CN105198411A - Large-strain low-drive electric field relaxation and ferroelectric composite lead-free piezoelectric ceramic and preparation method thereof - Google Patents
Large-strain low-drive electric field relaxation and ferroelectric composite lead-free piezoelectric ceramic and preparation method thereof Download PDFInfo
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Abstract
The invention discloses large-strain low-drive electric field relaxation and ferroelectric composite lead-free piezoelectric ceramic and a preparation method thereof. The method includes: acquiring a component A, (1-x1-y1)Bi0.5Na0.5TiO3-x1Bi0.5K0.5TiO3-y1AgNbO3, wherein 0.16</=x1</=0.22, 0.01</=y1</=0.03; or (1-x2-y2)Bi0.5Na0.5TiO3-x2BaTiO3-y2AgNbO3, wherein 5</=x2</=0.07, 0.01</=y2</=0.03; and a component B, (1-z)Bi0.5Na0.5TiO3-zBaTiO3, wherein 0.05</=z</=0.07; or (1-w)Bi0.5Na0.5TiO3-wBi0.5K0.5TiO3, wherein 0.16</=w</=0.22; after drying, heating, pre-sintering, ball-milling and drying, pre-sintering each component for 3 hours; after grinding, mixing ferroelectric lead-free ceramic B and relaxation lead-free piezoelectric ceramic B, performing ball-milling for 4 hours, and performing PVA granulating, dry-pressing forming, sintering and polishing to obtain the composite lead-free piezoelectric ceramic. The performance is improved, production technical difficulty is lowered, and cost is lowered.
Description
Technical field
The invention belongs to composite piezoelectric ceramic technical field, relate to a kind of large sstrain low driving electric field relaxation-ferroelectric compound leadless piezoelectric ceramics and preparation method thereof.
Background technology
In order to the lead base piezoelectric in alternative conventional multilayer piezo-activator, German scholar is at paper " Giantstraininlead-freepiezoceramicsBi
0.5na
0.5tiO
3-BaTiO
3-K
0.5na
0.5nbO
3system " report a kind of lead-free piezoceramic material with super large strain in (AppliedPhysicsLetters2007 91 volume 11 phase); and its electric field induced strain amount can reach 0.45%; but driving electric field is up to 8kV/mm, also has very large distance from practical.Korea S scholar is at " Electricfield-induceddeformationbehaviorinmixedBi
0.5na
0.5tiO
3andBi
0.5(Na
0.75k
0.25)
0.5tiO
3-BiAlO
3" reporting ferroelectric-relaxation compound lead-free piezoceramic material in (AppliedPhysicsLetters2011 the 99th volume the 6th phase); this compound piezoceramic material first prepares bismuth-sodium titanate (BNT) monocrystal material; then join in the bismuth sodium potassium titanate matrix of Bismuth Aluminate doping; then sintering forms 0-3 type composite piezoelectric ceramic; driving electric field can be reduced to 4kV/mm by this technology; electric field induced strain can reach 0.27%, but bismuth-sodium titanate single crystal preparation technique is comparatively complicated, and cost is also higher.
Current commercial piezoelectric ceramics and device are all adopt Pb (Zr, Ti) O
3(PZT) traditional plumbum-based material such as, PbO (or Pb
3o
4) accounting for 70% of total mass, so high Pb content makes piezoelectric device bring very large infringement to environment and human health after preparing, use and discarding.In order to prevent the pollution of the environment, the overwhelming majority of countries such as Europe, Japan, Korea S and China put into effect law in succession, forbid or limit the use of Pb in electronic product.In addition, there is the shortcomings such as piezoelectric strain is little, piezoelectric property is poor in the leadless piezoelectric ceramics researched and developed now, BNT-BT-KNN relaxation type leadless piezoelectric ceramics has the electric field induced strain also larger than soft PZT, great potential using value is had in piezo-activator, but required driving electric field is excessive, is difficult to practical application.
Summary of the invention
The object of this invention is to provide a kind of large sstrain low driving electric field relaxation-ferroelectric compound leadless piezoelectric ceramics and preparation method thereof, solve problems of the prior art, while maintenance relaxation leadless piezoelectric material material large sstrain, effectively reduce driving electric field, make the application of large sstrain lead-free piezoceramic material become possibility, be applicable to very much and manufacture large sstrain multilayer leadless piezoelectric actuator.
The technical solution adopted in the present invention is, large sstrain low driving electric field relaxation-ferroelectric compound leadless piezoelectric ceramics, be composited by relaxation type leadless piezoelectric ceramics A and ferroelectric lead-free ceramics B, the chemical composition of A and B meets following chemical formula: the composition of A is: (1-x
1-y
1) Bi
0.5na
0.5tiO
3-x
1bi
0.5k
0.5tiO
3-y
1agNbO
3, 0.16≤x
1≤ 0.22,0.01≤y
1≤ 0.03; Or (1-x
2-y
2) Bi
0.5na
0.5tiO
3-x
2baTiO
3-y
2agNbO
3, 0.05≤x
2≤ 0.07,0.01≤y
2≤ 0.03; The composition of B is: (1-z) Bi
0.5na
0.5tiO
3-zBaTiO
3, 0.05≤z≤0.07, or (1-w) Bi
0.5na
0.5tiO
3-wBi
0.5k
0.5tiO
3, 0.16≤w≤0.22.
Further, the volume ratio of the mixing of A and B is 90:10-50:50.
Further, this piezoelectric ceramics has the electric field induced strain of 0.22%-0.32% under the driving electric field of 4kV/mm.
Another technical scheme of the present invention is, large sstrain low driving electric field relaxation-ferroelectric compound leadless piezoelectric ceramics preparation method, carries out according to following steps:
1) BaCO is weighed according to stoichiometric ratio
3, TiO
2, Na
2cO
3, K
2cO
3, Bi
2o
3, Nb
2o
5and Ag
2cO
3after raw material, under ethanol medium, carry out ball milling mixing respectively, after oven dry, obtain the raw material powder of relaxation type lead-free piezoelectric ceramic powder A and ferroelectric lead-free ceramics powder B respectively;
The composition of the relaxation type lead-free piezoelectric ceramic powder A wherein obtained is: (1-x
1-y
1) Bi
0.5na
0.5tiO
3-x
1bi
0.5k
0.5tiO
3-y
1agNbO
3, 0.16≤x
1≤ 0.22,0.01≤y
1≤ 0.03; Or (1-x
2-y
2) Bi
0.5na
0.5tiO
3-x
2baTiO
3-y
2agNbO
3, 0.05≤x
2≤ 0.07,0.01≤y
2≤ 0.03;
The composition of ferroelectric lead-free ceramics powder B is: (1-z) Bi
0.5na
0.5tiO
3-zBaTiO
3, 0.05≤z≤0.07, or (1-w) Bi
0.5na
0.5tiO
3-wBi
0.5k
0.5tiO
3, 0.16≤w≤0.22;
2) in step 1, the raw material powder of A and B is dried, be respectively charged into crucible, put into retort furnace, in air atmosphere with the temperature rise rate of 5 DEG C/min, being warming up to temperature is 800 DEG C-850 DEG C, pre-burning 2 hours, 1 hour, obtains the ferroelectric lead-free ceramics powder B after the relaxation type lead-free piezoelectric ceramic powder A after pre-burning and pre-burning respectively;
3) the relaxation type lead-free piezoelectric ceramic powder A after pre-burning, the ferroelectric lead-free ceramics powder B after pre-burning, be medium difference ball milling 4 hours with ethanol after manual milling, after drying, put into crucible with cover secondary pre-burning 3 hours at 1080-1120 DEG C respectively, obtain relaxation ferroelectric ceramic powder A and the ferroelectric ceramic powder B of pure phase respectively;
4) the relaxation ferroelectric ceramic powder A of pure phase and ferroelectric ceramic powder B in step 3, after milling by hand respectively, according to molar percentage, being mixed by the relaxation type leadless piezoelectric ceramics A of ferroelectric lead-free ceramics B and the 90-50Vol% of 10-50Vol%, is then that medium ball milling was drying to obtain mixed powder C after 24 hours with ethanol;
5) mixed powder C is by dry-pressing formed under 120MPa pressure after PVA granulation, in air atmosphere, sinter 1 hour at 1100-1140 DEG C, and intensification and rate of temperature fall are 8-12 DEG C/min, namely obtain 0-3 type relaxation-ferroelectric compound leadless piezoelectric ceramics;
6) the 0-3 type relaxation described in step 5-ferroelectric compound leadless piezoelectric ceramics, behind surface of polishing, brush silver electrode, to obtain final product.
The invention has the beneficial effects as follows: adopt environmental protection lead-free piezoceramic material to substitute the leaded piezoceramic material (accounting for 70% of total mass containing PbO amount) of existing piezo-activator, can not environmental pollution be caused in production and after discarding.Adopt ferroelectric-relaxation 0-3 type composite piezoelectric ceramic substitute before report BNT base relaxation leadless piezoelectric ceramics, driving electric field can be reduced to 4kV/mm by 8kV/mm, meet actual multi-layer piezoelectric actuator to the requirement of driving electric field, and, the strain of 0-3 type compound leadless piezoelectric ceramics under 4kV/mm that the BNT-BT mixing 30% volume ratio in BNT-BT-AN obtains can reach 0.32%, and this value will double than the strain value 0.15% of current used soft lead base piezoceramic material.In addition, utilize in composite ceramics BNT-BT and BNT-BKT Lead-free ferroelectric ceramics powder substitute before the BNT single crystal particle of report, effectively can reduce producting process difficulty and reduce costs about 40%.
Accompanying drawing explanation
Fig. 1 is described in the embodiment of the present invention 1, works as x1=0.18, and when y1=0.02, z=0.06, A is 0.80Bi
0.5na
0.5tiO
3-0.18Bi
0.5k
0.5tiO
3-0.02AgNbO
3, B is 0.94Bi
0.5na
0.5tiO
3-0.06BaTiO
3, the B powder of 20% volume ratio is mixed in the A powder of 80% volume ratio, the X ray diffracting spectrum of then prepared after ball milling, granulation and sintering compound leadless piezoelectric ceramics;
Fig. 2 is described in the embodiment of the present invention 3, works as x1=0.21, and when y1=0.03, z=0.07, A is 0.76Bi
0.5na
0.5tiO
3-0.21Bi
0.5k
0.5tiO
3-0.03AgNbO
3, B is 0.93Bi
0.5na
0.5tiO
3-0.07BaTiO
3, the B powder of 30% volume ratio is mixed in the A powder of 70% volume ratio, the curve of the dielectric constant with temperature change of then prepared after ball milling, granulation and sintering compound leadless piezoelectric ceramics;
Fig. 3 is described in the embodiment of the present invention 5, works as x1=0.17, and when y1=0.02, w=0.19, A is 0.81Bi
0.5na
0.5tiO
3-0.17Bi
0.5k
0.5tiO
3-0.02AgNbO
3, B is 0.81Bi
0.5na
0.5tiO
3-0.19Bi
0.5k
0.5tiO
3, the B powder of 35% volume ratio is mixed in the A powder of 65% volume ratio, then prepared after ball milling, granulation and sintering compound leadless piezoelectric ceramics ferroelectric hysteresis loop at room temperature;
Fig. 4 is described in the embodiment of the present invention 7, works as x2=0.06, and when y2=0.03, z=0.06, A is 0.91Bi
0.5na
0.5tiO
3-0.06BaTiO
3-0.03AgNbO
3, B is 0.94Bi
0.5na
0.5tiO
3-0.06BaTiO
3, the B powder of 30% volume ratio is mixed in the A powder of 70% volume ratio, then prepared after ball milling, granulation and sintering compound leadless piezoelectric ceramics one pole strain curve at room temperature;
Fig. 5 is described in the embodiment of the present invention 9, works as x2=0.07, and when y2=0.02, z=0.05, A is 0.91Bi
0.5na
0.5tiO
3-0.07BaTiO
3-0.02AgNbO
3, B is 0.95Bi
0.5na
0.5tiO
3-0.05BaTiO
3, the B powder of 20% volume ratio is mixed in the A powder of 80% volume ratio, then prepared after ball milling, granulation and sintering compound leadless piezoelectric ceramics ferroelectric hysteresis loop at room temperature;
Fig. 6 is described in the embodiment of the present invention 12, works as x2=0.05, and when y2=0.03, z=0.19, A is 0.92Bi
0.5na
0.5tiO
3-0.05BaTiO
3-0.03AgNbO
3, B is 0.81Bi
0.5na
0.5tiO
3-0.19BaTiO
3, the B powder of 30% volume ratio is mixed in the A powder of 70% volume ratio, then prepared after ball milling, granulation and sintering compound leadless piezoelectric ceramics one pole strain curve at room temperature.
Embodiment
Below by way of specific embodiment, relaxation of the present invention-ferroelectric compound leadless piezoelectric ceramics is further described; what be necessary to herein means out is that described embodiment is just for further illustrating of the present invention; but any restriction that should not be understood as scope, the those of skill in the art in this field can make improvement and the adjustment of some non-intrinsically safes according to the content of foregoing invention.
Large sstrain low driving electric field relaxation-ferroelectric compound leadless piezoelectric ceramics, be composited by relaxation type leadless piezoelectric ceramics A and ferroelectric lead-free ceramics B, the chemical composition of A and B meets following chemical formula: the composition of A is: (1-x
1-y
1) Bi
0.5na
0.5tiO
3-x
1bi
0.5k
0.5tiO
3-y
1agNbO
3, 0.16≤x
1≤ 0.22,0.01≤y
1≤ 0.03; Or (1-x
2-y
2) Bi
0.5na
0.5tiO
3-x
2baTiO
3-y
2agNbO
3, 0.05≤x
2≤ 0.07,0.01≤y
2≤ 0.03; The composition of B is: (1-z) Bi
0.5na
0.5tiO
3-zBaTiO
3, 0.05≤z≤0.07, or (1-w) Bi
0.5na
0.5tiO
3-wBi
0.5k
0.5tiO
3, 0.16≤w≤0.22.
Further, the volume ratio of the mixing of A and B is 90:10-50:50.
Further, this piezoelectric ceramics has the electric field induced strain of 0.22%-0.32% under the driving electric field of 4kV/mm.
By adding bismuth sodium potassium titanate or bismuth sodium titanate-barium titanate binary ferroelectric mutual-assistance relaxation type ceramic matrix at bismuth-sodium titanate-bismuth potassium titanate-niobic acid silver of large sstrain or bismuth sodium titanate-barium titanate-niobic acid silver ternary relaxation type leadless piezoelectric ceramics while maintenance large sstrain, its driving electric field effectively reduces.Basic ideas are in the relaxation type piezoelectric base unit of low-k, be mixed into the ferroelectric particle with high-k, sinter 0-3 type composite ceramics into, if by ferroelectric phase and relaxation equivalent be the electric capacity of series connection mutually, under extra electric field, the internal electric field of composite ceramics there will be non-uniform Distribution, the electric field of the ferroelectric particle inside of high dielectric can be lower than impressed field, and the electric field of the relaxation matrix of low dielectric will be higher than impressed field, make relaxation matrix be easier to electroluminescent phase transformation occurs like this, thus driving electric field is reduced to 4kV/mm by 8kV/mm.
Concrete steps are as follows:
1) BaCO is weighed according to stoichiometric ratio
3, TiO
2, Na
2cO
3, K
2cO
3, Bi
2o
3, Nb
2o
5and Ag
2cO
3after raw material, under ethanol medium, carry out ball milling mixing respectively, after oven dry, obtain the raw material powder of relaxation type lead-free piezoelectric ceramic powder A and ferroelectric lead-free ceramics powder B respectively;
The composition of the relaxation type lead-free piezoelectric ceramic powder A wherein obtained is: (1-x
1-y
1) Bi
0.5na
0.5tiO
3-x
1bi
0.5k
0.5tiO
3-y
1agNbO
3, 0.16≤x
1≤ 0.22,0.01≤y
1≤ 0.03; Or (1-x
2-y
2) Bi
0.5na
0.5tiO
3-x
2baTiO
3-y
2agNbO
3, 0.05≤x
2≤ 0.07,0.01≤y
2≤ 0.03;
The composition of ferroelectric lead-free ceramics powder B is: (1-z) Bi
0.5na
0.5tiO
3-zBaTiO
3, 0.05≤z≤0.07, or (1-w) Bi
0.5na
0.5tiO
3-wBi
0.5k
0.5tiO
3, 0.16≤w≤0.22;
2) in step 1, the raw material powder of A and B is dried, be respectively charged into crucible, put into retort furnace, in air atmosphere with the temperature rise rate of 5 DEG C/min, being warming up to temperature is distinguish pre-burning 2 hours and 1 hour at 800 DEG C and 850 DEG C, obtains the ferroelectric lead-free ceramics powder B after the relaxation type lead-free piezoelectric ceramic powder A after pre-burning and pre-burning;
3) the ferroelectric lead-free ceramics powder B after the relaxation type lead-free piezoelectric ceramic powder A after pre-burning and pre-burning, be medium difference ball milling 24 hours with ethanol after manual milling, after drying, put into crucible with cover pre-burning 3 hours at 1080-1120 DEG C respectively, obtain relaxation ferroelectric ceramic powder A and the ferroelectric ceramic powder B of pure phase respectively;
4) the relaxation ferroelectric ceramic powder A of pure phase and ferroelectric ceramic powder B in step 3, after milling by hand respectively, according to molar percentage, being mixed by the relaxation type leadless piezoelectric ceramics A of ferroelectric lead-free ceramics B and the 90-50Vol% of 10-50Vol%, is then that medium ball milling was drying to obtain mixed powder C after 24 hours with ethanol;
5) mixed powder C is by dry-pressing formed under 120MPa pressure after PVA granulation, in air atmosphere, sinter 1 hour at 1100-1140 DEG C, and intensification and rate of temperature fall are 8-12 DEG C/min, namely obtain 0-3 type relaxation-ferroelectric compound leadless piezoelectric ceramics;
6) the 0-3 type relaxation described in step 5-ferroelectric compound leadless piezoelectric ceramics, behind surface of polishing, brush silver electrode, gets final product test performance.
Embodiment 1
According to general formula (1-x
1-y
1) Bi
0.5na
0.5tiO
3-x
1bi
0.5k
0.5tiO
3-y
1agNbO
3bismuth-sodium titanate-the bismuth potassium titanate represented-niobic acid silver ternary relaxation type leadless piezoelectric ceramics content is prepared burden, and prepares relaxation type ceramic powder A, according to general formula (1-z) Bi with conventional solid-state method
0.5na
0.5tiO
3-zBaTiO
3bismuth sodium titanate-barium titanate ferro-electricity ceramic powder B is prepared with conventional solid-state method; Work as x1=0.18, when y1=0.02, z=0.06, A is 0.80Bi
0.5na
0.5tiO
3-0.18Bi
0.5k
0.5tiO
3-0.02AgNbO
3, B is 0.94Bi
0.5na
0.5tiO
3-0.06BaTiO
3the B powder of 20% volume ratio is mixed in the A powder of 80% volume ratio, 1120 DEG C of sintering after 1 hour in air atmosphere after ball milling mixing, dry, granulation and dry-pressing slabbing, the relaxation obtained-ferroelectric composite ceramics, surface finish and tested under the choppy sea of 4kV/mm frequency 0.1Hz after silver electrode its one pole strain be 0.25%.The X ray diffracting spectrum of compound leadless piezoelectric ceramics as shown in Figure 1.
Embodiment 2
According to general formula (1-x
1-y
1) Bi
0.5na
0.5tiO
3-x
1bi
0.5k
0.5tiO
3-y
1agNbO
3bismuth-sodium titanate-the bismuth potassium titanate represented-niobic acid silver ternary relaxation type leadless piezoelectric ceramics content is prepared burden, and prepares relaxation type ceramic powder A, according to general formula (1-z) Bi with conventional solid-state method
0.5na
0.5tiO
3-zBaTiO
3bismuth sodium titanate-barium titanate ferro-electricity ceramic powder B is prepared with conventional solid-state method; Work as x1=0.20, when y1=0.03, z=0.06, A is 0.77Bi
0.5na
0.5tiO
3-0.20Bi
0.5k
0.5tiO
3-0.03AgNbO
3, B is 0.94Bi
0.5na
0.5tiO
3-0.06BaTiO
3the B powder of 30% volume ratio is mixed in the A powder of 80% volume ratio, 1130 DEG C of sintering after 1 hour in air atmosphere after ball milling mixing, dry, granulation and dry-pressing slabbing, the relaxation obtained-ferroelectric composite ceramics, surface finish and tested under the choppy sea of 4kV/mm frequency 0.1Hz after silver electrode its one pole strain be 0.30%.
Embodiment 3
According to general formula (1-x
1-y
1) Bi
0.5na
0.5tiO
3-x
1bi
0.5k
0.5tiO
3-y
1agNbO
3bismuth-sodium titanate-the bismuth potassium titanate represented-niobic acid silver ternary relaxation type leadless piezoelectric ceramics content is prepared burden, and prepares relaxation type ceramic powder A, according to general formula (1-z) Bi with conventional solid-state method
0.5na
0.5tiO
3-zBaTiO
3bismuth sodium titanate-barium titanate ferro-electricity ceramic powder B is prepared with conventional solid-state method; Work as x1=0.21, when y1=0.03, z=0.07, A is 0.76Bi
0.5na
0.5tiO
3-0.21Bi
0.5k
0.5tiO
3-0.03AgNbO
3, B is 0.93Bi
0.5na
0.5tiO
3-0.07BaTiO
3the B powder of 30% volume ratio is mixed in the A powder of 70% volume ratio, 1140 DEG C of sintering after 1 hour in air atmosphere after ball milling mixing, dry, granulation and dry-pressing slabbing, the relaxation obtained-ferroelectric composite ceramics, surface finish and tested under the choppy sea of 4kV/mm frequency 0.1Hz after silver electrode its one pole strain be 0.31%.The curve of the dielectric constant with temperature change of compound leadless piezoelectric ceramics as shown in Figure 2.
Embodiment 4
According to general formula (1-x
1-y
1) Bi
0.5na
0.5tiO
3-x
1bi
0.5k
0.5tiO
3-y
1agNbO
3bismuth-sodium titanate-the bismuth potassium titanate represented-niobic acid silver ternary relaxation type leadless piezoelectric ceramics content is prepared burden, and prepares relaxation type ceramic powder A, according to general formula (1-w) Bi with conventional solid-state method
0.5na
0.5tiO
3-wBi
0.5k
0.5tiO
3bismuth-sodium titanate-bismuth potassium titanate ferroelectric ceramic powder B is prepared with conventional solid-state method; Work as x1=0.16, when y1=0.03, w=0.18, A is 0.81Bi
0.5na
0.5tiO
3-0.16Bi
0.5k
0.5tiO
3-0.03AgNbO
3, B is 0.82Bi
0.5na
0.5tiO
3-0.18Bi
0.5k
0.5tiO
3the B powder of 25% volume ratio is mixed in the A powder of 75% volume ratio, 1120 DEG C of sintering after 1 hour in air atmosphere after ball milling mixing, dry, granulation and dry-pressing slabbing, the relaxation obtained-ferroelectric composite ceramics, surface finish and tested under the choppy sea of 4kV/mm frequency 0.1Hz after silver electrode its one pole strain be 0.29%.
Embodiment 5
According to general formula (1-x
1-y
1) Bi
0.5na
0.5tiO
3-x
1bi
0.5k
0.5tiO
3-y
1agNbO
3bismuth-sodium titanate-the bismuth potassium titanate represented-niobic acid silver ternary relaxation type leadless piezoelectric ceramics content is prepared burden, and prepares relaxation type ceramic powder A, according to general formula (1-w) Bi with conventional solid-state method
0.5na
0.5tiO
3-wBi
0.5k
0.5tiO
3bismuth-sodium titanate-bismuth potassium titanate ferroelectric ceramic powder B is prepared with conventional solid-state method; Work as x1=0.17, when y1=0.02, w=0.19, A is 0.81Bi
0.5na
0.5tiO
3-0.17Bi
0.5k
0.5tiO
3-0.02AgNbO
3, B is 0.81Bi
0.5na
0.5tiO
3-0.19Bi
0.5k
0.5tiO
3the B powder of 35% volume ratio is mixed in the A powder of 65% volume ratio, 1130 DEG C of sintering after 1 hour in air atmosphere after ball milling mixing, dry, granulation and dry-pressing slabbing, the relaxation obtained-ferroelectric composite ceramics, surface finish and tested under the choppy sea of 4kV/mm frequency 0.1Hz after silver electrode its one pole strain be 0.28%.Compound leadless piezoelectric ceramics ferroelectric hysteresis loop is at room temperature as Fig. 3.
Embodiment 6
According to general formula (1-x
1-y
1) Bi
0.5na
0.5tiO
3-x
1bi
0.5k
0.5tiO
3-y
1agNbO
3bismuth-sodium titanate-the bismuth potassium titanate represented-niobic acid silver ternary relaxation type leadless piezoelectric ceramics content is prepared burden, and prepares relaxation type ceramic powder A, according to general formula (1-w) Bi with conventional solid-state method
0.5na
0.5tiO
3-wBi
0.5k
0.5tiO
3bismuth-sodium titanate-bismuth potassium titanate ferroelectric ceramic powder B is prepared with conventional solid-state method; Work as x1=0.20, when y1=0.03, w=0.21, A is 0.77Bi
0.5na
0.5tiO
3-0.20Bi
0.5k
0.5tiO
3-0.03AgNbO
3, B is 0.79Bi
0.5na
0.5tiO
3-0.21Bi
0.5k
0.5tiO
3the B powder of 30% volume ratio is mixed in the A powder of 70% volume ratio, 1140 DEG C of sintering after 1 hour in air atmosphere after ball milling mixing, dry, granulation and dry-pressing slabbing, the relaxation obtained-ferroelectric composite ceramics, surface finish and tested under the choppy sea of 4kV/mm frequency 0.1Hz after silver electrode its one pole strain be 0.30%.
Embodiment 7
According to general formula (1-x
2-y
2) Bi
0.5na
0.5tiO
3-x
2baTiO
3-y
2agNbO
3the bismuth sodium titanate-barium titanate represented-niobic acid silver ternary relaxation type leadless piezoelectric ceramics content is prepared burden, and prepares relaxation type ceramic powder A, according to general formula (1-z) Bi with conventional solid-state method
0.5na
0.5tiO
3-zBaTiO
3bismuth sodium titanate-barium titanate ferro-electricity ceramic powder B is prepared with conventional solid-state method; Work as x2=0.06, when y2=0.03, z=0.06, A is 0.91Bi
0.5na
0.5tiO
3-0.06BaTiO
3-0.03AgNbO
3, B is 0.94Bi
0.5na
0.5tiO
3-0.06BaTiO
3the B powder of 30% volume ratio is mixed in the A powder of 70% volume ratio, 1140 DEG C of sintering after 1 hour in air atmosphere after ball milling mixing, dry, granulation and dry-pressing slabbing, the relaxation obtained-ferroelectric composite ceramics, surface finish and tested under the choppy sea of 4kV/mm frequency 0.1Hz after silver electrode its one pole strain be 0.32%.Compound leadless piezoelectric ceramics one pole strain curve at room temperature as shown in Figure 4.
Embodiment 8
According to general formula (1-x
2-y
2) Bi
0.5na
0.5tiO
3-x
2baTiO
3-y
2agNbO
3the bismuth sodium titanate-barium titanate represented-niobic acid silver ternary relaxation type leadless piezoelectric ceramics content is prepared burden, and prepares relaxation type ceramic powder A, according to general formula (1-z) Bi with conventional solid-state method
0.5na
0.5tiO
3-zBaTiO
3bismuth sodium titanate-barium titanate ferro-electricity ceramic powder B is prepared with conventional solid-state method; Work as x2=0.05, when y2=0.03, z=0.07, A is 0.92Bi
0.5na
0.5tiO
3-0.05BaTiO
3-0.03AgNbO
3, B is 0.93Bi
0.5na
0.5tiO
3-0.07BaTiO
3the B powder of 25% volume ratio is mixed in the A powder of 75% volume ratio, 1130 DEG C of sintering after 1 hour in air atmosphere after ball milling mixing, dry, granulation and dry-pressing slabbing, the relaxation obtained-ferroelectric composite ceramics, surface finish and tested under the choppy sea of 4kV/mm frequency 0.1Hz after silver electrode its one pole strain be 0.28%.
Embodiment 9
According to general formula (1-x
2-y
2) Bi
0.5na
0.5tiO
3-x
2baTiO
3-y
2agNbO
3the bismuth sodium titanate-barium titanate represented-niobic acid silver ternary relaxation type leadless piezoelectric ceramics content is prepared burden, and prepares relaxation type ceramic powder A, according to general formula (1-z) Bi with conventional solid-state method
0.5na
0.5tiO
3-zBaTiO
3bismuth sodium titanate-barium titanate ferro-electricity ceramic powder B is prepared with conventional solid-state method; Work as x2=0.07, when y2=0.02, z=0.05, A is 0.91Bi
0.5na
0.5tiO
3-0.07BaTiO
3-0.02AgNbO
3, B is 0.95Bi
0.5na
0.5tiO
3-0.05BaTiO
3the B powder of 20% volume ratio is mixed in the A powder of 80% volume ratio, 1120 DEG C of sintering after 1 hour in air atmosphere after ball milling mixing, dry, granulation and dry-pressing slabbing, the relaxation obtained-ferroelectric composite ceramics, surface finish and tested under the choppy sea of 4kV/mm frequency 0.1Hz after silver electrode its one pole strain be 0.23%.Compound leadless piezoelectric ceramics ferroelectric hysteresis loop at room temperature as shown in Figure 5.
Embodiment 10
According to general formula (1-x
2-y
2) Bi
0.5na
0.5tiO
3-x
2baTiO
3-y
2agNbO
3the bismuth sodium titanate-barium titanate represented-niobic acid silver ternary relaxation type leadless piezoelectric ceramics content is prepared burden, and prepares relaxation type ceramic powder A, according to general formula (1-w) Bi with conventional solid-state method
0.5na
0.5tiO
3-wBi
0.5k
0.5tiO
3bismuth-sodium titanate-bismuth potassium titanate ferroelectric ceramic powder B is prepared with conventional solid-state method; Work as x2=0.06, when y2=0.03, z=0.18, A is 0.91Bi
0.5na
0.5tiO
3-0.06BaTiO
3-0.03AgNbO
3, B is 0.82Bi
0.5na
0.5tiO
3-0.18BaTiO
3the B powder of 30% volume ratio is mixed in the A powder of 70% volume ratio, 1120 DEG C of sintering after 1 hour in air atmosphere after ball milling mixing, dry, granulation and dry-pressing slabbing, the relaxation obtained-ferroelectric composite ceramics, surface finish and tested under the choppy sea of 4kV/mm frequency 0.1Hz after silver electrode its one pole strain be 0.29%.
Embodiment 11
According to general formula (1-x
2-y
2) Bi
0.5na
0.5tiO
3-x
2baTiO
3-y
2agNbO
3the bismuth sodium titanate-barium titanate represented-niobic acid silver ternary relaxation type leadless piezoelectric ceramics content is prepared burden, and prepares relaxation type ceramic powder A, according to general formula (1-w) Bi with conventional solid-state method
0.5na
0.5tiO
3-wBi
0.5k
0.5tiO
3bismuth-sodium titanate-bismuth potassium titanate ferroelectric ceramic powder B is prepared with conventional solid-state method; Work as x2=0.05, when y2=0.02, z=0.20, A is 0.93Bi
0.5na
0.5tiO
3-0.05BaTiO
3-0.02AgNbO
3, B is 0.80Bi
0.5na
0.5tiO
3-0.20BaTiO
3the B powder of 35% volume ratio is mixed in the A powder of 65% volume ratio, 1110 DEG C of sintering after 1 hour in air atmosphere after ball milling mixing, dry, granulation and dry-pressing slabbing, the relaxation obtained-ferroelectric composite ceramics, surface finish and tested under the choppy sea of 4kV/mm frequency 0.1Hz after silver electrode its one pole strain be 0.22%.
Embodiment 12
According to general formula (1-x
2-y
2) Bi
0.5na
0.5tiO
3-x
2baTiO
3-y
2agNbO
3the bismuth sodium titanate-barium titanate represented-niobic acid silver ternary relaxation type leadless piezoelectric ceramics content is prepared burden, and prepares relaxation type ceramic powder A, according to general formula (1-w) Bi with conventional solid-state method
0.5na
0.5tiO
3-wBi
0.5k
0.5tiO
3bismuth-sodium titanate-bismuth potassium titanate ferroelectric ceramic powder B is prepared with conventional solid-state method; Work as x2=0.05, when y2=0.03, z=0.19, A is 0.92Bi
0.5na
0.5tiO
3-0.05BaTiO
3-0.03AgNbO
3, B is 0.81Bi
0.5na
0.5tiO
3-0.19BaTiO
3the B powder of 30% volume ratio is mixed in the A powder of 70% volume ratio, 1140 DEG C of sintering after 1 hour in air atmosphere after ball milling mixing, dry, granulation and dry-pressing slabbing, the relaxation obtained-ferroelectric composite ceramics, surface finish and tested under the choppy sea of 4kV/mm frequency 0.1Hz after silver electrode its one pole strain be 0.28%.Compound leadless piezoelectric ceramics one pole strain curve at room temperature as shown in Figure 6.
Claims (4)
1. large sstrain low driving electric field relaxation-ferroelectric compound leadless piezoelectric ceramics, is characterized in that, be composited by relaxation type leadless piezoelectric ceramics A and ferroelectric lead-free ceramics B, the chemical composition of A and B meets following chemical formula: the composition of A is: (1-x
1-y
1) Bi
0.5na
0.5tiO
3-x
1bi
0.5k
0.5tiO
3-y
1agNbO
3, 0.16≤x
1≤ 0.22,0.01≤y
1≤ 0.03; Or (1-x
2-y
2) Bi
0.5na
0.5tiO
3-x
2baTiO
3-y
2agNbO
3, 0.05≤x
2≤ 0.07,0.01≤y
2≤ 0.03; The composition of B is: (1-z) Bi
0.5na
0.5tiO
3-zBaTiO
3, 0.05≤z≤0.07, or (1-w) Bi
0.5na
0.5tiO
3-wBi
0.5k
0.5tiO
3, 0.16≤w≤0.22.
2. large sstrain according to claim 1 low driving electric field relaxation-ferroelectric compound leadless piezoelectric ceramics, is characterized in that: the volume ratio of the mixing of A and B is 90:10-50:50.
3. large sstrain according to claim 1 and 2 low driving electric field relaxation-ferroelectric compound leadless piezoelectric ceramics, is characterized in that, this piezoelectric ceramics has the electric field induced strain of 0.22%-0.32% under the driving electric field of 4kV/mm.
4. large sstrain low driving electric field relaxation-ferroelectric compound leadless piezoelectric ceramics preparation method as claimed in claim 1 or 2, is characterized in that, carry out according to following steps:
1) BaCO is weighed according to stoichiometric ratio
3, TiO
2, Na
2cO
3, K
2cO
3, Bi
2o
3, Nb
2o
5and Ag
2cO
3after raw material, under ethanol medium, carry out ball milling mixing respectively, after oven dry, obtain the raw material powder of relaxation type lead-free piezoelectric ceramic powder A and ferroelectric lead-free ceramics powder B respectively;
2) in step 1, the raw material powder of A and B is dried, be respectively charged into crucible, put into retort furnace, in air atmosphere with the temperature rise rate of 5 DEG C/min, being warming up to temperature is 800 DEG C of pre-burnings 2 hours, then 850 DEG C of pre-burnings 1 hour, the ferroelectric lead-free ceramics powder B after the relaxation type lead-free piezoelectric ceramic powder A after pre-burning and pre-burning is obtained;
3) the relaxation type lead-free piezoelectric ceramic powder A after pre-burning, the ferroelectric lead-free ceramics powder B after pre-burning, be medium difference ball milling 24 hours with ethanol after manual milling, after drying, put into crucible with cover secondary pre-burning 3 hours at 1080-1120 DEG C respectively, obtain relaxation ferroelectric ceramic powder A and the ferroelectric ceramic powder B of pure phase respectively;
4) the relaxation ferroelectric ceramic powder A of pure phase and ferroelectric ceramic powder B in step 3, after milling by hand respectively, according to molar percentage, being mixed by the relaxation type leadless piezoelectric ceramics A of ferroelectric lead-free ceramics B and the 90-50Vol% of 10-50Vol%, is then that medium ball milling was drying to obtain mixed powder C after 4 hours with ethanol;
5) mixed powder C is by dry-pressing formed under 120MPa pressure after PVA granulation, in air atmosphere, sinter 1 hour at 1100-1140 DEG C, and intensification and rate of temperature fall are 8-12 DEG C/min, namely obtain 0-3 type relaxation-ferroelectric compound leadless piezoelectric ceramics;
6) the 0-3 type relaxation described in step 5-ferroelectric compound leadless piezoelectric ceramics, behind surface of polishing, brush silver electrode, to obtain final product.
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| CN110963797A (en) * | 2019-11-22 | 2020-04-07 | 清华大学 | High-temperature giant electrostrictive ceramic material and preparation method thereof |
| CN110981468A (en) * | 2019-12-31 | 2020-04-10 | 西安理工大学 | Preparation method of sodium bismuth titanate-based piezoelectric ceramic |
| CN112592190A (en) * | 2020-12-10 | 2021-04-02 | 中国科学技术大学 | Piezoelectric ceramic and preparation method thereof |
| CN113321506A (en) * | 2021-07-08 | 2021-08-31 | 陕西科技大学 | Lead-free relaxor ferroelectric ceramic material and preparation method thereof |
| CN113964266A (en) * | 2021-10-13 | 2022-01-21 | 中国科学院光电技术研究所 | Method for preparing high-performance bismuth-based lead-free piezoelectric actuator |
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| CN106129242A (en) * | 2016-06-28 | 2016-11-16 | 武汉华思创新科技有限公司 | A kind of big strain multilamellar leadless piezoelectric actuator and preparation method thereof |
| CN110963797A (en) * | 2019-11-22 | 2020-04-07 | 清华大学 | High-temperature giant electrostrictive ceramic material and preparation method thereof |
| CN110963797B (en) * | 2019-11-22 | 2020-12-01 | 清华大学 | High-temperature giant electrostrictive ceramic material and preparation method thereof |
| CN110981468A (en) * | 2019-12-31 | 2020-04-10 | 西安理工大学 | Preparation method of sodium bismuth titanate-based piezoelectric ceramic |
| CN110981468B (en) * | 2019-12-31 | 2022-03-22 | 西安理工大学 | Preparation method of sodium bismuth titanate-based piezoelectric ceramic |
| CN112592190A (en) * | 2020-12-10 | 2021-04-02 | 中国科学技术大学 | Piezoelectric ceramic and preparation method thereof |
| CN113321506A (en) * | 2021-07-08 | 2021-08-31 | 陕西科技大学 | Lead-free relaxor ferroelectric ceramic material and preparation method thereof |
| CN113964266A (en) * | 2021-10-13 | 2022-01-21 | 中国科学院光电技术研究所 | Method for preparing high-performance bismuth-based lead-free piezoelectric actuator |
| CN113964266B (en) * | 2021-10-13 | 2023-09-19 | 中国科学院光电技术研究所 | Method for preparing high-performance bismuth-based leadless piezoelectric driver |
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