CN101109048A - Process for producing potassium-sodium niobate/copper piezo-electricity composite material - Google Patents
Process for producing potassium-sodium niobate/copper piezo-electricity composite material Download PDFInfo
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- CN101109048A CN101109048A CNA2007101207413A CN200710120741A CN101109048A CN 101109048 A CN101109048 A CN 101109048A CN A2007101207413 A CNA2007101207413 A CN A2007101207413A CN 200710120741 A CN200710120741 A CN 200710120741A CN 101109048 A CN101109048 A CN 101109048A
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Abstract
The invention relates to a sodium-potassium niobate or copper piezoelectric composite material preparation method, which belongs to the piezoelectricity driver technology field. By taking a lead-free piezoelectric ceramic as a matrix and a metal copper as a second phase, the invention prepares the sodium-potassium niobate or copper piezoelectric composite material through controlling oxygen partial pressure of the sintering atmosphere. The sintering temperature of the sodium-potassium niobate or copper piezoelectric composite material is between 1020 DEG C. and 1080 DEG C.; the oxygen content of the sintering atmosphere is 0.5 per cent to 3 ppm; the second-phase copper content is of 1 vol per cent to 20vol per cent. The control of the atmosphere sintering realizes the compound sintering of the lead-free piezoelectric ceramic sodium-potassium niobate and metal copper, the invention has the advantages of the low production cost and no environmental pollution. The prepared sodium-potassium niobate or copper piezoelectric composite material has the following prominent advantages that the second-phase copper content change is capable of regulating and controlling the piezoelectric performance of the sodium-potassium niobate piezoelectric ceramic and forming the gradient change; in addition, the second-phase copper has dispersion strengthening and anti-cracking and toughening effects to the sodium-potassium niobate ceramic matrix.
Description
Technical field
The invention belongs to the piezoelectric actuator technical field, relate to a kind of potassium-sodium niobate ((K, Na) NbO
3, KNN) leadless piezoelectric ceramics and pure metal copper carry out complex sintered method, are particularly suitable for making piezoelectric driving devices such as the piezoelectric relay of function gradient structure or piezoelectric micropump.
Background technology
Functionally Graded Materials can effectively solve the interface cracking problem that traditional double chip type piezoelectric actuator exists.For example, the Kahn of Virginia, USA etc. are in order to reduce the stress concentration of piezoelectric actuator inside, form the graded of piezoelectric property by blended metal oxide, thereby produce stress deformation (the M.Kahn et al. that coordinates mutually, " Actuator with graded activity ", U.S. Patent number: US5519278A (1996)).The Wu of US Naval Research Laboratory etc. are by the diffusion of control boronation zinc, prepared single-chip piezoelectric actuator replacement traditional twin lamella driving mechanism (C.C.M.Wu, et al., the J. Am.Ceram.Soc. of resistance along the thickness direction graded, Vol.79,809-812 (1996)).Meng Zhongyan etc. take the lead in conducting a research at home, successively design and synthetic dielectric type and two kinds of function gradient structure piezoelectric actuators of resistor-type (X.Zhu and Z.Meng, Sensors and ActuatorsA, Vol.48,169-176 (1995)).Yet,, there is no obvious improvement by the mechanical property of adding the formed pottery/ceramic composite of heterogeneous pottery for above-mentioned function gradient structure piezoelectric actuator.The Li Jing of Tsing-Hua University cutting edge of a knife or a sword etc. utilize metal platinum (Pt) as second with piezoelectric ceramics Pb-based lanthanumdoped zirconate titanates (Pb (Zr, Ti) O
3, PZT) complex sintered, prepared PZT/Pt function gradient structure piezoelectric actuator (K.Takagi, J.-F.Li, et al., J. Eur.Ceram.Soc., Vol.23,1577-1583 (2003)).University of Science ﹠ Technology, Beijing's Zhang Hailong etc. has prepared PZT/Ag function gradient structure piezoelectric actuator (Zhang Hailong etc. with argent (Ag) mutually as second, " piezoelectric driving device of a kind of function gradient structure and preparation method thereof ", patent publication No.: CN1945869 (2007)).Piezoelectric ceramics/metal function gradient-structure piezoelectric actuator has not only improved the interfacial stress of twin lamella piezoelectric actuator to be concentrated, and the dispersion-strengthened effect of metal second phase has significantly improved the matrix strength and the fracture toughness property of piezo-electricity composite material.
Although PZT/Pt or PZT/Ag function gradient structure piezoelectric actuator have excellent comprehensive performances, however following 2 limited its widespread use in practice.At first, the price of Pt or Ag costliness has increased production cost; Secondly, use lead-containing materials PZT that environment is caused serious harm.At the problems referred to above, the metallic copper (Cu) that the present invention is intended to cheapness replaces Pt and Ag, and replaces PZT with leadless piezo-electric ceramic K NN, preparation KNN/Cu piezo-electricity composite material.When sintering prepares the KNN/Cu matrix material, have some characteristics different with normal sintering or vacuum sintering: as if sintering in air, oxidation takes place in metal Cu; If sintering in a vacuum, it is rotten that deoxidation takes place the KNN of perovskite structure.Core content of the present invention will solve above-mentioned subject matter exactly.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of potassium-sodium niobate/copper piezo-electricity composite material, solved the complex sintered preparation difficult problem of leadless piezoelectric ceramics potassium-sodium niobate and plain metal copper.
The preparation potassium-sodium niobate/copper piezo-electricity composite material carries out as follows:
1) prepares the lithium doping potassium-sodium niobate lead-free piezoelectric ceramics according to the oxide compound hybrid system: with K
2CO
3, Na
2CO
3, Li
2CO
3, Nb
2O
5In powder is raw material, according to chemical formula Li
xK
0.5-0.5xNa
0.5-0.5xNbO
3(0.04≤x≤0.06) is prepared burden, is mixed, calcining, pulverizing, sintering;
2) the potassium-sodium niobate ceramic block fragmentation that sintering is obtained, and and copper preparation mixed powder, copper accounts for 1～20vol% of mixed powder total amount; In order to prepare mixed powder more uniformly, grind half an hour at least during the preparation mixed powder, and in mixed powder, add the binding agent of 0.1～0.5vol%, wherein binding agent is that polyvinyl alcohol content is the aqueous solution of 3～7wt%;
3) the potassium-sodium niobate/copper mixed powder with different Cu content is laid in the mould, uses tabletting machine moulded section under 80～130MP;
4) sample after the moulded section is put into crucible, again crucible is put into process furnace.Begin to be warming up to 1020～1080 ℃ with the speed of 40～60 ℃/min from room temperature, be incubated 1～2 hour and carry out sintering under 1020～1080 ℃ of temperature, furnace cooling obtains potassium-sodium niobate/copper piezo-electricity composite material.The whole process that is warming up to sintering temperature, heat preservation sintering, furnace cooling from room temperature, in process furnace, feed oxygen level at 0.5% (oxygen partial pressure value 5 * 10
2Pa, technical pure nitrogen)～3ppm (oxygen partial pressure value 3 * 10
-1Pa, high pure nitrogen) protective atmosphere between, feeding gaseous tension is 1.2～1.8 normal atmosphere (0.12～0.18MPa).
5) prepared potassium-sodium niobate/copper piezo-electricity composite material only comprises potassium-sodium niobate and copper two-phase, and does not have other dephasign, and wherein the content of the second phase copper is between 1-20vol%.According to the difference of sintering temperature, the density of piezo-electricity composite material is between 71～93%.
The invention has the advantages that: by feeding the oxygen level of shielding gas in the control sintering process; the oxygen partial pressure of sintering atmosphere is controlled in the specified range; make that the decomposition of both having avoided potassium sodium niobate piezoelectric ceramics in the sintering process is rotten; avoid the oxidation of metallic copper again; thereby preparation only contains potassium-sodium niobate and copper biphase piezo-electricity composite material, as depicted in figs. 1 and 2.If, then Cu can occur with the direct sintering in air of potassium-sodium niobate/copper piezo-electricity composite material
2O and oxidations such as CuO mutually, as shown in Figure 3.Potassium-sodium niobate/copper piezo-electricity composite material is used to make the function gradient structure piezoelectric actuator, is applied to driving elements such as piezoelectric relay, piezoelectric micropump.The content of the second phase copper can be regulated and control the piezoelectric property of potassium-sodium niobate ceramic matrix, forms graded; The second phase copper splits job stability and the service life that toughening effect can significantly improve piezoelectric actuator for the dispersion-strengthened of potassium-sodium niobate ceramic matrix and resistance, thus be particluarly suitable in the specific environment when long, the Primary Component and the equipment of non-stop run.Compare with the function gradient structure piezoelectric actuator of Pb-based lanthanumdoped zirconate titanates/platinum or Pb-based lanthanumdoped zirconate titanates/silver-colored system, copper replaces platinum and silver to reduce production cost; Potassium-sodium niobate replaces Pb-based lanthanumdoped zirconate titanates to reduce environmental pollution.Preparation technology proposed by the invention is simple relatively, and production cost is lower, non-environmental-pollution, thereby have broad application prospects.
Description of drawings
Fig. 1 is the XRD figure of potassium-sodium niobate/copper piezo-electricity composite material spectrum during sintering in industrial nitrogen.
Fig. 2 is the XRD figure of potassium-sodium niobate/copper piezo-electricity composite material spectrum during sintering in high pure nitrogen.
Fig. 3 is the XRD figure of potassium-sodium niobate/copper piezo-electricity composite material spectrum during sintering in air.
Embodiment
K used in the present invention
2CO
3, Na
2CO
3, Li
2CO
3, Nb
2O
5, raw materials such as Cu are commercially available.
Embodiment 1:
With commercially available K
2CO
3(Beijing chemical reagent factory, purity＞99.0%), Na
2CO
3(Beijing chemical reagent factory, purity＞99.8%), Li
2CO
3(Beijing chemical reagent factory, purity＞99.0%), Nb
2O
5(tantalum niobium company limited of Yifeng, Jiangxi osmanthus family, purity＞99.9%), Cu powder (Beijing lark waffle company limited that learns a skill, purity＞99.0%, granularity～45 micron) are raw material, at first according to chemical formula Li
xK
0.5-0.5xNa
0.5-0.5xNbO
3(0.04≤x≤0.06) is prepared burden, is mixed, calcining, pulverizing, sintering; Again according to 99vol% potassium-sodium niobate-1vol% copper configuration mixed powder, in the moulding of 80MPa dip mold; Sample behind the pressing mold is put into crucible and placed process furnace, begin speed with 40 ℃/min from room temperature and be warming up to 1020 ℃ and be incubated 1 hour, furnace cooling feeds industrial nitrogen (oxygen level＜0.5%) and protects in the whole process, feeding gaseous tension is 1.8 normal atmosphere; Sintering obtains the piezo-electricity composite material that composition consists of 99vol% potassium-sodium niobate-1vol% copper.The XRD detected result as shown in Figure 1, prepared potassium-sodium niobate/copper piezo-electricity composite material does not have dephasign and produces, density is about 75%.
Embodiment 2:
With commercially available K
2CO
3(Beijing chemical reagent factory, purity＞99.0%), Na
2CO
3(Beijing chemical reagent factory, purity＞99.8%), Li
2CO
3(Beijing chemical reagent factory, purity＞99.0%), Nb
2O
5(tantalum niobium company limited of Yifeng, Jiangxi osmanthus family, purity＞99.9%), Cu powder (Beijing lark waffle company limited that learns a skill, purity＞99.0%, granularity～45 micron) are raw material, at first according to chemical formula Li
xK
0.5-0.5xNa
0.5-0.5xNbO
3(0.04≤x≤0.06) is prepared burden, is mixed, calcining, pulverizing, sintering; Again according to 90vol% potassium-sodium niobate-10vol% copper configuration mixed powder, in the moulding of 110MPa dip mold; Sample behind the pressing mold is put into crucible and placed process furnace, begin speed with 50 ℃/min from room temperature and be warming up to 1050 ℃ and be incubated 1.5 hours, furnace cooling feeds industrial nitrogen (oxygen level＜0.5%) and protects in the whole process, feeding gaseous tension is 1.5 normal atmosphere; Sintering obtains the piezo-electricity composite material that composition consists of 90vol% potassium-sodium niobate-10vol% copper.XRD detects and shows that prepared potassium-sodium niobate/copper piezo-electricity composite material does not have dephasign and produces, and density is about 86%.
Embodiment 3:
With commercially available K
2CO
3(Beijing chemical reagent factory, purity＞99.0%), Na
2CO
3(Beijing chemical reagent factory, purity＞99.8%), Li
2CO
3(Beijing chemical reagent factory, purity＞99.0%), Nb
2O
5(tantalum niobium company limited of Yifeng, Jiangxi osmanthus family, purity＞99.9%), Cu powder (Beijing lark waffle company limited that learns a skill, purity＞99.0%, granularity～45 micron) are raw material, at first according to chemical formula Li
xK
0.5-0.5xNa
0.5-0.5xNbO
3(0.04≤x≤0.06) is prepared burden, is mixed, calcining, pulverizing, sintering; Again according to 80vol% potassium-sodium niobate-20vol% copper configuration mixed powder, in the moulding of 130MPa dip mold; Sample behind the pressing mold is put into crucible and placed process furnace, begin speed with 60 ℃/min from room temperature and be warming up to 1080 ℃ and be incubated 2 hours, furnace cooling, feed in the whole process high pure nitrogen (oxygen level＜3ppm) protect, feeding gaseous tension is 1.2 normal atmosphere; Sintering obtains the piezo-electricity composite material that composition consists of 80vol% potassium-sodium niobate-20vol% copper.The XRD detected result as shown in Figure 3, prepared potassium-sodium niobate/copper piezo-electricity composite material does not have dephasign and produces, density is about 93%.
Claims (2)
1. the preparation method of a potassium-sodium niobate/copper piezo-electricity composite material, it is characterized in that: processing step is:
(1) prepares the lithium doping potassium-sodium niobate lead-free piezoelectric ceramics according to the oxide compound hybrid system: with K
2CO
3, Na
2CO
3, Li
2CO
3, Nb
2O
5Powder is a raw material, according to chemical formula Li
xK
0.5-0.5xNa
0.5-0.5xNbO
3Prepare burden, mix, calcining, pulverizing, sintering, wherein, 0.04≤x≤0.06;
(2) the potassium-sodium niobate ceramic block fragmentation that sintering is obtained, and and copper preparation mixed powder, copper accounts for 1～20vol% of mixed powder total amount; At least grind half an hour during the preparation mixed powder, and add the binding agent of 0.1～0.5vol% in mixed powder, wherein binding agent is that polyvinyl alcohol content is the aqueous solution of 3～7wt%;
(3) the potassium-sodium niobate/copper mixed powder with different Cu content is laid in the mould, uses tabletting machine moulded section under 80～130MP;
(4) product after the moulded section is put into crucible, again crucible is put into process furnace; Begin to be warming up to 1020～1080 ℃ with the speed of 40～60 ℃/min from room temperature, be incubated 1～2 hour and carry out sintering under 1020～1080 ℃ of temperature, furnace cooling obtains potassium-sodium niobate/copper piezo-electricity composite material.
2. in accordance with the method for claim 1; it is characterized in that: the whole process that is warming up to sintering temperature, heat preservation sintering, furnace cooling from room temperature; feed the protective atmosphere of oxygen level between 0.5%～3ppm in process furnace, feeding gaseous tension is 1.2～1.8 normal atmosphere.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101661991B (en) * | 2009-09-16 | 2011-04-13 | 四川大学 | Lead-free piezoceramic-polyvinyl alcohol (PVA) piezoelectric composite material and preparation method thereof |
| CN109239189A (en) * | 2018-09-20 | 2019-01-18 | 河南理工大学 | High-temperature pipe supersonic guide-wave based on functionally graded material monitors system and method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3362473B2 (en) * | 1993-09-08 | 2003-01-07 | 株式会社村田製作所 | Piezoelectric ceramic composition |
| CN100352790C (en) * | 2006-06-27 | 2007-12-05 | 西北工业大学 | Sodium potassium tantalate niobate -base piezoelectric ceramic and process for preparing same |
-
2007
- 2007-08-24 CN CNB2007101207413A patent/CN100465312C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101661991B (en) * | 2009-09-16 | 2011-04-13 | 四川大学 | Lead-free piezoceramic-polyvinyl alcohol (PVA) piezoelectric composite material and preparation method thereof |
| CN109239189A (en) * | 2018-09-20 | 2019-01-18 | 河南理工大学 | High-temperature pipe supersonic guide-wave based on functionally graded material monitors system and method |
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| Publication number | Publication date |
|---|---|
| CN100465312C (en) | 2009-03-04 |
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Granted publication date: 20090304 Termination date: 20110824 |