CN101289318A - Sodion compensating potassium and sodium niobate based leadless piezoelectric ceramics and method for preparing same - Google Patents
Sodion compensating potassium and sodium niobate based leadless piezoelectric ceramics and method for preparing same Download PDFInfo
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- CN101289318A CN101289318A CNA2008101147737A CN200810114773A CN101289318A CN 101289318 A CN101289318 A CN 101289318A CN A2008101147737 A CNA2008101147737 A CN A2008101147737A CN 200810114773 A CN200810114773 A CN 200810114773A CN 101289318 A CN101289318 A CN 101289318A
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Abstract
The invention relates to Na<+> compensatory potassium-sodium niobate lithium base leadless piezoelectric ceramics and a low-temperature sintering method thereof, which belongs to the filed of functional ceramic materials. The general formula of chemical composition can be represented as (Naa+xKbLic)NbO3; wherein, a, b, and c represent the molar fraction of the components such as Na, K, Li respectively; and a plus b plus c equals to 1; x represent the molar fraction of the compensatory Na<+>; the value range of each parameter is that: a is more than 0.20 and less than 0.80, b is more than 0.20 and less than 0.80, c is more than 0.00 and less than 0.30, and x is more than 0.00 and equal or less than 0.20. The preparation method of the ceramics system comprises the processing steps of mixing raw materials, baking, molding, sintering, baking sliver and polarization, etc. The Na<+> compensatory potassium-sodium niobate lithium base leadless piezoelectric ceramics and the low-temperature sintering method of the invention have the advantages of effectively reducing the baking temperature of potassium-sodium niobate lithium base leadless piezoelectric ceramics by the compensation of Na<+> and preparing leadless piezoelectric ceramics with good property material at the low temperature of 800 to 1000 DEG C.
Description
Technical field
The invention belongs to the ceramic material field, the synthetic sodium compensation of a kind of low temperature potassium niobate sodium-based leadless piezoelectric ceramic and preparation method thereof is provided especially.
Background technology
Piezoelectric ceramics is important, the widely used new and high technology material of a class, but extensive use is the lead base piezoelectric ceramics at present, because its lead content up to more than 60%, in preparation, application, and brings serious harm to the mankind and living environment thereof in the discarded process.Therefore research and develop leadless piezoelectric ceramics beyond doubt one urgent, have a problem of great society and economic implications.
In the leadless piezoelectric ceramics system, potassium niobate sodium-based leadless piezoelectric ceramic (K, Na) NbO
3(being abbreviated as KNN) because of it has high Curie temperature and high electromechanical coupling factor, is considered to the candidate material of the most promising replacement lead base piezoelectric ceramics.But the pure KNN ceramic dense of ordinary process agglomerating degree is lower, and its piezoelectric constant can not surpass 100pC/N usually.Be expected to improve its performance by adjusting measures such as preparation technology or doping vario-property.The main technique of this ceramic systems of preparation has at present: pressure sintering, forge hot, discharge plasma sintering etc.These technology equipment used complexity, production cost are higher, be not suitable for scale operation.The tradition non-pressure sintering technology is not owing to need special experimental installation, and is with low cost and receive much concern.Data shows that the synthesis temperature of pressureless sintering is higher at present, discloses the titanate MTiO that adds divalent metal in the KNN system as patent CN1810711A
3(M is at least a among Ca, Mg, Ba and the Sr) and MnO
2, its sintering temperature all is higher than 1050 ℃, and after adding titanate, the piezoelectric property of material is unsatisfactory.Patent CN1919791A discloses in the KNN system and has added CuO, though the Q of material
mHigher, but its piezoelectric property is relatively poor, and sintering temperature is also more than 1050 ℃.Patent CN1511802A adds Ta or Sb in the KNN system, disclose class general formula (Li
xNa
yK
1-x-y) (Nb
1-zR
z) O
3The multi constituent niobate lead-free piezoelectric ceramics of (wherein R is Ta or Sb) expression, sintering temperature is 1100-1200 ℃, the piezoelectric constant of this type of material is up to 150pC/N.Patent CN1958511A adds Ta and Sb simultaneously in the KNN system, though the piezoelectric property of material obviously improves, sintering temperature is still more than 1050 ℃.Patent CN101066868 adds the Mg element in the LKNN system, though sintering temperature decreases, its piezoelectric property is unsatisfactory.
Table 1 has been enumerated the sintering temperature and the performance of the KNN base piezoelectric ceramic of the pressureless sintering preparation that relates in low sintering KNN based leadless piezoelectric ceramics provided by the present invention and other patent.
The potassium niobate sodium-based leadless piezoelectric ceramic performance of table 1 pressureless sintering relatively
| Patent | Increase composition | Sintering temperature (℃) | d 33(pC/N) |
| CN1511802A | Ta, Sb and rare earth class manganate | 1100-1200 | 120-157 |
| CN1699280A | Ta, Sb and SrTiO 3 | 1100-1250 | Below 120 |
| CN1810711A | MnO 2And titanates of alkali-earth metals | 1070-1190 | 30-222 |
| CN1919791A | CuO | 1050-1130 | 90-120 |
| CN1958511A | Ta、Sb | 1085-1220 | 109-252 |
| CN101066868 | Mg | 800-1040 | 80-230 |
| The present invention | Na | 800-1000 | 80-262 |
In sum, the pressureless sintering temperature of the leadless piezoelectric ceramics of better performances all is higher than 1050 ℃ at present.And in the relevant patent of being found, there is no in the KNN system by existing composition Na in the former pottery of excessive interpolation
+, with Na
2O, Na
2CO
3And the sodium bicarbonate form adds the report that reduces sintering temperature.
Summary of the invention
The object of the present invention is to provide the potassium niobate sodium-based leadless piezoelectric ceramic and the preparation method of the synthetic sodium compensation of a kind of low temperature, and the pottery that makes has piezoelectric property preferably.
The present invention adopts traditional non-pressure sintering technology, need not to add other sintering agent, by excessive compensation Na
+Molar fraction, under lower sintering temperature 800-1000 ℃, synthesized the KNN leadless piezoelectric ceramics, be lower than the sintering temperature of present document and patent report.The one-tenth of this pottery is grouped into available chemical general formula and is expressed as (Na
A+xK
bLi
c) NbO
3, wherein a, b, c represent the molar fraction of Na, K, Li component respectively, a+b+c=1, x represent to compensate Na
+Molar fraction.Its span is: 0.20＜a＜0.80,0.20＜b＜0.80,0.00＜c＜0.30,0.00＜x≤0.20.
The preparation process of low-temperature sintered ceramics of the present invention is:
(1) raw material is pressed chemical formula (Na respectively
A+xK
bLi
c) NbO
3Carrying out weighing, batching, is medium with dehydrated alcohol, and after 3-24 hour, oven dry obtains dry powder with the planetary ball mill ball milling; X represents the Na that compensates in the general formula
+Molar fraction, its span is: 0.00＜x≤0.20; The Na of compensation
+With Na
2O, Na
2CO
3Or any form adds in the sodium bicarbonate;
(2) dry powder is warming up to 700-900 ℃ continuously in the temperature programmed control box-type furnace, is incubated 2-10 hour, carry out the synthetic of niobate;
(3) in the good powder of roasting, add binding agent, put into mould, with the compression moulding under 200MPa of manual tabletting machine;
(4) biscuit of compression moulding is put into the temperature programmed control box-type furnace, be warming up to 800-1000 ℃ continuously, sintering 2-5 hour, be cooled to room temperature;
(5) ceramic disks that makes with the polishing of 600 order fine sandpapers is evenly coated the silver slurry in two upper and lower surfaces afterwards, is incubated 30min roasting silver down at 520 ℃.Ceramic plate behind the roasting silver is put into silicone oil and is heated to 100-200 ℃, keeps 20-50min to polarize under 2-5kV/mm voltage.Obtain the piezoelectric ceramics finished product of excellent property.
The present invention is raw materials used to be commercial Na
2CO
3(99.8%) or Na
2O or NaHCO
3, K
2CO
3(99%), Li
2CO
3(99.5%) and Nb
2O
5(99.95%).
The invention has the advantages that,, effectively reduce the sintering temperature of potassium niobate sodium-based leadless piezoelectric ceramic, synthesized the leadless piezoelectric ceramics sample of excellent property under 800-1000 ℃ low temperature by excessive adding Na element.
Embodiment
The invention provides a kind of method of effective reduction potassium niobate sodium-based leadless piezoelectric ceramic sintering temperature.Its preparation method comprises mixing raw material, roasting, moulding, sintering, roasting silver, polarization.
Exemplify basic inventive embodiment below.
Embodiment 1:
According to (Na
0.211+0.001K
0.77Li
0.019) NbO
3(x=0.001) prescription is with electronic balance difference weighing 0.389gNa
2CO
3, 1.812gK
2CO
3, 0.024gLi
2CO
3, and 4.533gNb
2O
5, as medium, with planetary ball mill grinding batch mixing 24h, rotating speed is 250rpm with dehydrated alcohol, slip obtains the siccative powder 80 ℃ of oven dry.Dry powder is through 700 ℃, and insulation 10h carries out the synthetic of niobate.Get powder 0.3g and pack in the mould of Φ 10mm compression moulding into.The disk of moulding is put into temperature programmed control box-type furnace sintering, carries out sintering under 1000 ℃, and insulation 2h is cooled to room temperature, makes ceramic disks.After the polishing of 600 order fine sandpapers, be coated with roasting silver electrode on two surfaces and make the silver-colored ceramic plate of roasting, put into silicone oil and be heated to 100 ℃, under 5kV/mm voltage, keep 20min to polarize, cool to room temperature again, finish polarization.
Embodiment 2:
According to (Na
0.732+0.20K
0.204Li
0.064) NbO
3(x=0.20) prescription is with electronic balance difference weighing 0.84gNa
2O, 0.507gK
2CO
3, 0.085gLi
2CO
3, and 4.786gNb
2O
5, as medium, with planetary ball mill grinding batch mixing 3h, rotating speed is 250rpm with dehydrated alcohol, slip obtains the siccative powder 80 ℃ of oven dry.Dry powder is through 750 ℃, and insulation 7h carries out the synthetic of niobate.Get powder 0.3g and pack in the mould of Φ 10mm compression moulding into.The disk of moulding is put into temperature programmed control box-type furnace sintering, carries out sintering under 800 ℃, and insulation 5h is cooled to room temperature, makes ceramic disks.After the polishing of 600 order fine sandpapers, be coated with roasting silver electrode on two surfaces and make the silver-colored ceramic plate of roasting, put into silicone oil and be heated to 200 ℃, under 5kV/mm voltage, keep 30min to polarize, cool to room temperature again, finish polarization.
Embodiment 3:
According to (Na
0.516+0.01-K
0.446Li
0.038) NbO
3(x=0.01) prescription is with electronic balance difference weighing 1.553gNaHCO
3, 1.082gK
2CO
3, 0.049gLi
2CO
3, and 4.673gNb
2O
5, as medium, with planetary ball mill grinding batch mixing 12h, rotating speed is 250rpm with dehydrated alcohol, slip obtains the siccative powder 80 ℃ of oven dry.Dry powder is through 850 ℃, and insulation 5h carries out the synthetic of niobate.Get powder 0.3h and pack in the mould of Φ 10mm compression moulding into.The disk of moulding is put into temperature programmed control box-type furnace sintering, carries out sintering under 940 ℃, and insulation 4h is cooled to room temperature and makes ceramic disks.After the polishing of 600 order fine sandpapers, be coated with roasting silver electrode on two surfaces and make the silver-colored ceramic plate of roasting, put into silicone oil and be heated to 140 ℃, under 4kV/mm voltage, keep 50min to polarize, cool to room temperature again, finish polarization.
Embodiment 4:
According to (Na
0.497+0.012K
0.467Li
0.036) NbO
3(x=0.012) prescription is with electronic balance difference weighing 0.955gNa
2CO
3, 1.131gK
2CO
3, 0.047gLi
2CO
3, and 4.664gNb
2O
5, as medium, with planetary ball mill grinding batch mixing 4h, rotating speed is 250rpm with dehydrated alcohol, slip obtains the siccative powder 80 ℃ of oven dry.Dry powder is through 900 ℃, and insulation 2h carries out the synthetic of niobate.Get powder 0.3g and pack in the mould of Φ 10mm compression moulding into.The disk of moulding is put into temperature programmed control box-type furnace sintering, carries out sintering under 970 ℃, and insulation 3h is cooled to room temperature and makes ceramic disks.After the polishing of 600 order fine sandpapers, be coated with roasting silver electrode on two surfaces and make the silver-colored ceramic plate of roasting, put into silicone oil and be heated to 160 ℃, under 4.5kV/mm voltage, keep 40min to polarize, cool to room temperature again, finish polarization.
The prescription of other embodiment and piezoelectric constant d
33(pC/N) see Table 2.
The prescription and the piezoelectric constant d of table 2 sodium compensation leadless piezoelectric ceramics
33(pC/N)
Claims (2)
1, a kind of low temperature synthetic sodion compensating potassium and sodium niobate based leadless piezoelectric ceramics is characterized in that: material constitutional chemistry formula general formula is (Na
A+xK
bLi
c) NbO
3, wherein a, b, c represent the molar fraction of Na, K, Li component, a+b+c=1 respectively; X represents to compensate Na
+Molar fraction; Its span is: 0.20＜a＜0.80,0.20＜b＜0.80,0.00＜c＜0.30,0.00＜x≤0.20; The Na of compensation
+With Na
2O, Na
2CO
3Or any form adds in the sodium bicarbonate.
2, a kind of preparation method of sodion compensating potassium and sodium niobate based leadless piezoelectric ceramics according to claim 1 is characterized in that its preparation technology is:
(1) raw material is pressed general formula (Na respectively
A+xK
bLi
c) NbO
3Proportioning carry out weighing, batching, use dehydrated alcohol to be medium, after 3-24 hour, oven dry obtains dry powder with the planetary ball mill ball milling;
(2) dry powder is warming up to 700-900 ℃ continuously in the temperature programmed control box-type furnace, is incubated 2-10 hour, carry out the synthetic of niobate;
(3) in the roasting powder of preparation, behind the adding binding agent, put into mould, with the compression moulding under 200MPa of manual tabletting machine;
(4) biscuit of compression moulding is put into the temperature programmed control box-type furnace, be warming up to 800-1000 ℃ continuously, sintering 2-5 hour, be cooled to room temperature;
(5) ceramic disks that makes with the polishing of 600 order fine sandpapers, be coated with roasting silver electrode on two surfaces afterwards, make the roasting silver-colored ceramic plate after, put into silicone oil and be heated to 100-200 ℃, under 2-5kV/mm voltage, keep 20-50min to polarize, make the potassium niobate sodium-based leadless piezoelectric ceramic of excess sodium compensation.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786880A (en) * | 2010-02-11 | 2010-07-28 | 中国科学院上海硅酸盐研究所 | Sodium potassium niobate-potassium lithium niobate piezoelectric ceramics and preparation method thereof |
| CN101935215A (en) * | 2010-09-07 | 2011-01-05 | 聊城大学 | Potassium-sodium lithium niobate-base lead-free piezoelectric ceramic complex with good temperature stability |
| CN102584194A (en) * | 2012-02-14 | 2012-07-18 | 桂林电子科技大学 | Perovskite leadless piezoelectric ceramic used at high temperature and preparation method thereof |
| CN107353002A (en) * | 2017-08-10 | 2017-11-17 | 内蒙古科技大学 | Reversible and controllable fluorescence photochromic piezoelectric and preparation method thereof |
| CN110041073A (en) * | 2019-05-31 | 2019-07-23 | 河南科技大学 | A kind of preparation method of potassium sodium niobate ceramic |
| CN111635229A (en) * | 2020-05-29 | 2020-09-08 | 上海甚恒生物科技有限公司 | Preparation method of lead-free piezoelectric ceramic material |
-
2008
- 2008-06-12 CN CNA2008101147737A patent/CN101289318A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786880A (en) * | 2010-02-11 | 2010-07-28 | 中国科学院上海硅酸盐研究所 | Sodium potassium niobate-potassium lithium niobate piezoelectric ceramics and preparation method thereof |
| CN101786880B (en) * | 2010-02-11 | 2012-06-06 | 中国科学院上海硅酸盐研究所 | Sodium potassium niobate-potassium lithium niobate piezoelectric ceramics and preparation method thereof |
| CN101935215A (en) * | 2010-09-07 | 2011-01-05 | 聊城大学 | Potassium-sodium lithium niobate-base lead-free piezoelectric ceramic complex with good temperature stability |
| CN102584194A (en) * | 2012-02-14 | 2012-07-18 | 桂林电子科技大学 | Perovskite leadless piezoelectric ceramic used at high temperature and preparation method thereof |
| CN102584194B (en) * | 2012-02-14 | 2013-12-25 | 桂林电子科技大学 | Perovskite leadless piezoelectric ceramic used at high temperature and preparation method thereof |
| CN107353002A (en) * | 2017-08-10 | 2017-11-17 | 内蒙古科技大学 | Reversible and controllable fluorescence photochromic piezoelectric and preparation method thereof |
| CN110041073A (en) * | 2019-05-31 | 2019-07-23 | 河南科技大学 | A kind of preparation method of potassium sodium niobate ceramic |
| CN111635229A (en) * | 2020-05-29 | 2020-09-08 | 上海甚恒生物科技有限公司 | Preparation method of lead-free piezoelectric ceramic material |
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Application publication date: 20081022 |