacking mutually, and its general formula is (Bi
2O
2)
2+(A
M-1B
mO
3m+1)
2-, A is for being suitable for 12 coordinate heavy ions, as K in the formula
+, Na
+, Ca
2+Deng, B is for being fit to the small ion of octahedral coordination, as Ti
4+, Nb
5+, Ta
5+Deng, m=1,2,3,4,5.Niobic acid bismuth calcium (chemical formula CaBi
2Nb
2O
9) belonging to the bismuth laminated of m=2, its Curie temperature is up to 943 ℃, and has good high-temperature stability, and its piezoelectric property umpolarization just when reaching Curie temperature has good application prospects in the high temperature field.But the piezoelectric property of the niobic acid bismuth calcium pottery of this undoped modification is relatively poor, its d
33Have only 6pC/N, also have certain distance from practical application.People such as Haixue Yan have carried out texturing by the method for plasma sintering to niobic acid bismuth calcium pottery, make d
33Brought up to 19pC/N[Haixue Yan, Hongtao Zhang, Rick Ubic, Michael JReece, Jing Liu, Zhijian Shen, Zhen Zhang.A lead-Free High-Curie-Piont FerroelectricCeramic CaBi2NbO9.ADVANVED MATERIALS, 2005,17,1261-1265.], but plasma sintering cost height, complex process and be not suitable for large batch of suitability for industrialized production.
Summary of the invention
The purpose of this invention is to provide a kind of transition metal element doped niobic acid bismuth calcium ceramic material and preparation method thereof, to overcome in the prior art the not deficiency of the niobic acid bismuth calcium ceramic material of doping vario-property, described transition metal element doped niobic acid bismuth calcium ceramic material not only has Curie temperature and the high-temperature stability more than 900 ℃, and has good piezoelectric property.
To achieve these goals, the present invention adopts following technical scheme:
A kind of transition metal element doped niobic acid bismuth calcium ceramic material, its chemical ingredients meets chemical general formula Ca
1-xA
xBi
2Nb
2O
9, wherein, A is selected from transition metal Fe, Mn or Co; The span of x is 0.01≤x≤0.2.
Preferably, x=0.05.
Element lower right corner part is represented mol ratio in the described chemical general formula.
A kind of preparation method of transition metal element doped niobic acid bismuth calcium ceramic material comprises the steps:
1) according to chemical general formula Ca
1-xA
xBi
2Nb
2O
9The stoichiometric ratio of middle Ca, Bi, Nb and A takes by weighing raw material: CaCO
3Powder, Bi
2O
3Powder, Nb
2O
5Powder, and the oxide compound of A or carbonate, wherein 0.01≤x≤0.2.
Preferably, the oxide compound of described A or carbonate are Fe
2O
3, MnCO
3, MnO
2And Co
2O
3
Described CaCO
3, Bi
2O
3, Nb
2O
5, Fe
2O
3, MnCO
3, MnO
2And Co
2O
3Purity be analytical pure, can be from market directly buy powder.
2) raw material that step 1) took by weighing is obtained mixed powder through ball milling mixing, pre-burning, secondary ball milling, oven dry, grinding technics successively.
Preferably, described calcined temperature is 750～950 ℃, and the pre-burning time is 2～4h; Further, described calcined temperature is 900 ℃, and the pre-burning time is 2h.
The time of described ball milling and secondary ball milling is 24h.
Described ball milling adopts wet ball-milling, and ball-milling medium is a dehydrated alcohol.
3) with step 2) mixed powder compressing tablet, plastic removal, the sintering of gained obtain described transition metal element doped niobic acid bismuth calcium ceramic material.
Preferably, the temperature of described plastic removal is 550 ℃.
Preferably, described agglomerating temperature is 1100～1250 ℃, and the sintered heat insulating time is 2～4h; Further, described agglomerating temperature is 1200 ℃, and the sintered heat insulating time is 4h.
Preferably, described mixed powder can be pressed into the green sheet that diameter is 10mm.
It is the 0.4mm thin slice that the ceramic material sample of gained is worn into thickness, Pt electrode on the upper and lower surface quilt of thin slice, in 200 ℃ of silicone oil, the voltage of 10KV/mm-20KV/mm polarization 10min. down obtains transition metal element doped niobic acid bismuth calcium pottery, test the performance of described transition metal element doped niobic acid bismuth calcium pottery, as piezoelectric property d
33, Curie temperature etc., the d of wherein said transition metal element doped niobic acid bismuth calcium pottery
33More than 10pC/N.
Transition metal element doped niobic acid bismuth calcium ceramic material of the present invention is the bismuth laminated lead-free piezoceramic material of niobic acid bismuth calcium, and its Curie temperature is more than 900 ℃, piezoelectric property d
33Can reach 14pC/N, and have good high-temperature stability, its piezoelectric property is the ability umpolarization when reaching Curie temperature, in high temperature field such as industries such as aerospace, steel-making good application prospects is arranged.
The preparation of the niobic acid bismuth calcium ceramic material of described transition metal element doped modification can get by the preparation method of conventional ceramic, preparation cost is low, simple and the suitable large batch of suitability for industrialized production of technology, the niobic acid bismuth calcium ceramic material piezoelectric property of described doping vario-property improves a lot than the piezoelectric property (6pC/N) of unadulterated niobic acid bismuth calcium pottery, its d under the situation that keeps high curie point
33Be more than doubled, advanced the application progress of high-temperature piezoelectric material.
Description of drawings
Fig. 1 is the X ray diffracting spectrum of the niobic acid bismuth calcium pottery of doped F e during x=0.05 among the embodiment 1.
Fig. 2 is the SEM of the niobic acid bismuth calcium pottery of doped F e figure during x=0.05 among the embodiment 1.
Fig. 3 is the X ray diffracting spectrum of the niobic acid bismuth calcium pottery of doped with Mn during x=0.05 among the embodiment 2.
Fig. 4 is the SEM of the niobic acid bismuth calcium pottery of doped with Mn figure during x=0.05 among the embodiment 2.
Fig. 5 is the X ray diffracting spectrum of the niobic acid bismuth calcium pottery of doping Co during x=0.05 among the embodiment 3.
Fig. 6 is the SEM of the niobic acid bismuth calcium pottery of doping Co figure during x=0.05 among the embodiment 3.
Embodiment
Further describe technical scheme of the present invention below by specific embodiment.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.
Embodiment 1:
Preparation meets chemical general formula Ca
1-xFe
xBi
2Nb
2O
9, and the adulterated niobic acid bismuth of the Fe calcium pottery during x=0.05.
With analytically pure powder raw material: 0.100g Fe
2O
3, 2.377g CaCO
3, 11.882gBi
2O
3And 6.645gNb
2O
5Preparation technology prepares burden by conventional ceramic, then raw material is mixed back ball milling 24 hours with alcohol, has both obtained the adulterated niobic acid bismuth of Fe calcium bismuth laminated leadless piezoelectric ceramic material at 900 ℃ of pre-burning 2h, secondary ball milling 24 hours, oven dry, grinding in mortar, compressing tablet, 550 ℃ of plastic removals, 1200 ℃ of sintering 4h.The ceramics sample of gained is ground to the thin slice of thick 0.4mm, the upper and lower surface of thin slice by on the Pt electrode, in 200 ℃ of silicone oil, its electrical property is tested in the polarization 10 minutes down of 10KV/mm-20KY/mm voltage.The d of gained ceramics sample
33Be 10pC/N.
Fig. 1 has illustrated the crystalline structure of niobic acid bismuth calcium ceramic material of transient metal doped modification and pure niobic acid bismuth calcium crystalline structure basically identical, its but (020) and (200) are bimodal to be compared pure niobic acid bismuth calcium ceramic material and trends towards being merged into unimodal, the doping that transition metal is described makes the lattice distortion of niobic acid bismuth calcium pottery, thereby has improved its piezoelectric property.
Fig. 2 has illustrated that the niobic acid bismuth calcium ceramic material microtexture of doping vario-property still is sheet structure, but with the pure Comparatively speaking thickness increase of its sheet structure of niobic acid bismuth calcium ceramic material, length and width reduce, and have changed the sintering character of niobic acid bismuth calcium in conjunction with X diffracting spectrum explanation doping vario-property.
Embodiment 2:
Preparation meets chemical general formula Ga
1-xMn
xBi
2Nb
2O
9, and the adulterated niobic acid bismuth of the Mn calcium pottery during x=0.05.
With analytically pure powder raw material: 0.144g MnCO
3, 2.377g CaCO
3, 11.882gBi
2O
3And 6.645gNb
2O
5Preparation technology prepares burden by conventional ceramic, then raw material is mixed back ball milling 24 hours with alcohol, has both obtained the adulterated niobic acid bismuth of Mn calcium bismuth laminated leadless piezoelectric ceramic material at 900 ℃ of pre-burning 2h, secondary ball milling 24 hours, oven dry, grinding in mortar, compressing tablet, 550 ℃ of plastic removals, 1200 ℃ of sintering 4h.The ceramics sample of gained is ground to the thin slice of thick 0.4mm, the upper and lower surface of thin slice by on the Pt electrode, in 200 ℃ of silicone oil, its electrical property is tested in the polarization 10 minutes down of 10KV/mm-20KV/mm voltage.The d of gained ceramics sample
33Be 14pC/N.
Fig. 3 has illustrated the crystalline structure of niobic acid bismuth calcium ceramic material of transient metal doped modification and pure niobic acid bismuth calcium crystalline structure basically identical, its but (020) and (200) are bimodal to be compared pure niobic acid bismuth calcium ceramic material and trends towards being merged into unimodal, the doping that transition metal is described makes the lattice distortion of niobic acid bismuth calcium pottery, thereby has improved its piezoelectric property.
Fig. 4 has illustrated that the niobic acid bismuth calcium ceramic material microtexture of doping vario-property still is sheet structure, but with the pure Comparatively speaking thickness increase of its sheet structure of niobic acid bismuth calcium ceramic material, length and width reduce, and have changed the sintering character of niobic acid bismuth calcium in conjunction with X diffracting spectrum explanation doping vario-property.
Embodiment 3:
Preparation meets chemical general formula Ca
1-xCo
xBi
2Nb
2O
9, and the adulterated niobic acid bismuth of the Co calcium pottery during x=0.05.
With analytically pure powder raw material: 0.104g Co
2O
3, 2.377g CaCO
3, 11.882gBi
2O
3And 6.645gNb
2O
5Preparation technology prepares burden by conventional ceramic, then raw material is mixed back ball milling 24 hours with alcohol, has both obtained the adulterated niobic acid bismuth of Co calcium bismuth laminated leadless piezoelectric ceramic material at 900 ℃ of pre-burning 2h, secondary ball milling 24 hours, oven dry, grinding in mortar, compressing tablet, 550 ℃ of plastic removals, 1200 ℃ of sintering 4h.The ceramics sample of gained is ground to the thin slice of thick 0.4mm, the upper and lower surface of thin slice by on the Pt electrode, in 200 ℃ of silicone oil, its electrical property is tested in the polarization 10 minutes down of 10KV/mm-20KV/mm voltage.The d of gained ceramics sample
33Be 10pC/N.
Fig. 5 has illustrated the crystalline structure of niobic acid bismuth calcium ceramic material of transient metal doped modification and pure niobic acid bismuth calcium crystalline structure basically identical, its but (020) and (200) are bimodal to be compared pure niobic acid bismuth calcium ceramic material and trends towards being merged into unimodal, the doping that transition metal is described makes the lattice distortion of niobic acid bismuth calcium pottery, thereby has improved its piezoelectric property.
Fig. 6 has illustrated that the niobic acid bismuth calcium ceramic material microtexture of doping vario-property still is sheet structure, but with the pure Comparatively speaking thickness increase of its sheet structure of niobic acid bismuth calcium ceramic material, length and width reduce, and have changed the sintering character of niobic acid bismuth calcium in conjunction with X diffracting spectrum explanation doping vario-property.
Claims (7)
1. transition metal element doped niobic acid bismuth calcium ceramic material, its chemical ingredients meets chemical general formula Ca
1-xA
xBi
2Nb
2O
9, wherein, A is selected from transition metal Fe, Mn or Co; The span of x is 0.01≤x≤0.2.
2. transition metal element doped niobic acid bismuth calcium ceramic material as claimed in claim 1 is characterized in that x=0.05.
3. the preparation method of transition metal element doped niobic acid bismuth calcium ceramic material as claimed in claim 1 or 2 comprises the steps:
1) according to chemical general formula Ca
1-xA
xBi
2Nb
2O
9The stoichiometric ratio of middle Ca, Bi, Nb and A takes by weighing raw material: CaCO
3Powder, Bi
2O
3Powder, Nb
2O
5Powder, and the oxide compound of A or carbonate, wherein 0.01≤x≤0.2;
2) raw material that step 1) took by weighing is obtained mixed powder through ball milling mixing, pre-burning, secondary ball milling, oven dry, grinding technics successively;
3) with step 2) mixed powder compressing tablet, plastic removal, the sintering of gained obtain described transition metal element doped niobic acid bismuth calcium ceramic material.
4. the preparation method of transition metal element doped niobic acid bismuth calcium ceramic material as claimed in claim 3 is characterized in that oxide compound or the carbonate of described A are selected from Fe
2O
3, MnCO
3, MnO
2Or Co
2O
3
5. the preparation method of transition metal element doped niobic acid bismuth calcium ceramic material as claimed in claim 3 is characterized in that described calcined temperature is 750～950 ℃, and the pre-burning time is 2～4h.
6. the preparation method of transition metal element doped niobic acid bismuth calcium ceramic material as claimed in claim 3 is characterized in that described agglomerating temperature is 1100～1250 ℃, and the sintered heat insulating time is 2～4h.
7. the transition metal element doped application of niobic acid bismuth calcium ceramic material in aerospace and field of steel-making as claimed in claim 1 or 2.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112088441A (en) * | 2018-05-08 | 2020-12-15 | 赛尔科技有限公司 | Electrical component comprising a multilayer thin-film ceramic member, electrical component comprising such an electrical component, and use thereof |
| CN114560698A (en) * | 2022-04-15 | 2022-05-31 | 中国科学院合肥物质科学研究院 | Method for enhancing performance of calcium bismuth niobate high-temperature piezoelectric ceramic by inducing texture through oxide sintering aid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1335284A (en) * | 2000-07-28 | 2002-02-13 | Tdk株式会社 | Piezoelectric ceramics |
| CN1814570A (en) * | 2005-02-01 | 2006-08-09 | 四川大学 | Bi.Na.K.Li Ag titanate series lead-free piezoelectric ceramics |
-
2010
- 2010-09-09 CN CN 201010277247 patent/CN101948310A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1335284A (en) * | 2000-07-28 | 2002-02-13 | Tdk株式会社 | Piezoelectric ceramics |
| CN1814570A (en) * | 2005-02-01 | 2006-08-09 | 四川大学 | Bi.Na.K.Li Ag titanate series lead-free piezoelectric ceramics |
Non-Patent Citations (1)
| Title |
|---|
| 《Materials Chemistry and Physics》 20091231 Chun-Ming Wang et al. Electromechanical properties of calcium bismuth niobate (CaBi2Nb2O9) ceramics at elevated temperature 21-24 1-7 第118卷, * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112088441A (en) * | 2018-05-08 | 2020-12-15 | 赛尔科技有限公司 | Electrical component comprising a multilayer thin-film ceramic member, electrical component comprising such an electrical component, and use thereof |
| CN114560698A (en) * | 2022-04-15 | 2022-05-31 | 中国科学院合肥物质科学研究院 | Method for enhancing performance of calcium bismuth niobate high-temperature piezoelectric ceramic by inducing texture through oxide sintering aid |
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Application publication date: 20110119 |