CN101786880A - Sodium potassium niobate-potassium lithium niobate piezoelectric ceramics and preparation method thereof - Google Patents
Sodium potassium niobate-potassium lithium niobate piezoelectric ceramics and preparation method thereof Download PDFInfo
- Publication number
- CN101786880A CN101786880A CN 201010109269 CN201010109269A CN101786880A CN 101786880 A CN101786880 A CN 101786880A CN 201010109269 CN201010109269 CN 201010109269 CN 201010109269 A CN201010109269 A CN 201010109269A CN 101786880 A CN101786880 A CN 101786880A
- Authority
- CN
- China
- Prior art keywords
- niobate
- potassium
- powder
- piezoelectric ceramics
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention relates to sodium potassium niobate-potassium lithium niobate piezoelectric ceramics and a preparation method thereof. The chemical formula of the sodium potassium niobate-potassium lithium niobate piezoelectric ceramics is (1-y) (K1-xNax) NbO3- (y/5.15) K2.9Li1.95Nb5.15O15.3, wherein 0.3<=x<=0.7, and 0<y<=0.50. The preparation method prepares the sodium potassium niobate-potassium lithium niobate piezoelectric ceramics through a two-step solid-phase reaction sintering process: first, pure-phase sodium potassium niobate and potassium lithium niobium is pre-synthesized, and then the two are mixed and pressed into tablets for reaction sintering. The prepared sodium potassium niobate-lithium potassium niobate has excellent piezoelectric properties, d33 reaches about 219pC/N, kP reaches above 47 percent, and the curie temperature TC reaches above 488DEG C. The high-performance lead-free piezoelectric ceramic niobate system prepared by the method of the invention has important application value in a transceiving piezoelectric transducer under a high temperature condition.
Description
Technical field
The present invention relates to a kind of potassium-sodium niobate-lithium niobate piezoelectric ceramics and preparation method thereof, belong to environmentally friendly leadless piezoelectric ceramics field.
Background technology
Ferroelectric piezoelectric ceramics is the hi-tech material that a class is important, irreplaceable, international competition is very fierce, be widely used in devices such as making ultrasonic transducer, piezoelectric transformer, wave filter, piezoelectric buzzer, have very widely in fields such as information, laser, space flight and medical treatment and use.Traditional ferroelectric piezoelectric ceramics mainly is leaded pottery, as PZT, PMN-PT, PZN-PT etc.These leaded potteries have all demonstrated very excellent ferroelectric piezoelectric property near its accurate homotype phase boundary.But this class material oxidation lead content is up to 60%～70%, preparation, use and discarded last handling process in bring serious harm all can for the mankind and ecotope.
In recent years, along with the demand of environment protection and human social, the friendly type leadless piezoelectric ceramics of research novel environmental has become one of focus material that world developed country endeavours to study.Calendar year 2001, European Parliament passed through the decree about " limiting objectionable impurities in electrical equipment and the electronics ", and implemented in 2006, just comprised lead in the objectionable impurities that wherein is limited to use.The U.S., Japan and China electronics and information industry portion also prepare by similar decree in succession, and strengthen the supporting dynamics to the leadless piezoelectric ceramics project year by year.Therefore greatly develop environmentally friendly non-plumbum ferroelectric piezoelectric ceramics and device thereof, have important social and economic implications.
At present, the leadless piezoelectric ceramics system of having developed is broadly divided into barium phthalate base, contains bismuth laminated, bismuth sodium titanate based and niobate lead-free piezoelectric ceramics etc., and wherein niobate lead-free piezoelectric ceramics is divided into tungsten bronze structure niobate and perovskite structure potassium sodium niobate piezoelectric ceramics again.
The tungsten bronze structure niobate is the second largest electronic ceramics that is only second to perovskite structural material, and its constitutional features is that the niobium oxygen octahedra links to each other at the angle altogether, forms three kinds of rooms, promptly pentagonal A1 position, tetragonal A2 position and leg-of-mutton C position.So its general general formula is written as (A1)
4(A2)
2C
4Nb
10O
30This class material has high-curie temperature, low-k, low mechanical quality factor and excellent non-linear optical property, photoelectric properties and photodamage resistant performance.Wherein, it is big that representative materials lithium potassium niobate (KLN) monocrystalline also has a spontaneous polarization, and electromechanical coupling factor kt is up to 0.64 characteristics.It is widely studied for many years as the photoelectricity monocrystalline always, but as pottery, its dielectric ferroelectric properties research seldom is difficult to find relevant report.
The piezoelectric property of perovskite structure potassium-sodium niobate (KNN) based leadless piezoelectric ceramics is good, is considered to one of material system that very likely replaces the lead base piezoelectric ceramics.At present, people have done big quantity research by doping vario-property to potassium niobate sodium-based leadless piezoelectric ceramic, mainly contain KNN-LiMO
3(M=Nb, Ta, Sb), KNN-AgMO
3(M=Nb, Ta, Sb), KNN-MTiO
3(M=Mg, Ca, Sr, Ba), KNN-Bi
0.5M
0.5TiO
3(M=Na, K) etc.Accurate homotype phase boundary occurs along with the variation of doping content has in discovery, and has obtained compactness, KNN based leadless piezoelectric ceramics that ferroelectric piezoelectric property is good near accurate homotype phase boundary.But its performance and leaded ceramic phase ratio still have gap, and are attended by the situation that Curie temperature reduces more.And these doping solid solutions are confined between the compound of the potassium-sodium niobate of perovskite structure and (class) perovskite structure.
2009, people such as Ceng Jiangtao [J.Am.Ceram.Soc., vol.92, no.3, pp.752-754, Mar.2009.] report was studied (1-x) (K
0.5Na
0.5) NbO
3-xK
3Li
2Nb
5O
15(x=0,0.02,0.03,0.04,0.05) ceramic systems.This is to be doping solid solution between the tungsten bronze structure niobate of representative first with potassium-sodium niobate and with the lithium potassium niobate.But these research dopings are less, get a little fewly, and it is synthetic in advance with single stage method together directly will to contain the compound of K, Na, Li, Nb element during preparation, separately not synthetic lithium potassium niobate, and lithium potassium niobate crystalline structure instability during by strict stoichiometric ratio only is present in rich niobium zone.And the piezo-electric modulus of report is lower, less than 160pC/N.
Therefore, the doping solid solution of potassium-sodium niobate and tungsten bronze structure niobate has wide research space and prospect.
Summary of the invention
The object of the present invention is to provide a kind of potassium-sodium niobate-lithium niobate piezoelectric ceramics and preparation method thereof, to overcome the deficiencies in the prior art with higher piezo-electric modulus and Curie temperature.
The present invention solves above technical problem by the following technical solutions:
A kind of potassium-sodium niobate-lithium niobate piezoelectric ceramics of the present invention (being called for short xKNN-yKLN) is characterized in that chemical formula is (1-y) (K
1-xNa
x) NbO
3-(y/5.15) K
2.9Li
1.95Nb
5.15O
15.3, 0.3≤x≤0.7,0＜y≤0.50 wherein.
Above-mentioned chemical formula (1-y) (K
1-xNa
x) NbO
3-(y/5.15) K
2.9Li
1.95Nb
5.15O
15.3In, bottom right mark numeral and alphabetical x, y all represent the stoichiometry molar relationship between the corresponding chemical element.
Preferably, above-mentioned chemical formula (1-y) (K
1-xNa
x) NbO
3-(y/5.15) K
2.9Li
1.95Nb
5.15O
15.3In, 0.3≤x≤0.7,0.02≤y≤0.25.
The present invention also provides a kind of preparation method of above-mentioned potassium-sodium niobate-lithium niobate piezoelectric ceramics, it is characterized in that, the chemical formula of pre-synthetic pure phase is (K respectively earlier
1-xNa
x) NbO
3Potassium-sodium niobate and the chemical formula of pure phase be K
2.9Li
1.95Nb
5.15O
15.3Lithium potassium niobate, then with the two according to chemical formula (1-y) (K
1-xNa
x) NbO
3-(y/5.15) K
2.9Li
1.95Nb
5.15O
15.3In stoichiometric ratio mix, carry out reaction sintering behind the compressing tablet; Wherein, 0.3≤x≤0.7,0＜y≤0.50.
Above-mentioned preparation method specifically may further comprise the steps:
1) presses chemical formula (K
1-xNa
x) NbO
3In stoichiometric ratio take by weighing sylvite, sodium salt and Niobium Pentxoxide, carry out ball milling then, oven dry back is crossed 60～200 mesh sieve and is obtained dry powder;
2) press chemical formula K
2.9Li
1.95Nb
5.15O
15.3In stoichiometric ratio take by weighing sylvite, lithium salts and Niobium Pentxoxide, carry out ball milling then, oven dry back is crossed 60～200 mesh sieve and is obtained dry powder;
3), after sieving, grinding obtains the (K of perovskite structure again with the powder of gained in the step 1) pre-Synthetic 2～6 hours in 500～850 ℃ air
1-xNa
x) NbO
3Powder; Be preferable over pre-synthesizing 4～6 hours in 700～850 ℃ air;
4) with step 2) in the powder of gained pre-Synthetic 2～10 hours in 700～1000 ℃ air, after grinding is sieved, obtain the K of tungsten bronze structure again
2.9Li
1.95Nb
5.15O
15.3Powder; Be preferable over pre-synthesizing 4～6 hours in 960～1000 ℃ air;
5) with the powder of gained in step 3) and the step 4), according to chemical formula (1-y) (K
1-xNa
x) NbO
3-(y/5.15) K
2.9Li
1.95Nb
5.15O
15.3In stoichiometric ratio batching, carry out ball milling then and mix, the oven dry back is added tackiness agent and is mixed granulation;
6) powder with the step 5) gained carries out compressing tablet in 100～300MPa, again in 500～700 ℃ of plastic removals, and sintering 2～5 hours in 1000～1150 ℃ of air then, furnace cooling obtains ceramic plate.
Among the above-mentioned preparation method, described sylvite, sodium salt, lithium salts and Niobium Pentxoxide are preferably the exsiccant anhydrous substances, are preferably in to dry processing before the use guaranteeing its drying regime, as before use in 120 ℃ of dryings 24 hours.
Described sylvite is preferably salt of wormwood or saltpetre; Described sodium salt is preferably yellow soda ash or SODIUMNITRATE; Described lithium salts is preferably Quilonum Retard or lithium nitrate.
Among the above-mentioned preparation method, described tackiness agent adopt in this area the conventional tackiness agent that uses all can, be 5wt% polyvinyl alcohol (PVA) as concentration, its addition is preferably and accounts for described in the step 5) 8～25wt% of gained powder after the oven dry; Be preferably 8～20wt%.
Preferably, in step 3) and the step 4), be warming up to described pre-synthesis temperature with the temperature rise rate of 2～10 ℃/min, preferably the speed with 2～5 ℃/min heats up.
Can be applicable to transceiver type PZT (piezoelectric transducer) under the hot conditions by the high-performance niobate system leadless piezoelectric ceramics of the inventive method preparation.
Compare with existing potassium sodium niobate piezoelectric ceramics technology of preparing, the present invention has following characteristics and advantage:
A) the present invention has systematically studied the doping solid solution between the lithium potassium niobate of potassium-sodium niobate and tungsten bronze structure first, has opened up the frontier of potassium sodium niobate piezoelectric ceramics research.
B) the present invention adopts two single-step solid phase reaction sintering first, promptly synthesizes in advance respectively after the potassium-sodium niobate and lithium potassium niobate of pure phase, and the two mixed pressuring plate is carried out reaction sintering.The disposable process of finishing the synthetic and ceramic post sintering of compound, this helps obtaining the tiny and uniform pottery of crystal grain, improves the density of pottery, has improved the sintering characteristic of potassium sodium niobate piezoelectric ceramics effectively, and then has improved its electric property.
C) the prepared potassium-sodium niobate-lithium niobate piezoelectric ceramics of the present invention is compared with traditional niobate ceramics, and the integrated electronic performance strengthens greatly, especially piezoelectric coefficient d
33Reach 219pC/N, k
PReach 47%, Curie temperature reaches 488 ℃, reached can practical application performance index.
D) the selected cost of material of the present invention is cheap, the preparation method is simple, the process control process stabilizing, and non-environmental-pollution is easy to promote.
Description of drawings
Fig. 1 is K
2.9Li
1.95Nb
5.15O
15.3Pre-synthetic powder is the X-ray diffractogram of (25 ℃) at room temperature.As seen from the figure, be incubated 6 hours down, the tungsten bronze structure lithium potassium niobate of synthetic pure phase through 960 ℃.
Fig. 2 is (1-y) (K
1-xNa
x) NbO
3-(y/5.15) K
2.9Li
1.95Nb
5.15O
15.3Pottery, the X-ray diffractogram of (25 ℃) at room temperature when x=0.52.
Among the figure, the potassium-sodium niobate-lithium niobate piezoelectric ceramics when KNN-KLN2 represents y=0.02, the rest may be inferred.As seen from the figure, the KNN pottery after the doping still belongs to perovskite structure, and a small amount of tungsten bronze structure begins to occur mutually when y 〉=0.12.When y≤0.10, structure quadrature phase.And when y 〉=0.20, structure becomes cubic phase.
Fig. 3 is (1-y) (K
1-xNa
x) NbO
3-(y/5.15) K
2.9Li
1.95Nb
5.15O
15.3Pottery, the dielectric temperature spectrum when x=0.52.Among the figure, the potassium-sodium niobate-lithium niobate piezoelectric ceramics when KNN-KLN2 represents y=0.02, the rest may be inferred.
Fig. 4 is (1-y) (K
1-xNa
x) NbO
3-(y/5.15) K
2.9Li
1.95Nb
5.15O
15.3Pottery, the at room temperature specific inductivity and the dielectric loss of (25 ℃) when x=0.52.
Fig. 5 is (1-y) (K
1-xNa
x) NbO
3-(y/5.15) K
2.9Li
1.95Nb
5.15O
15.3Pottery, the piezo-electric modulus when x=0.52.
Fig. 6 is (1-y) (K
1-xNa
x) NbO
3-(y/5.15) K
2.9Li
1.95Nb
5.15O
15.3Pottery, the Curie temperature when x=0.52 and quadrature phase-tetragonal phase converting temperature.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment, should be understood that these embodiment only are used to the present invention is described and are not used in restriction protection scope of the present invention.
The raw material condition that needs in the embodiment of the invention is as follows:
Carbon Dioxide lithium (Li
2CO
3), purity is 98%;
Anhydrous sodium carbonate (Na
2CO
3), purity is 99.8%;
Anhydrous potassium carbonate (K
2CO
3), purity is 99%;
Niobium Pentxoxide (Nb
2O
5), purity is 99.5%.
Testing method:
It is thick that the ceramic plate of gained is milled to 0.5mm with sand paper, the two-sided silver slurry back burning infiltration silver electrode under 600～800 ℃ of conditions of coating.The slice, thin piece of burned silver polarizes in 80～160 ℃ silicone oil oil bath, and polarization condition is that 3～4kV/mm kept 10～30 minutes.Place and carry out electrical performance testing after 24 hours.
The present invention adopts X-ray diffraction analyser (XRD) to determine the crystalline structure and the phase structure of pre-synthetic powder and ceramics sample.The volume density of pottery utilizes Archimedes' principle to measure according to the measuring method of international " GB2412-81 " piezoelectric ceramics volume density.Measure electromechanical coupling factor and the mechanical quality factor and the dielectric properties of polarization back ceramics sample by Agilent 4294A electric impedance analyzer.The ZJ-3A type quasistatic survey meter that adopts Acoustical Inst., Chinese Academy of Sciences to produce is measured piezoelectric coefficient d
33
A kind of potassium-sodium niobate-lithium niobate piezoelectric ceramics of present embodiment, its chemical formula are (1-y) (K
1-xNa
x) NbO
3-(y/5.15) K
2.9Li
1.95Nb
5.15O
15.3, mol ratio x=0.52 wherein, y=0.02.
The set-up procedure of present embodiment is:
1) Anhydrous potassium carbonate, anhydrous sodium carbonate, Carbon Dioxide lithium, Niobium Pentxoxide were dried at loft drier in 120 ℃ in dry 24 hours, respectively by stoichiometric ratio (K
0.48Na
0.52) NbO
3, K
2.9Li
1.95Nb
5.15O
15.3Batching;
2) raw materials mixed described in the step (1) is respectively that medium carries out ball milling with the dehydrated alcohol, and the oven dry back is crossed 120 mesh sieve and obtained dry powder;
3) with gained in the step (2) by (K
0.48Na
0.52) NbO
3Proportioning blended powder grinds the (K that obtains perovskite structure after sieving with temperature rise rate pre-synthesizing 4 hours in 800 ℃ of air of 2 ℃/min
0.48Na
0.52) NbO
3Powder;
4) with the K that presses of gained in the step (2)
2.9Li
1.95Nb
5.15O
15.3Proportioning blended powder grinds the K that obtains tungsten bronze structure after sieving with temperature rise rate pre-synthesizing 6 hours in 960 ℃ of air of 5 ℃/min
2.9Li
1.95Nb
5.15O
15.3Powder;
5) with (K of step (3) gained
0.48Na
0.52) NbO
3And the K of the middle gained of step (4)
2.9Li
1.95Nb
5.15O
15.3According to stoichiometric ratio 0.98 (K
0.48Na
0.52) NbO
3-(0.02/5.15) K
2.9Li
1.95Nb
5.15O
15.3Preparing burden, is that medium carries out the ball milling mixing with the dehydrated alcohol, and adding the concentration that accounts for the heavy 10wt% of powder material behind the oven dry powder is the PVA tackiness agent mixing of 5wt%, granulation;
6) dry-pressing formed with 300MPa with the powder of step (5) gained is that diameter 15mm, thickness are the round billet sheet of 2.3mm, at 650 ℃ of plastic removals, and sintering 2 hours in 1120 ℃ of air then, furnace cooling obtains the ceramic of compact sheet;
7) it is thick the ceramic plate of step (6) gained to be milled to 0.5mm with sand paper, the two-sided silver slurry back burning infiltration silver electrode under 800 ℃ of conditions of coating.The slice, thin piece of burned silver polarizes in 100 ℃ silicone oil oil bath, and polarization condition is that 4kV/mm kept 30 minutes.Place and carry out electrical performance testing after 24 hours.
Raw material salt of wormwood, yellow soda ash and Quilonum Retard in the present embodiment all can be substituted by saltpetre, SODIUMNITRATE and lithium nitrate, and prepared potassium-sodium niobate-lithium potassium niobate performance is as shown in table 1:
Table 1
| ????ε 33 T/ε 0????(1kHz) | ??tanδ??(1kHz) | ??d 33??(pC/N) | ????k t????(％) | ????T O-T????(℃) | ????T c????(℃) |
| ????466 | ??0.03 | ??128 | ????36.5 | ????190 | ????422 |
A kind of potassium-sodium niobate-lithium niobate piezoelectric ceramics of embodiment, its chemical formula are (1-y) (K
1-xNa
x) NbO
3-(y/5.15) K
2.9Li
1.95Nb
5.15O
15.3, mol ratio x=0.52 wherein, y=0.05.
The set-up procedure of present embodiment is:
(1) Anhydrous potassium carbonate, anhydrous sodium carbonate, Carbon Dioxide lithium, Niobium Pentxoxide were dried at loft drier in 120 ℃ in dry 24 hours, respectively by stoichiometric ratio (K
0.48Na
0.52) NbO
3, K
2.9Li
1.95Nb
5.15O
15.3Batching;
(2) institute's raw materials mixed is respectively that medium carries out ball milling with the dehydrated alcohol in the step (1), and the oven dry back is crossed 120 mesh sieve and obtained dry powder;
(3) with gained in the step (2) by (K
0.48Na
0.52) NbO
3Proportioning blended powder grinds the (K that obtains perovskite structure after sieving with temperature rise rate pre-synthesizing 5 hours in 750 ℃ of air of 5 ℃/min
0.48Na
0.52) NbO
3Powder;
(4) with the K that presses of gained in the step (2)
2.9Li
1.95Nb
5.15O
15.3Proportioning blended powder grinds the K that obtains tungsten bronze structure after sieving with temperature rise rate pre-synthesizing 4 hours in 1000 ℃ of air of 2 ℃/min
2.9Li
1.95Nb
5.15O
15.3Powder;
(5) with (K of step (3) gained
0.48Na
0.52) NbO
3And the K of the middle gained of step (4)
2.9Li
1.95Nb
5.15O
15.3According to stoichiometric ratio 0.95 (K
0.48Na
0.52) NbO
3-(0.05/5.15) K
2.9Li
1.95Nb
5.15O
15.3Preparing burden, is that medium carries out the ball milling mixing with the dehydrated alcohol, and adding the concentration that accounts for the heavy 12wt% of powder material behind the oven dry powder is the PVA tackiness agent mixing of 5wt%, granulation;
(6) dry-pressing formed with 200MPa with the powder of step (5) gained is that diameter 15mm, thickness are the round billet sheet of 2.6mm, at 600 ℃ of plastic removals, and sintering 3 hours in 1110 ℃ of air then, furnace cooling obtains the ceramic of compact sheet;
(7) it is thick the ceramic plate of step (6) gained to be milled to 0.5mm with sand paper, the two-sided silver slurry back burning infiltration silver electrode under 700 ℃ of conditions of coating.The slice, thin piece of burned silver polarizes in 80 ℃ silicone oil oil bath, and polarization condition is that 3～4kV/mm kept 30 minutes.
Potassium-sodium niobate-lithium potassium niobate the performance of present embodiment preparation is as shown in table 2:
Table 2
| ????ε 33 T/ε 0????(1kHz) | ??tanδ??(1kHz) | ??d 33??(pC/N) | ????k t????(％) | ????T O-T????(℃) | ????T c????(℃) |
| ????466 | ??0.03 | ??126 | ????42.5 | ????173 | ????434 |
A kind of potassium-sodium niobate-lithium niobate piezoelectric ceramics of present embodiment, its chemical formula are (1-y) (K
1-xNa
x) NbO
3-(y/5.15) K
2.9Li
1.95Nb
5.15O
15.3, mol ratio x=0.4 wherein, y=0.10.
The set-up procedure of present embodiment is:
(1) Anhydrous potassium carbonate, anhydrous sodium carbonate, Carbon Dioxide lithium, Niobium Pentxoxide were dried at loft drier in 120 ℃ in dry 24 hours, respectively by stoichiometric ratio (K
0.6Na
0.4) NbO
3, K
2.9Li
1.95Nb
5.15O
15.3Batching;
(2) institute's raw materials mixed is respectively that medium carries out ball milling with the dehydrated alcohol in the step (1), and the oven dry back is crossed 120 mesh sieve and obtained dry powder;
(3) with gained in the step (2) by (K
0.6Na
0.4) NbO
3Proportioning blended powder grinds the (K that obtains perovskite structure after sieving with temperature rise rate pre-synthesizing 4 hours in 850 ℃ of air of 3 ℃/min
0.6Na
0.4) NbO
3Powder;
(4) with the K that presses of gained in the step (2)
2.9Li
1.95Nb
5.15O
15.3Proportioning blended powder grinds the K that obtains tungsten bronze structure after sieving with temperature rise rate pre-synthesizing 4 hours in 960 ℃ of air of 2 ℃/min
2.9Li
1.95Nb
5.15O
15.3Powder;
(5) with (K of step (3) gained
0.6Na
0.4) NbO
3And the K of the middle gained of step (4)
2.9Li
1.95Nb
5.15O
15.3According to stoichiometric ratio 0.9 (K
0.6Na
0.4) NbO
3-(0.10/5.15) K
2.9Li
1.95Nb
5.15O
15.3Preparing burden, is that medium carries out the ball milling mixing with the dehydrated alcohol, and adding the concentration that accounts for the heavy 15wt% of powder material behind the oven dry powder is the PVA tackiness agent mixing of 5wt%, granulation;
(6) dry-pressing formed with 300MPa with the powder of step (5) gained is that diameter 15mm, thickness are the round billet sheet of 2.3mm, at 700 ℃ of plastic removals, and sintering 2 hours in 1100 ℃ of air then, furnace cooling obtains the ceramic of compact sheet;
(7) it is thick the ceramic plate of step (6) gained to be milled to 0.5mm with sand paper, the two-sided silver slurry back burning infiltration silver electrode under 750 ℃ of conditions of coating.The slice, thin piece of burned silver polarizes in 150 ℃ silicone oil oil bath, and polarization condition is that 3～4kV/mm kept 30 minutes.
Potassium-sodium niobate-lithium potassium niobate the performance of present embodiment preparation is as shown in table 3:
Table 3
| ????ε 33 T/ε 0????(1kHz) | ??tanδ??(1kHz) | ??d 33??(pC/N) | ????k t????(％) | ????T O-T????(℃) | ????T c????(℃) |
| ????468 | ??0.03 | ??137 | ????40 | ????120 | ????454 |
A kind of potassium-sodium niobate-lithium niobate piezoelectric ceramics of present embodiment, its chemical formula are (1-y) (K
1-xNa
x) NbO
3-(y/5.15) K
2.9Li
1.95Nb
5.15O
15.3, mol ratio x=0.6 wherein, y=0.15.
The set-up procedure of present embodiment is:
(1) Anhydrous potassium carbonate, anhydrous sodium carbonate, Carbon Dioxide lithium, Niobium Pentxoxide were dried at loft drier in 120 ℃ in dry 24 hours, respectively by stoichiometric ratio (K
0.4Na
0.6) NbO
3, K
2.9Li
1.95Nb
5.15O
15.3Batching;
(2) institute's raw materials mixed is respectively that medium carries out ball milling with the dehydrated alcohol in the step (1), and the oven dry back is crossed 120 mesh sieve and obtained dry powder;
(3) with gained in the step (2) by (K
0.4Na
0.6) NbO
3Proportioning blended powder grinds the (K that obtains perovskite structure after sieving with temperature rise rate pre-synthesizing 6 hours in 700 ℃ of air of 2 ℃/min
0.4Na
0.6) NbO
3Powder;
(4) with the K that presses of gained in the step (2)
2.9Li
1.95Nb
5.15O
15.3Proportioning blended powder grinds the K that obtains tungsten bronze structure after sieving with temperature rise rate pre-synthesizing 6 hours in 1000 ℃ of air of 5 ℃/min
2.9Li
1.95Nb
5.15O
15.3Powder;
(5) with (K of step (3) gained
0.4Na
0.6) NbO
3And the K of the middle gained of step (4)
2.9Li
1.95Nb
5.15O
15.3According to stoichiometric ratio 0.85 (K
0.4Na
0.6) NbO
3-(0.15/5.15) K
2.9Li
1.95Nb
5.15O
15.3Preparing burden, is that medium carries out the ball milling mixing with the dehydrated alcohol, and adding the concentration that accounts for the heavy 20wt% of powder material behind the oven dry powder is the PVA tackiness agent mixing of 5wt%, granulation;
(6) dry-pressing formed with 200MPa with the powder of step (5) gained is that diameter 15mm, thickness are the round billet sheet of 2.6mm, at 550 ℃ of plastic removals, and sintering 3 hours in 1090 ℃ of air then, furnace cooling obtains the ceramic of compact sheet;
(7) it is thick the ceramic plate of step (6) gained to be milled to 0.5mm with sand paper, the two-sided silver slurry back burning infiltration silver electrode under 600 ℃ of conditions of coating.The slice, thin piece of burned silver polarizes in 150 ℃ silicone oil oil bath, and polarization condition is that 3～4kV/mm kept 30 minutes.
Potassium-sodium niobate-lithium potassium niobate the performance of present embodiment preparation is as shown in table 4:
Table 4
| ????ε 33 T/ε 0????(1kHz) | ????tanδ????(1kHz) | ??d 33??(pC/N) | ????k t????(％) | ????T O-T????(℃) | ????T c????(℃) |
| ????563 | ????0.02 | ??183 | ????47 | ????61 | ????471 |
A kind of potassium-sodium niobate-lithium niobate piezoelectric ceramics of present embodiment, its chemical formula are (1-y) (K
1-xNa
x) NbO
3-(y/5.15) K
2.9Li
1.95Nb
5.15O
15.3, mol ratio x=0.7 wherein, y=0.18.
The set-up procedure of present embodiment is:
(1) Anhydrous potassium carbonate, anhydrous sodium carbonate, Carbon Dioxide lithium, Niobium Pentxoxide were dried at loft drier in 120 in dry 24 hours, respectively by stoichiometric ratio (K
0.3Na
0.7) NbO
3, K
2.9Li
1.95Nb
5.15O
15.3Batching;
(2) institute's raw materials mixed is respectively that medium carries out ball milling with the dehydrated alcohol in the step (1), and the oven dry back is crossed 120 mesh sieve and obtained dry powder;
(3) with gained in the step (2) by (K
0.3Na
0.7) NbO
3Proportioning blended powder grinds the (K that obtains perovskite structure after sieving with temperature rise rate pre-synthesizing 6 hours in 850 ℃ of air of 2 ℃/min
0.3Na
0.7) NbO
3Powder;
(4) with the K that presses of gained in the step (2)
2.9Li
1.95Nb
5.15O
15.3Proportioning blended powder grinds the K that obtains tungsten bronze structure after sieving with temperature rise rate pre-synthesizing 6 hours in 1000 ℃ of air of 2 ℃/min
2.9Li
1.95Nb
5.15O
15.3Powder;
(5) with (K of step (3) gained
0.3Na
0.7) NbO
3And the K of the middle gained of step (4)
2.9Li
1.95Nb
5.15O
15.3According to stoichiometric ratio 0.82 (K
0.3Na
0.7) NbO
3-(0.18/5.15) K
2.9Li
1.95Nb
5.15O
15.3Preparing burden, is that medium carries out the ball milling mixing with the dehydrated alcohol, and adding the concentration that accounts for the heavy 8wt% of powder material behind the oven dry powder is the PVA tackiness agent mixing of 5wt%, granulation;
(6) dry-pressing formed with 300MPa with the powder of step (5) gained is that diameter 15mm, thickness are the round billet sheet of 2.3mm, at 500 ℃ of plastic removals, and sintering 5 hours in 1040 ℃ of air then, furnace cooling obtains the ceramic of compact sheet;
(7) it is thick the ceramic plate of step (6) gained to be milled to 0.5mm with sand paper, the two-sided silver slurry back burning infiltration silver electrode under 800 ℃ of conditions of coating.The slice, thin piece of burned silver polarizes in 150 ℃ silicone oil oil bath, and polarization condition is that 3～4kV/mm kept 30 minutes.
Potassium-sodium niobate-lithium potassium niobate the performance of present embodiment preparation is as shown in table 5:
Table 5
| ????ε 33 T/ε 0????(1kHz) | ??tanδ??(1kHz) | ??d 33??(pC/N) | ????k t????(％) | ????T O-T????(℃) | ????T c????(℃) |
| ????690 | ??0.05 | ??219 | ????36.8 | ????23 | ????479 |
A kind of potassium-sodium niobate-lithium niobate piezoelectric ceramics of present embodiment, its chemical formula are (1-y) (K
1-xNa
x) NbO
3-(y/5.15) K
2.9Li
1.95Nb
5.15O
15.3, mol ratio x=0.3 wherein, y=0.25.
The set-up procedure of present embodiment is:
(1) Anhydrous potassium carbonate, anhydrous sodium carbonate, Carbon Dioxide lithium, Niobium Pentxoxide were dried at loft drier in 120 ℃ in dry 24 hours, respectively by stoichiometric ratio (K
0.7Na
0.3) NbO
3, K
2.9Li
1.95Nb
5.15O
15.3Batching;
(2) institute's raw materials mixed is respectively that medium carries out ball milling with the dehydrated alcohol in the step (1), and the oven dry back is crossed 120 mesh sieve and obtained dry powder;
(3) with gained in the step (2) by (K
0.7Na
0.3) NbO
3Proportioning blended powder grinds the (K that obtains perovskite structure after sieving with temperature rise rate pre-synthesizing 6 hours in 700 ℃ of air of 2 ℃/min
0.7Na
0.3) NbO
3Powder;
(4) with the K that presses of gained in the step (2)
2.9Li
1.95Nb
5.15O
15.3Proportioning blended powder grinds the K that obtains tungsten bronze structure after sieving with temperature rise rate pre-synthesizing 6 hours in 960 ℃ of air of 5 ℃/min
2.9Li
1.95Nb
5.15O
15.3Powder;
(5) with (K of step (3) gained
0.7Na
0.3) NbO
3And the K of the middle gained of step (4)
2.9Li
1.95Nb
5.15O
15.3According to stoichiometric ratio 0.75 (K
0.7Na
0.3) NbO
3-(0.25/5.15) K
2.9Li
1.95Nb
5.15O
15.3Preparing burden, is that medium carries out the ball milling mixing with the dehydrated alcohol, and adding the concentration that accounts for the heavy 9wt% of powder material behind the oven dry powder is the PVA tackiness agent mixing of 5wt%, granulation;
(6) dry-pressing formed with 200MPa with the powder of step (5) gained is that diameter 15mm, thickness are the round billet sheet of 2.6mm, at 700 ℃ of plastic removals, and sintering 4 hours in 1020 ℃ of air then, furnace cooling obtains the ceramic of compact sheet;
(7) it is thick the ceramic plate of step (6) gained to be milled to 0.5mm with sand paper, the two-sided silver slurry back burning infiltration silver electrode under 650 ℃ of conditions of coating.The slice, thin piece of burned silver polarizes in 150 ℃ silicone oil oil bath, and polarization condition is that 3～4kV/mm kept 30 minutes.
Potassium-sodium niobate-lithium potassium niobate the performance of present embodiment preparation is as shown in table 6:
Table 6
| ??ε 33 T/ε 0??(1kHz) | ??tanδ??(1kHz) | ??d 33??(pC/N) | ????k t????(％) | ????T O-T????(℃) | ????T c????(℃) |
| ??542 | ??0.01 | ??135 | ????30.08 | ????-18 | ????488 |
Claims (7)
1. a potassium-sodium niobate-lithium niobate piezoelectric ceramics is characterized in that, chemical formula is (1-y) (K
1-xNa
x) NbO
3-(y/5.15) K
2.9Li
1.95Nb
5.15O
15.3, 0.3≤x≤0.7,0＜y≤0.50 wherein.
2. potassium-sodium niobate-lithium niobate piezoelectric ceramics as claimed in claim 1 is characterized in that, 0.3≤x≤0.7,0.02≤y≤0.25.
3. the preparation method of a potassium-sodium niobate-lithium niobate piezoelectric ceramics as claimed in claim 1 or 2 is characterized in that, the chemical formula of pre-synthetic pure phase is (K respectively earlier
1-xNa
x) NbO
3Potassium-sodium niobate and the chemical formula of pure phase be K
2.9Li
1.95Nb
5.15O
15.3Lithium potassium niobate, then with the two according to chemical formula (1-y) (K
1-xNa
x) NbO
3-(y/5.15) K
2.9Li
1.95Nb
5.15O
15.3In stoichiometric ratio mix, carry out reaction sintering behind the compressing tablet.
4. the preparation method of potassium-sodium niobate-lithium niobate piezoelectric ceramics as claimed in claim 3 is characterized in that, specifically may further comprise the steps:
1) presses chemical formula (K
1-xNa
x) NbO
3In stoichiometric ratio take by weighing sylvite, sodium salt and Niobium Pentxoxide, carry out ball milling then, sieving after the oven dry obtains dry powder;
2) press chemical formula K
2.9Li
1.95Nb
5.15O
15.3In stoichiometric ratio take by weighing sylvite, lithium salts and Niobium Pentxoxide, carry out ball milling then, sieving after the oven dry obtains dry powder;
3), after sieving, grinding obtains the (K of perovskite structure again with the powder of gained in the step 1 pre-Synthetic 2～6 hours in 500～850 ℃ air
1-xNa
x) NbO
3Powder;
4), after sieving, grinding obtains the K of tungsten bronze structure again with the powder of gained in the step 2 pre-Synthetic 2～10 hours in 700～1000 ℃ air
2.9Li
1.95Nb
5.15O
15.3Powder;
5) with the powder of gained in step 3 and the step 4, according to chemical formula (1-y) (K
1-xNa
x) NbO
3-(y/5.15) K
2.9Li
1.95Nb
5.15O
15.3In stoichiometric ratio batching, carry out ball milling then and mix, the oven dry back is added tackiness agent and is mixed granulation;
6) powder with step 5 gained carries out compressing tablet in 100～300MPa, again in 500～700 ℃ of plastic removals, and sintering 2～5 hours in 1000～1150 ℃ of air then, furnace cooling obtains ceramic plate.
5. the preparation method of potassium-sodium niobate-lithium niobate piezoelectric ceramics as claimed in claim 4 is characterized in that, in step 3 and the step 4, is warming up to described pre-synthesis temperature with the temperature rise rate of 2～10 ℃/min.
6. the preparation method of potassium-sodium niobate-lithium niobate piezoelectric ceramics as claimed in claim 4 is characterized in that, the addition of described tackiness agent is the 8～25wt% that accounts for the back of oven dry described in the step 5 gained powder weight.
7. the application of potassium-sodium niobate-lithium niobate piezoelectric ceramics as claimed in claim 1 or 2 in transceiver type PZT (piezoelectric transducer).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101092695A CN101786880B (en) | 2010-02-11 | 2010-02-11 | Sodium potassium niobate-potassium lithium niobate piezoelectric ceramics and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101092695A CN101786880B (en) | 2010-02-11 | 2010-02-11 | Sodium potassium niobate-potassium lithium niobate piezoelectric ceramics and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101786880A true CN101786880A (en) | 2010-07-28 |
| CN101786880B CN101786880B (en) | 2012-06-06 |
Family
ID=42530280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101092695A Active CN101786880B (en) | 2010-02-11 | 2010-02-11 | Sodium potassium niobate-potassium lithium niobate piezoelectric ceramics and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101786880B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276256A (en) * | 2011-06-03 | 2011-12-14 | 南京航空航天大学 | Lead-less potassium sodium niobate piezoelectric ceramics and preparation method thereof |
| CN104874805A (en) * | 2015-06-10 | 2015-09-02 | 北京科技大学 | Nonlinear optical material lead-lithium niobate, and preparation method and application of powder thereof |
| CN105789600A (en) * | 2016-04-27 | 2016-07-20 | 宁德时代新能源科技股份有限公司 | Lithium battery positive electrode material, preparation method thereof and lithium ion battery containing material |
| CN107176837A (en) * | 2017-05-31 | 2017-09-19 | 哈尔滨理工大学 | A kind of preparation method of ultra-high dielectric coefficient potassium tantalate-niobate ceramics |
| CN109456057A (en) * | 2018-11-01 | 2019-03-12 | 歌尔股份有限公司 | Barium calcium zirconate titanate based leadless piezoelectric ceramics and preparation method thereof |
| CN110357629A (en) * | 2019-08-20 | 2019-10-22 | 南京大学 | A kind of solid solution and preparation method of tungsten bronze and perovskite structure oxide formation |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289318A (en) * | 2008-06-12 | 2008-10-22 | 北京科技大学 | Sodion compensating potassium and sodium niobate based leadless piezoelectric ceramics and method for preparing same |
-
2010
- 2010-02-11 CN CN2010101092695A patent/CN101786880B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289318A (en) * | 2008-06-12 | 2008-10-22 | 北京科技大学 | Sodion compensating potassium and sodium niobate based leadless piezoelectric ceramics and method for preparing same |
Non-Patent Citations (1)
| Title |
|---|
| 《J.Am.Ceram.Soc.》 20090331 Jiangtao Zeng et al. Enhanced Ferroelectric Properties of Potassium Sodium Niobate Ceramics Modified by Small Amount of K3Li2Nb5O15 752-754 1，2，7 第92卷, 第3期 2 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276256A (en) * | 2011-06-03 | 2011-12-14 | 南京航空航天大学 | Lead-less potassium sodium niobate piezoelectric ceramics and preparation method thereof |
| CN104874805A (en) * | 2015-06-10 | 2015-09-02 | 北京科技大学 | Nonlinear optical material lead-lithium niobate, and preparation method and application of powder thereof |
| CN104874805B (en) * | 2015-06-10 | 2017-05-10 | 北京科技大学 | Nonlinear optical material lead-lithium niobate, and preparation method and application of powder thereof |
| CN105789600A (en) * | 2016-04-27 | 2016-07-20 | 宁德时代新能源科技股份有限公司 | Lithium battery positive electrode material, preparation method thereof and lithium ion battery containing material |
| CN105789600B (en) * | 2016-04-27 | 2019-05-07 | 宁德时代新能源科技股份有限公司 | Lithium battery positive electrode material, preparation method thereof and lithium ion battery containing material |
| CN107176837A (en) * | 2017-05-31 | 2017-09-19 | 哈尔滨理工大学 | A kind of preparation method of ultra-high dielectric coefficient potassium tantalate-niobate ceramics |
| CN107176837B (en) * | 2017-05-31 | 2019-12-06 | 哈尔滨理工大学 | Preparation method of potassium tantalate niobate ceramic with ultrahigh dielectric constant |
| CN109456057A (en) * | 2018-11-01 | 2019-03-12 | 歌尔股份有限公司 | Barium calcium zirconate titanate based leadless piezoelectric ceramics and preparation method thereof |
| CN109456057B (en) * | 2018-11-01 | 2021-10-08 | 歌尔微电子股份有限公司 | Barium zirconate titanate calcium-based leadless piezoelectric ceramic and preparation method thereof |
| CN110357629A (en) * | 2019-08-20 | 2019-10-22 | 南京大学 | A kind of solid solution and preparation method of tungsten bronze and perovskite structure oxide formation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101786880B (en) | 2012-06-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102311266B (en) | Preparation method of (K05Na05) NbO3 (KNN) lead-free piezoelectric ceramic material | |
| CN101200369B (en) | Titanium niobic zincic acid bismuth sodium system leadless piezo-electric ceramic and preparation method thereof | |
| CN101462875A (en) | Bismuth sodium titanate based leadless piezoelectric ceramic and preparation technique thereof | |
| CN101786880B (en) | Sodium potassium niobate-potassium lithium niobate piezoelectric ceramics and preparation method thereof | |
| CN102910902B (en) | BNT-BT-BKT-based perovskite system multielement lead-free piezoelectric ceramic and production method thereof | |
| CN101234895A (en) | Bismuth sodium titanate based leadless piezoelectric ceramic | |
| CN105198417B (en) | A kind of preparation method of zirconic acid bismuth sodium lithium cerium dopping potassium-sodium niobate base ceramic material | |
| CN102757220B (en) | Bi0.5, Na0.5 and TiO3 based ternary-system lead-free piezoelectric ceramic and preparation thereof | |
| CN102167585B (en) | Multielement-doped bismuth titanate group lead-free piezoceramic material and preparation method thereof | |
| CN102924078A (en) | BCTZ-based perovskite system multi-component lead-free piezoelectric ceramic and preparation method thereof | |
| JPWO2007099901A1 (en) | Piezoelectric ceramic composition | |
| CN101343182B (en) | Doped five-membered low-temperature melt piezoelectric ceramic material and preparation thereof | |
| CN105837200A (en) | Manganese-doped cerium lithium calcium titanoniobate-based ceramic material and preparation method thereof | |
| CN101302106A (en) | Potassium-sodium niobate-based leadless piezoelectric material and preparation thereof | |
| CN104098333A (en) | (K0.5Na0.5)NbO3-Sr(Sc0.5Nb0.5)O3 lead-free transparent ferroelectric ceramic material and preparation method thereof | |
| CN103833354A (en) | Solid solution-modified sodium bismuth titanate leadless piezoelectric ceramics and preparation method thereof | |
| CN109704762A (en) | A kind of SrNb2 O6 base class antiferroelectric ceramics and its preparation method and application | |
| CN102320828B (en) | Unleaded piezoelectric ceramic consisting of B-site composite Bi-based compound and preparation method thereof | |
| CN106518071B (en) | A kind of high-curie temperature, piezoceramic material of high-temperature stability and its preparation method and application | |
| Li et al. | Piezoelectric and dielectric properties of PbNb2O6-based piezoelectric ceramics with high Curie temperature | |
| CN101337814B (en) | Low temperature sintering lithium antimonite doped quinary system piezoelectric ceramics material and method for preparing same | |
| CN101219892A (en) | Solid-phase sintering technique for manufacturing bismuth titanate orientation ceramic | |
| CN106588007B (en) | High-quality-factor lead-free piezoelectric ceramic | |
| CN106518058B (en) | A kind of unleaded compound ferroelectric ceramics being made of bismuth potassium titanate and zinc oxide and preparation | |
| JIANG et al. | Structure and piezoelectric properties of (1–x) K0. 5Na0. 5NbO3–xLiBiO3 lead-free piezoelectric ceramics |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |