CN100424037C - Tantalum substitutional sodium potassium niobate based piezoelectric ceramics without plumbum, and preparation method - Google Patents
Tantalum substitutional sodium potassium niobate based piezoelectric ceramics without plumbum, and preparation method Download PDFInfo
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- CN100424037C CN100424037C CNB2006101049487A CN200610104948A CN100424037C CN 100424037 C CN100424037 C CN 100424037C CN B2006101049487 A CNB2006101049487 A CN B2006101049487A CN 200610104948 A CN200610104948 A CN 200610104948A CN 100424037 C CN100424037 C CN 100424037C
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Abstract
This invention discloses a Ta-substituted (K, Na) NbO3-based Pb-free piezoelectric ceramic, whose general formula is (K0.44Na0.52Li0.04) (Nb0.96-xTaxSb0.04) O3, where, x is 0.00-0.40. The preparation method comprises: pre-treating the raw materials, mixing, pre-sintering, granulating, producing green bodies, gel-casting, sintering, coating with Ag, polarizing and examining. The obtained Ta-substituted (K, Na) NbO3-based Pb-free piezoelectric ceramic has a piezoelectric constant d33 of 252 pC/N, an electromechanical coupling coefficient KP of 0.42, a dielectric constant epsivr of 1503, and a dielectric loss tan delta of 0.025. The Ta-substituted (K,Na)NbO3-based Pb-free piezoelectric ceramic has such advantages as high dielectric parameters, high piezoelectric parameters, high time stability and simple process, and can be used to prepare acoustic generators, ultrasonic transdecuers and resonators.
Description
Technical field
The invention belongs to the material technology field.Be specifically related to be used for piezoelectric device or electrostretch device.
Background technology
Piezoceramic material is a material of making piezo-electric acoustic generator, ultrasonic transducer, resonator, chip multilayer transformer, micro-displacement sensor and other transmitter, driving mechanism etc.The piezoelectric researchdevelopment is very rapid, be widely used in becoming the preparation material of indispensable modernized critical material and new electronic component in the electronics of products such as notebook computer, mobile phone, liquid-crystal display, digital camera, duplicating machine, charger and sophisticated technologies such as Aeronautics and Astronautics and national defence.
The piezoceramic material that is extensive use of at present and has a premium properties is to contain plumbous Pb (Zr, Ti) O
3(being abbreviated as PZT) base is main polycrystalline material, wherein PbO (or Pb
3O
4) accounting for 70% of raw material gross weight, this class stupalith causes serious harm all can in production, use and waste treatment process the mankind and ecotope.Therefore, must adopt unleaded piezoceramic material to substitute traditional PZT based piezoelectric ceramic materials, reduce the pollution of environment.In the material technology field, developing high performance lead-free piezoceramic material has become the current technical problem that presses for solution.
(K, Na) NbO
3(being abbreviated as KNN) is a kind of in the base metal niobate material, because of it has high Curie temperature and piezoelectric property, is considered to one of material of the most promising replacement PZT base.Adopt hot-pressing technique can make the density of pottery reach 99% of theoretical density, piezoelectric constant d
33Can reach 160pC/N, electromechanical coupling factor k
pCan reach 0.45.Yet K and Na are at high temperature volatile, adopt traditional ceramics technology to be difficult to obtain the good ceramic body of compactness, make the piezoelectric ceramics degradation.It is reported its piezoelectric constant d
3370pC/N is only arranged, electromechanical coupling factor k
pOnly have 0.25.In addition, the small variation of component has caused the formation of piezoelectric ceramics dephasign, makes piezoelectric ceramics be easy to deliquescence.Adopt hot pressing, heat is forged, spark sintering process can obtain compactness and good electrical property piezoelectric ceramics, but equipment complexity, production cost are higher, the scantling size is restricted, and is difficult to practicability.Conventional piezoelectric ceramic process cost is low, and method is simple, can be used for scale operation.The scholar and the research institution of countries in the world have carried out number of research projects, attempt by exploitation (K, Na) NbO
3Means such as base new system or doping vario-property are prepared high performance piezoelectric ceramics with conventional solid-state method.Though improve but the result shows the partial properties parameter of piezoelectric ceramics, another part performance perameter is worsened.The practicability of leadless piezoelectric ceramics should be prerequisite with piezoelectric ceramics over-all properties Parameter Optimization.
Summary of the invention
A technical problem to be solved by this invention is to overcome above-mentioned PZT base piezoelectric ceramic and (K, Na) NbO
3The shortcoming of based piezoelectric ceramic materials, the potassium niobate sodium-based leadless piezoelectric ceramic that provides good, practical, the easy production of a kind of performance, non-environmental-pollution, tantalum adulterated, that component is many to replace.
Another technical problem to be solved by this invention is to provide the preparation method of the potassium niobate sodium-based leadless piezoelectric ceramic that a kind of tantalum replaces.
Solving the problems of the technologies described above the scheme that is adopted is: with general formula (K
0.44Na
0.52Li
0.04) (Nb
0.96-xTa
xSb
0.04) O
3The material of expression is formed, and x represents the atomicity of component in the formula, 0.00≤x≤0.40.
The present invention general formula (K
0.04Na
0.52Li
0.04) (Nb
0.96-xTa
xSb
0.04) O
3The material of expression is formed, and x represents the atomicity of component in the formula, the preferred span of x: 0.15≤x≤0.25.
The present invention general formula (K
0.44Na
0.52Li
0.04) (Nb
0.96-xTa
xSb
0.04) O
3The material of expression is formed, and x represents the atomicity of component in the formula, and the best value of x is 0.20.
The preparation method of the potassium niobate sodium-based leadless piezoelectric ceramic that above-mentioned tantalum replaces comprises that step is as follows:
1, raw materials pretreatment
Respectively with general formula (K
0.44Na
0.52Li
0.04) (Nb
0.96-xTa
xSb
0.04) O
3Each raw material put into culture dish, culture dish is put into baking oven, 200 ℃ of down bakings 4 hours, to remove the moisture that adsorbs in the raw material.
2, mixing raw material
Raw material after step 1 processing is pressed general formula (K
0.44Na
0.52Li
0.04) (Nb
0.96-xTa
xSb
0.04) O
3Proportioning carry out weighing, batching, use dehydrated alcohol to be medium respectively, carry out wet-milling with planetary ball mill, 400 rev/mins of ball millings 12 hours are put into baking oven, 80 ℃ of oven dry down, grind with agate mortar, cross 100 mesh sieves, make dry powder.
3, pre-burning
Dry powder is put into alumina crucible, add a cover, will cover and open wide 1/4, put into the temperature programmed control box-type furnace, be warming up to 850 ℃ continuously, be incubated 9 hours, be cooled to room temperature, take out powder, levigate with agate mortar, cross 100 mesh sieves, be prepared into the pre-burning powder.
4, granulation
The pre-burning powder of step 3 preparation is put into agate mortar, and adding concentration is 5% polyvinyl alcohol, and total add-on equals 50～80% of pre-burning powder weight, fully grind with agate mortar, and seasoning, 100 mesh sieves are crossed in granulation, make spherical powder.
5, make biscuit
To put into stainless steel mould through the spherical powder after the granulation, 300MPa is pressed into biscuit with oil press.
6, binder removal
The biscuit of having made is put on the zirconium white plate of aluminum oxide saggar of uncovered, puts into the temperature programmed control box-type furnace, is warming up to 500 ℃ continuously, is incubated 1 hour, and power cutoff naturally cools to room temperature.
7, sintering
Biscuit behind step 6 binder removal is put on the zirconium white plate of aluminum oxide saggar of lid, put into the temperature programmed control box-type furnace, be warming up to 1085～1220 ℃ continuously, sintering 2 hours is cooled to room temperature, makes ceramic plain sheet.
8, by silver
The ceramic plain sheet of step 7 preparation is polished with 800 order fine sandpapers, with power is the ultrasonic cleaning machine of 50W, ultrasonic cleaning that frequency is 40KHz 30 minutes, silver slurry on two surface brush of the plain sheet of pottery, put into 120 ℃ of oven dry of baking oven, be placed on the silk screen, put into the temperature programmed control box-type furnace, be warming up to 850 ℃ continuously, be incubated 30 minutes, be cooled to room temperature, make by silver-colored ceramic plate.
9, polarization
The silver-colored ceramic plate of quilt of step 8 preparation is put into the silicone oil of polarization device, and oil bath is heated to 80 ℃, and the polarization 15 minutes down of 3kV/mm voltage is placed and worn out in 24 hours, makes the potassium niobate sodium-based leadless piezoelectric ceramic of tantalum replacement.
10, check
Test according to the piezoelectric device standard (IRE) that American Institute of Radio Engineer formulates.
Adopt the tantalum replacement sodium potassium niobate base leadless piezoelectric ceramics material of the inventive method preparation to test piezoelectric constant d
33Be 252pC/N, electromechanical coupling factor k
pBe 0.42, DIELECTRIC CONSTANT
rBe 1503, dielectric loss tan δ can be low to moderate 0.025, and the dielectric properties of piezoceramic material, the time stability of piezoelectric property are good.Tantalum of the present invention replaces potassium niobate sodium-based leadless piezoelectric ceramic and has advantages such as dielectric properties parameter and piezoelectric property parameters height, time stability are good, preparation technology's simple and stable, can be used for making the material of devices such as rattler, ultrasonic transducer, resonator.
Description of drawings
Fig. 1 is the X ray diffracting spectrum of the different pottery of Ta content.
Fig. 2 is that Ta content is the surface (a) of 0.00 pottery and the stereoscan photograph of section (b).
Fig. 3 is that Ta content is the surface (a) of 0.05 pottery and the stereoscan photograph of section (b).
Fig. 4 is that Ta content is the surface (a) of 0.10 pottery and the stereoscan photograph of section (b).
Fig. 5 is that Ta content is the surface (a) of 0.15 pottery and the stereoscan photograph of section (b).
Fig. 6 is that Ta content is the surface (a) of 0.20 pottery and the stereoscan photograph of section (b).
Fig. 7 is that Ta content is the surface (a) of 0.25 pottery and the stereoscan photograph of section (b).
Fig. 8 is that Ta content is the surface (a) of 0.30 pottery and the stereoscan photograph of section (b).
Fig. 9 is that Ta content is the surface (a) of 0.40 pottery and the stereoscan photograph of section (b).
Embodiment
To the detailed description of the invention, but the invention is not restricted to these embodiment below in conjunction with drawings and Examples.
Used raw material 100kg is an example with production product of the present invention, and x is 0.20 o'clock, with general formula (K
0.44Na
0.52Li
0.04) (Nb
0.76Ta
0.20Sb
0.04) O
3The raw material and the weight proportion thereof of expression are:
The Anhydrous potassium carbonate 14.53kg of purity 99%
The anhydrous sodium carbonate 13.06kg of purity 99.8%
The Quilonum Retard 0.71kg of purity 98%
The Niobium Pentxoxide 48.01kg of purity 99.5%
The tantalum pentoxide 20.90kg of purity 99.99%
The antimonous oxide 2.79kg of purity 99%
Its preparation methods steps is as follows:
1, raw materials pretreatment
Respectively each raw material is put into culture dish, culture dish is put into baking oven, dries by the fire 4 hours down at 200 ℃, to remove the moisture that adsorbs in the raw material.
2, mixing raw material
Raw material after step 1 processing is pressed general formula (K
0.44Na
0.52Li
0.04) (Nb
0.76Ta
0.20Sb
0.04) O
3Proportioning prepare burden, use dehydrated alcohol to be medium respectively, carry out wet-milling with ball mill, 400 rev/mins of ball millings 12 hours are put into baking oven, 80 ℃ of oven dry down, grind with agate mortar, cross 100 mesh sieves, make dry powder.
3, pre-burning
Dry powder is put into alumina crucible, add a cover, will cover and open wide 1/4, put into the temperature programmed control box-type furnace, be warming up to 850 ℃ continuously, be incubated 9 hours, be cooled to room temperature, take out powder, levigate with agate mortar, cross 100 mesh sieves, be prepared into the pre-burning powder.
4, granulation
The pre-burning powder of processing step 3 preparations is put into agate mortar, and adding concentration is 5% polyvinyl alcohol, and total add-on equals 65% of pre-burning powder weight, fully grind with agate mortar, and seasoning, 100 mesh sieves are crossed in granulation, make spherical powder.
5, make biscuit
To put into stainless steel mould through the spherical powder after the granulation, 300MPa is pressed into biscuit with oil press.
6, binder removal
The biscuit of having made is put on the zirconium plate of aluminum oxide saggar of uncovered, puts into the temperature programmed control box-type furnace, is warming up to 500 ℃ continuously, is incubated 1 hour, and power cutoff naturally cools to room temperature.
7, sintering
Biscuit behind step 6 binder removal is put on the zirconium plate of aluminum oxide saggar of lid, put into the temperature programmed control box-type furnace, be warming up to 1125 ℃ continuously, sintering 2 hours is cooled to room temperature, makes ceramic plain sheet.
8, by silver
The ceramic plain sheet of step 7 preparation is polished with 800 order fine sandpapers, with power is the ultrasonic cleaning machine of 50W, ultrasonic cleaning that frequency is 40KHz 30 minutes, silver slurry on two surface brush of the plain sheet of pottery, put into 120 ℃ of oven dry of baking oven, be placed on the silk screen, put into the temperature programmed control box-type furnace, be warming up to 850 ℃ continuously, be incubated 30 minutes, be cooled to room temperature, make by silver-colored ceramic plate.
9, polarization
The silver-colored ceramic plate of quilt of step 8 preparation is put into the silicone oil of polarization device, and oil bath is heated to 80 ℃, and the polarization 15 minutes down of 3kV/mm voltage is placed and worn out in 24 hours, makes the potassium niobate sodium-based leadless piezoelectric ceramic of tantalum replacement.
10, check
Test according to the piezoelectric device standard (IRE) that American Institute of Radio Engineer formulates.
Embodiment 2
Used raw material 100kg is an example with production product of the present invention, and x is 0.00 o'clock, with general formula [(K
0.44Na
0.52Li
0.04) (Nb
0.96Sb
0.44) O
3The raw material and the weight proportion thereof of expression are:
The Anhydrous potassium carbonate 15.83kg of purity 99%
The anhydrous sodium carbonate 14.24kg of purity 99.8%
The Quilonum Retard 0.78kg of purity 98%
The Niobium Pentxoxide 66.11kg of purity 99.5%
The antimonous oxide 3.04kg of purity 99%
Its preparation method is as follows:
Present embodiment is pressed general formula (K in mixing procedure step 2
0.44Na
0.52Li
0.04) (Nb
0.96Sb
0.04) O
3The raw material of expression is prepared burden, and in granulation process step 4, the pre-burning powder of processing step 3 preparations is put into agate mortar, adding concentration is 5% polyvinyl alcohol, and total add-on equals 50% of pre-burning powder weight, in sintering process step 7, be warming up to 1100 ℃ continuously, sintering 2 hours.Other processing step is identical with embodiment 1.
Embodiment 3
Used raw material 100kg is an example with production product of the present invention, and x is 0.05 o'clock, with general formula (K
0.04Na
0.52Li
0.04) (Nb
0..91Ta
0.05Sb
0.04) O
3The raw material and the weight proportion thereof of expression are:
The Anhydrous potassium carbonate 15.49kg of purity 99%
The anhydrous sodium carbonate 13.92kg of purity 99.8%
The Quilonum Retard 0.76kg of purity 98%
The Niobium Pentxoxide 61.29kg of purity 99.5%
The tantalum pentoxide 5.57kg of purity 99.99%
The antimonous oxide 2.97kg of purity 99%
Its preparation method is as follows:
Present embodiment is pressed general formula (K in mixing procedure step 2
0.44Na
0.52Li
0.04) (Nb
0..91Ta
0.05Sb
0.04) O
3The raw material of expression is prepared burden, and in granulation process step 4, the pre-burning powder of processing step 3 preparations is put into agate mortar, adding concentration is 5% polyvinyl alcohol, and total add-on equals 80% of pre-burning powder weight, in sintering process step 7, be warming up to 1110 ℃ continuously, sintering 2 hours.Other processing step is identical with embodiment 1.
Embodiment 4
Used raw material 100kg is an example with production product of the present invention, and x is 0.10 o'clock, with general formula (K
0.44Na
0.52Li
0.04) (Nb
0.86Ta
0.10Sb
0.04) O
3The raw material and the weight proportion thereof of expression are:
The Anhydrous potassium carbonate 15.15kg of purity 99%
The anhydrous sodium carbonate 13.62kg of purity 99.8%
The Quilonum Retard 0.75kg of purity 98%
The Niobium Pentxoxide 56.67kg of purity 99.5%
The tantalum pentoxide 10.90kg of purity 99.99%
The antimonous oxide 2.91kg of purity 99%
Its preparation method is as follows:
Present embodiment is pressed general formula (K in mixing procedure step 2
0.44Na
0.52Li
0.04) (Nb
0.86Ta
0.10Sb
0.04) O
3The raw material of expression is prepared burden, and in sintering process step 7, is warming up to 1115 ℃ continuously, sintering 2 hours.Other processing step is identical with embodiment 1.
Embodiment 5
Used raw material 100kg is an example with production product of the present invention, and x is 0.15 o'clock, with general formula (K
0.44Na
0.52Li
0.04) (Nb
0.81Ta
0.15Sb
0.04) O
3The raw material and the weight proportion thereof of expression are:
The Anhydrous potassium carbonate 14.83kg of purity 99%
The anhydrous sodium carbonate 13.34kg of purity 99.8%
The Quilonum Retard 0.73kg of purity 98%
The Niobium Pentxoxide 52.25kg of purity 99.5%
The tantalum pentoxide 16.01kg of purity 99.99%
The antimonous oxide 2.84kg of purity 99%
Its preparation method is as follows:
Present embodiment is pressed general formula (K in mixing procedure step 2
0.44Na
0.52Li
0.04) (Nb
0.81Ta
0.15Sb
0.04) O
3The raw material of expression is prepared burden, and in sintering process step 7, is warming up to 1115 ℃ continuously, sintering 2 hours.Other processing step is identical with embodiment 1.
Embodiment 6
Used raw material 100kg is an example with production product of the present invention, and x is 0.25 o'clock, with general formula (K
0.44Na
0.52Li
0.04) (Nb
0.71Ta
0.25Sb
0.04) O
3The raw material and the weight proportion thereof of expression are:
The Anhydrous potassium carbonate 14.23kg of purity 99%
The anhydrous sodium carbonate 12.79kg of purity 99.8%
The Quilonum Retard 0.70kg of purity 98%
The Niobium Pentxoxide 43.95kg of purity 99.5%
The tantalum pentoxide 25.60kg of purity 99.99%
The antimonous oxide 2.73kg of purity 99%
Its preparation method is as follows:
Present embodiment is pressed general formula (K in mixing procedure step 2
0.44Na
0.52Li
0.04) (Nb
0.71Ta
0.25Sb
0.04) O
3The raw material of expression is prepared burden, and in sintering process step 7, is warming up to 1150 ℃ continuously, sintering 2 hours.Other processing step is identical with embodiment 1.
Embodiment 7
Used raw material 100kg is an example with production product of the present invention, and x is 0.30 o'clock, with general formula (K
0.44Na
0.52Li
0.04) (Nb
0.66Ta
0.30Sb
0.04) O
3The raw material and the weight proportion thereof of expression are:
The Anhydrous potassium carbonate 13.95kg of purity 99%
The anhydrous sodium carbonate 12.54kg of purity 99.8%
The Quilonum Retard 0.69kg of purity 98%
The Niobium Pentxoxide 40.04kg of purity 99.5%
The tantalum pentoxide 30.11kg of purity 99.99%
The antimonous oxide 2.67kg of purity 99%
Its preparation method is as follows:
Present embodiment is pressed general formula (K in mixing procedure step 2
0.44Na
0.52Li
0.04) (Nb
0.66Ta
0.30Sb
0.04) O
3The raw material of expression is prepared burden, and in sintering process step 7, is warming up to 1165 ℃ continuously, sintering 2 hours.Other processing step is identical with embodiment 1.
Embodiment 8
Used raw material 100kg is an example with production product of the present invention, and x is 0.40 o'clock, with general formula (K
0.44Na
0.52Li
0.04) (Nb
0.56Ta
0.40Sb
0.04) O
3The raw material and the weight proportion thereof of expression are:
The Anhydrous potassium carbonate 13.42kg of purity 99%
The anhydrous sodium carbonate 12.06kg of purity 99.8%
The Quilonum Retard 0.66kg of purity 98%
The Niobium Pentxoxide 32.68kg of purity 99.5%
The tantalum pentoxide 38.61kg of purity 99.99%
The antimonous oxide 2.57kg of purity 99%
Its preparation method is as follows:
Present embodiment is pressed general formula (K in mixing procedure step 2
0.44Na
0.52Li
0.04) (Nb
0.56Ta
0.40Sb
0.04) O
3The raw material of expression is prepared burden, and in sintering process step 7, is warming up to 1200 ℃ continuously, sintering 2 hours.Other processing step is identical with embodiment 1.
In order to determine optimum weight proportioning of the present invention and best preparation method, according to the IRE standard, the contriver has carried out dielectric, the piezoelectric property test experiments of the potassium niobate sodium-based leadless piezoelectric ceramic crossed at 1085～1220 ℃ of following sintering, and various experiment situations are as follows:
Testing tool: the accurate LCR bridge test of HP4294A type instrument, produce by Anjelen Sci. ﹠ Tech. Inc; Quasistatic d
33Tester is produced by Acoustical Inst., Chinese Academy of Sciences; The accurate electric impedance analyzer of HP4294A is produced by Anjelen Sci. ﹠ Tech. Inc; X-ray diffractometer (D/max-2200) is produced by Japan company of science; Scanning electron microscope (Quanta 200) is produced by Dutch Philips FEI Co..
1, Ta content is to the influence of ceramic phase structure
Test the phase structure of the prepared piezoelectric ceramics of different Ta content by the testing method of instrument with X-ray diffractometer (D/max-2200).Test result is seen Fig. 1.
As seen from Figure 1, the prepared piezoelectric ceramics of different Ta content all is a perovskite structure.When x was 0.00, piezoelectric ceramics was a rhombic system.Along with the increase of x, piezoelectric ceramics has taken place from the transformation of quadrature to tetragonal system.When x was 0.20, piezoelectric ceramics was a tetragonal system.Continue to increase x, piezoelectric ceramics has taken place again from the four directions to the transformation of pseudo-isometric system.When x was 0.40, piezoceramic material was pseudo-isometric system.
2, Ta content is to the influence of ceramic surface and section microscopic appearance
Promptly adopting x with scanning electron microscopic observation embodiment 1～8 is 0.00,0.05,0.10,0.15,0.20,0.25,0.30,0.40 o'clock, the prepared piezoelectric ceramics surface and the microscopic appearance of section.Observed result is seen Fig. 2～9.
As seen from Figure 2, when x was 0.00, the ceramic crystalline grain size was inhomogeneous, be 2～10 μ m, and ceramic pore was very many.As seen from Figure 3, along with x increases to 0.05, the median size of pottery descends, and ceramic pore begins to reduce.As seen from Figure 4, when x increased to 0.10, the median size of pottery continued to descend.The pottery pore continues to reduce.As seen from Figure 5, when x increased to 0.15, the median size of pottery continued to descend, and grain size begins to become evenly, and ceramic pore is considerably less.As seen from Figure 6, when x was 0.20, the ceramic crystalline grain particle diameter was little and big or small evenly, is 1～4 μ m.Pottery does not have pore substantially, and is very fine and close.As seen from Figure 7, increase x by 0.25 o'clock, the median size of pottery changes little, and pottery begins to occur pore.As seen from Figure 8, increase x by 0.30 o'clock, the median size of pottery changes little, and ceramic pore has increased.As seen from Figure 9, continue to increase x by 0.40 o'clock, the median size of pottery changes little, and ceramic pore is very many.When x is 0.20, can obtain the little and big or small homogeneous of particle diameter, very fine and close piezoelectric ceramics.
3, mix the influence of tantalum content and sintering temperature to the dielectric and the piezoelectric property parameters of piezoelectric ceramics
Different Ta content, the prepared piezoelectric ceramics of different sintering temperature are measured its dielectric properties parameter and piezoelectric property parameters.
Measure the dielectric characteristics parameter: adopt capacitor C and the dielectric loss tan δ of pottery under 10kHz under the accurate LCR bridge test of HP4294A type different components, the different sintering temperature, calculate DIELECTRIC CONSTANT
rIts calculation formula is:
ε
r＝4Ct/(πε
0d
2)
Wherein, t is the thickness of piezoelectric ceramic piece, ε
0Be permittivity of vacuum (8.85*10
-12F/m), d is the diameter of piezoelectric ceramic piece.
Measure piezoelectric property parameters: adopt quasistatic d
33Tester is measured the piezoelectric constant d of the piezoelectric ceramics under different components, the different sintering temperature by the working method of instrument
33Measure the resonant frequency f of piezoelectric ceramics according to resonance-antiresonance method with the accurate electric impedance analyzer of HP4294A
r, anti-resonance frequency f
aWith corresponding resonance impedance R
f, calculate electromechanical coefficient K
pWith mechanical quality factor Q
a, its calculation formula is:
K
p＝[0395f
r/(f
a-f
r)+0.574]
-1/2
Q
m＝f
a 2[2πR
fCf
r(f
a 2-f
r 2)]
-1
Test and dielectric properties parameter and the piezoelectric property parameters calculated the results are shown in Table 1.
(K under the different sintering temperatures of table 1
0.44Na
0.52Li
0.04) (Nb
0.96-xTa
xSb
0.04) O
3The dielectric of piezoelectric ceramics and piezoelectric property parameters
As shown in Table 1:
(1) sintering temperature has influence to the pottery of same component.X is 0.00,0.05,0.10,0.15,0.20,0.25,0.30,0.40 piezoceramic material, and its optimal sintering temperature is respectively 1100 ℃, 1110 ℃, 1115 ℃, 1115 ℃, 1125 ℃, 1150 ℃, 1165 ℃, 1200 ℃.In the composition of piezoelectric ceramics, mix Ta content difference, agglomerating optimum temps difference.
(2) under the optimal sintering temperature condition, tantalum content changes its dielectric characteristics parameter to piezoelectric ceramics and piezoelectric property parameters is changed significantly with mixing.X is 0.00 o'clock, d
33Be 123pC/N, K
pBe 0.23, ε
rHave 550, tan δ is up to 0.052.Along with the increase of Ta content, d
33, K
pAnd ε
rIncrease sharply, tan δ reduces rapidly.X is 0.20 o'clock, d
33Up to 252pC/N, K
pUp to 0.42, ε
rUp to 1503, tan δ is low to moderate 0.025.Along with the continuation increase of Ta content, d
33And K
pBegin to reduce ε
rContinuing increases, and tan δ begins to raise.In addition, Q
aIts variation of increase with Ta content is not clearly, always less than 100.Mix x and be 0.15～0.25 tantalum, can improve (K, Na) NbO greatly
3The piezoelectricity and the dielectric properties parameter of base.
(3) to sum up, when tantalum content in x is 0.15～0.25 scope and between 1115～1150 ℃ of the sintering temperatures, can obtain high performance tantalum (K, Na) NbO of mixing
3Base piezoelectric ceramic, its performance perameter is: d
33Be 196～252pC/N, K
pBe 0.33～0.42, Q
aBe 52～53, ε
rBe 1356～1598, tan δ is 0.025～0.031.Its best ceramic component x is 0.20, and its optimal sintering temperature is 1125 ℃, and piezoelectric ceramics has optimum comprehensive electrochemical properties parameter, its d
33Be 252pC/N, K
pBe 0.42, Q
aBe 52, ε
rBe 1503, tan δ is 0.025.
4, the performance perameter of leadless piezoelectric ceramics situation over time
With x is piezoelectric ceramics 1～9 week of placement of 0.15 and 0.20 preparation, tests its d
33, K
pReach tan δ situation over time, determine the time stability of piezoelectric ceramics performance perameter.With the accurate LCR bridge test of HP4294A type instrument, the dielectric loss tan δ of working method test piezoelectric ceramics under 10kHz according to instrument uses quasistatic d
33Tester is according to the piezoelectric constant d of the working method test pottery of instrument
33With the accurate electric impedance analyzer of HP4294A, measure the resonant frequency f of pottery according to resonance-antiresonance method
rWith anti-resonance frequency f
a, calculate electromechanical coefficient K
p, its calculation formula is:
K
p＝[0.395f
r/(f
a-f
r)+0.574]
-1/2
X is the d of 0.15 o'clock piezoelectric ceramics
33, K
pTest over time with tan δ and calculation result sees Table 2.
X is the d of 0.20 o'clock piezoelectric ceramics
33, K
pTest over time with tan δ and calculation result sees Table 3.
Table 2x is the d of 0.15 o'clock piezoelectric ceramics
33, K
pWith tan δ variation relation in time
| Storage period (week) | 0.14 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
| d 33 | 226 | 226 | 223 | 221 | 220 | 219 | 218 | 217 | 217 | 217 |
| K p | 0.40 | 0.40 | 0.39 | 0.39 | 0.39 | 0.39 | 0.39 | 0.39 | 0.39 | 0.39 |
| tanδ | 0.031 | 0.032 | 0.032 | 0.034 | 0.033 | 0.032 | 0.031 | 0.031 | 0.030 | 0.034 |
As can be seen from Table 2, after 9 weeks, d
339pC/N has only fallen, k
pFallen 0.01, tan δ has only raise 0.003, illustrates that this piezoelectric ceramics has good time stability.
Table 3x is the d of 0.20 o'clock pottery
33, K
pWith tan δ variation relation in time
| Storage period (week) | 0.14 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
| d 33 | 252 | 251 | 250 | 249 | 247 | 246 | 245 | 245 | 244 | 244 |
| K p | 0.42 | 0.42 | 0.42 | 0.41 | 0.41 | 0.41 | 0.41 | 0.41 | 0.41 | 0.41 |
| tanδ | 0.025 | 0.028 | 0.028 | 0.030 | 0.030 | 0.031 | 0.030 | 0.030 | 0.031 | 0.033 |
As can be seen from Table 3, after 9 weeks, d
338pC/N has only fallen, k
pFallen 0.01, tan δ has only raise 0.008, illustrates that this piezoelectric ceramics has good time stability.
When x is 0.15～0.20, (K
0.44Na
0.52Li
0.04) (Nb
0.96-xTa
xSb
0.04) O
3Stupalith has good time stability.
Conclusion: adopt the tantalum replacement sodium potassium niobate base leadless piezoelectric ceramics material test result of the inventive method preparation to show piezoelectric constant d
33Up to 252pC/N, electromechanical coupling factor K
pUp to 0.42, DIELECTRIC CONSTANT
rBe 1503, dielectric loss tan δ can be low to moderate 0.025, and the dielectric properties of piezoceramic material, the time stability of piezoelectric property are good.Tantalum of the present invention replaces potassium niobate sodium-based leadless piezoelectric ceramic and has advantages such as dielectric properties parameter and piezoelectric property parameters height, time stability are good, preparation technology's simple and stable, can be used for making the material of devices such as rattler, ultrasonic transducer, resonator.
Claims (1)
1. the preparation method of the potassium niobate sodium-based leadless piezoelectric ceramic of a tantalum replacement is characterized in that it comprises the steps:
(1) raw materials pretreatment
Respectively with general formula (K
0.44Na
0.52Li
0.04) (Nb
0.96-xTa
xSb
0.04) O
3Each raw material put into culture dish, x represents the atomicity of component in the formula, 0.00≤x≤0.40, culture dish is put into baking oven, 200 ℃ of down bakings 4 hours;
(2) mixing raw material
Raw material after step (1) processing is pressed general formula (K
0.44Na
0.52Li
0.04) (Nb
0.96-xTa
xSb
0.04) O
3Proportioning carry out weighing, batching, use dehydrated alcohol to be medium respectively, carry out wet-milling with ball mill, 400 rev/mins of ball millings 12 hours are put into baking oven, 80 ℃ of oven dry down, grind with agate mortar, cross 100 mesh sieves, make dry powder;
(3) pre-burning
Dry powder is put into alumina crucible, add a cover, will cover and open wide 1/4, put into the temperature programmed control box-type furnace, be warming up to 850 ℃ continuously, be incubated 9 hours, be cooled to room temperature, take out powder, levigate with agate mortar, cross 100 mesh sieves, be prepared into the pre-burning powder;
(4) granulation
The pre-burning powder of step (3) preparation is put into agate mortar, and adding concentration is 5% polyvinyl alcohol, and total add-on equals 50～80% of pre-burning powder weight, fully grind with agate mortar, and seasoning, 100 mesh sieves are crossed in granulation, make spherical powder;
(5) make biscuit
To put into stainless steel mould through the spherical powder after the granulation, 300MPa is pressed into biscuit with oil press;
(6) binder removal
The biscuit of having made is put on the zirconium plate of aluminum oxide saggar of uncovered, puts into the temperature programmed control box-type furnace, is warming up to 500 ℃ continuously, is incubated 1 hour, and power cutoff naturally cools to room temperature;
(7) sintering
Biscuit behind step (6) binder removal is put on the zirconium plate of aluminum oxide saggar of lid, put into the temperature programmed control box-type furnace, be warming up to 1085～1220 ℃ continuously, sintering 2 hours is cooled to room temperature, makes ceramic plain sheet;
(8) by silver
The ceramic plain sheet of step (7) preparation is polished with 800 order fine sandpapers, with power is the ultrasonic cleaning machine of 50W, ultrasonic cleaning that frequency is 40KHz 30 minutes, silver slurry on two surface brush of the plain sheet of pottery, put into 120 ℃ of oven dry of baking oven, be placed on the silk screen, put into the temperature programmed control box-type furnace, be warming up to 850 ℃ continuously, be incubated 30 minutes, be cooled to room temperature, make by silver-colored ceramic plate;
(9) polarization
The silver-colored ceramic plate of quilt of step (8) preparation is put into the silicone oil of polarization device, and oil bath is heated to 80 ℃, and the polarization 15 minutes down of 3kV/mm voltage is placed and worn out in 24 hours, makes the potassium niobate sodium-based leadless piezoelectric ceramic of tantalum replacement.
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| CN101456733B (en) * | 2008-09-24 | 2011-11-30 | 陕西师范大学 | Method for preparing potassium niobate sodium base leadless piezoelectric ceramic thin sheet |
| CN101503294B (en) * | 2009-03-04 | 2011-12-14 | 中国科学院上海硅酸盐研究所 | Niobate leadless piezoelectric ceramic with orderedly arranged paracrystal and preparation thereof |
| CN101863661B (en) * | 2010-06-04 | 2016-01-06 | 中国科学院上海硅酸盐研究所 | The preparation method of textured potassium niobate sodium-based leadless piezoelectric ceramic |
| CN101857436B (en) * | 2010-06-12 | 2013-03-13 | 中国地质大学（武汉） | Preparation methodof potassium-sodium niobate base lead-free piezoelectric ceramic powder |
| CN102249677A (en) * | 2011-05-30 | 2011-11-23 | 西南科技大学 | Silver niobate-based lead-free piezoelectric ceramic and preparation method thereof |
| CN102910906A (en) * | 2012-10-22 | 2013-02-06 | 天津大学 | High-performance potassium-sodium niobate-based leadless piezoelectric ceramic and preparation method thereof |
| CN103469307B (en) * | 2013-09-29 | 2016-04-27 | 哈尔滨工业大学 | The potassium-sodium niobate-based piezoquartz of Tetragonal lithium antimony tantalum codoped |
| CN106350869B (en) * | 2016-09-20 | 2019-04-12 | 哈尔滨工业大学 | A kind of orthorhombic phase Mn doping niobium tantalum potassium antimonate sodium lithium leadless piezoelectric monocrystalline of extra-high voltage performance and preparation method thereof |
| CN115286386B (en) * | 2022-08-27 | 2023-07-18 | 四川大学 | Non-stoichiometric Nb 5+ Potassium sodium bismuth niobate tantalum zirconium iron acid ceramic and preparation method thereof |
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| CN1511802A (en) * | 2002-12-27 | 2004-07-14 | 四川大学 | Multi constituent niobate lead-free piezoelectric ceramics |
| CN1699280A (en) * | 2005-06-02 | 2005-11-23 | 武汉理工大学 | Niobate leadless piezoelectric material material and preparation method thereof |
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| CN1699280A (en) * | 2005-06-02 | 2005-11-23 | 武汉理工大学 | Niobate leadless piezoelectric material material and preparation method thereof |
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