CN101343182B - Doped five-membered low-temperature melt piezoelectric ceramic material and preparation thereof - Google Patents
Doped five-membered low-temperature melt piezoelectric ceramic material and preparation thereof Download PDFInfo
- Publication number
- CN101343182B CN101343182B CN2008101507446A CN200810150744A CN101343182B CN 101343182 B CN101343182 B CN 101343182B CN 2008101507446 A CN2008101507446 A CN 2008101507446A CN 200810150744 A CN200810150744 A CN 200810150744A CN 101343182 B CN101343182 B CN 101343182B
- Authority
- CN
- China
- Prior art keywords
- hours
- sintering
- ball
- alumina crucible
- preparation
- 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.)
- Expired - Fee Related
Links
Images
Abstract
Disclosed is a doped quinary system low-temperature sintered piezoelectric ceramic material, comprising the following materials of a general formula: 0.02Pb(Mg[1/2]W[1/2])O3-yPb(Sb[1/2]Nb[1/2]O3-(0.39-y)Pb(Ni[1/3]Nb[2/3])O3-Pb0.59(Zr0.38Ti0.21)O3+xBa(Cu[1/2]W[1/2])O3, wherein 0.00 wt.% <= x <= 0.40 wt.%, 0.000 < y <= 0.030mol. A preparation method thereof includes the process steps of: preparation of barium tungsten-cuprum, synthesis of ingredients, pre-sintering, granulation, tabletting, glue dumping, sintering, silver sintering and polarization. Results of mass laboratory research experiments show that the prepared low-temperature sintered quinary system piezoelectric ceramic material with high piezoelectric constant and high plane piezoelectric constant has the obviously reduced mechanical quality factor Qm and dielectric loss tan Delta, significantly increased piezoelectric constant d33 and the plane electromechanical coupling factor Kp, and distinctly reduced sintering temperature to 930 DEG C from 1200 DEG C as compared with the properties of the similar ceramic materials reported in literature, and the ceramic material has the advantages of simple preparation process, good repeatability, high rate of finished products and low cost.
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
Piezoelectric be a kind of can be with mechanical energy and the electric energy ceramic material of conversion mutually.It is a kind of material with piezoelectric effect.It can produce electric field because of mechanical deformation, also can produce mechanical deformation because of electric field action, this inherent machine-coupling effect makes that piezoelectric has obtained using widely in engineering, and the piezoelectric of a new generation also has the ability of trained reflex and instruction analysis.This unique function of piezoelectric makes it have more wide application prospect in the intelligent material system.
The PZT piezoelectric ceramics is one of the electronic material of wide range of commercial the most that uses at present.Piezoelectric ceramic devices are as a kind of novel all-in-one solid electronic device, compare with traditional electrical magnetic-type device, have that simple in structure, body is light in a small amount, no iron loss, humidity, noiselessness, be not afraid of advantage such as short circuit, be specially adapted to electron device and develop to direction integrated, sheetization.In recent years, the application development of piezoelectric ceramics on Jacquard comb, loud speaker and bus drive etc. is very rapid, requires piezoelectric to have high electromechanical coupling factor K
p, DIELECTRIC CONSTANT
r, piezoelectric constant d
33And low mechanical quality factor Q
m, dielectric loss tan δ.Piezoceramic multilayer device for widespread use in recent years, because piezoelectric ceramics sintering temperature height (1200～1300 ℃), must be with precious metals such as platinum, palladiums as interior electrode, improved the manufacturing cost of device greatly, if can reduce the sintering temperature of piezoceramic material, then can adopt the Ag-Pd slurry or the pure Ag of the low palladium content that conductivity is good, price is lower to starch as interior electrode, thereby lower the production cost of device greatly, this preparation and application for material has significance.Also avoiding ceramic composition to depart from, reduce energy loss and preventing that high temperature from bringing PbO volatilization and important economic and social benefit is all arranged aspect the contaminate environment.Therefore, exploitation high-performance, high reliability, low sintering temperature, low-cost multilayer piezoelectric ceramic material have become important research direction.
At present, research work mainly concentrates on the piezoceramic material of two component system, three component system and quaternary system, as: PZT, PMN-PZT, PZN-PMS-PZT, PNW-PMN-PZT.But studying five yuan is and obtains high piezoelectric constant d simultaneously
33, high planar electromechanical coupling factor K
p, high-k ε
rWith low mechanical quality factor Q
m, low dielectric loss tan δ, low system is still rare.The applicant has applied for that application number is: 200810150177.4, denomination of invention is: driving mechanism is with containing five one-component system piezoelectric ceramics materials of niobium Naples yellow and preparation method's patent, it has good piezoelectric property, but sintering temperature is than higher (1150 ℃～1200 ℃).Therefore to be intended to find out a kind of suitable additive be Pb (Mg to reduce by five yuan in this work
1/2W
1/2) O
3-Pb (Sb
1/2Nb
1/2) O
3-Pb (Ni
1/3Nb
2/3) O
3Take into account high electrical property in the time of-PZT (PMWSN-PNN-PZT) ceramic sintering temperature.By inquiring into Ba (Cu
1/2W
1/2) O
3Content is to the sintering temperature of PMWSN-PNN-PZT pottery and the influence of electrical property, thereby seek a best component and preparation technology, have high piezoelectric constant, high planar electromechanical coupling factor, high-k and low mechanical quality factor, low dielectric loss and take into account the piezoelectric ceramic actuator material of sintering temperature and low with preparation.
Summary of the invention
A technical problem to be solved by this invention is to provide a kind of high piezoelectric constant, high planar electromechanical coupling factor, low-temperature sintering and temperature range is wide, performance is good, practical, the adulterated five-membered low-temperature melt piezoelectric ceramic material of easy production.
Another technical problem to be solved by this invention is to provide a kind of preparation method of adulterated five-membered low-temperature melt piezoelectric ceramic material.
Solving the problems of the technologies described above the scheme that is adopted is to form with the material that following general formula is represented: 0.02Pb (Mg
1/2W
1/2) O
3-yPb (Sb
1/2Nb
1/2)] O
3-(0.39-y) Pb (Ni
1/3Nb
2/3) O
3-Pb
0.59(Zr
0.38Ti
0.21) O
3+ xBa (Cu
1/2W
1/2) O
3, 0.10wt.%≤x in the formula≤0.40wt.%, 0.000＜y≤0.030mol.
The preparation method of above-mentioned adulterated five-membered low-temperature melt piezoelectric ceramic material comprises that step is as follows:
1, preparation tungsten barium cuprate
With BaCO
3With CuO, WO
3Be mixing in 2: 1: 1 in molar ratio, pack in the nylon jar, adding dehydrated alcohol is that dispersion agent and zirconia ball are ball-milling medium, and the weight ratio of dehydrated alcohol and raw material is 1: 1.5～2.5, uses ball mill ball milling 12 hours, rotating speed is 400 rev/mins, separation of oxygenated zirconium ball is put into loft drier with compound, 80 ℃ of dryings 10 hours, put into mortar again and ground 30 minutes, cross 80 mesh sieves.Material after sieving places in the alumina crucible, and being densified to loose density with the agate rod is 1.2～1.5g/cm
3, add a cover 2～4 hours synthetic Ba (Cu of 680～760 ℃ of pre-burnings in resistance furnace
1/2W
1/2) O
3, naturally cool to room temperature, come out of the stove, the pre-burning powder to be smashed to pieces ground 1 hour, in the nylon jar of packing into, the same technology is carried out the ball milling dry for standby.
2, batching is synthetic
With Ba (Cu
1/2W
1/2) O
3, Pb
3O
4, ZrO
2, TiO
2, Mg (OH)
2MgCO
36H
2O, WO
3, Sb
2O
5, Nb
2O
5, NiO mixes by the stoichiometric ratio of general formula, pack in the nylon jar, adding dehydrated alcohol is that dispersion agent and zirconia ball are ball-milling medium, and the mass ratio of dehydrated alcohol and compound is 1: 2, uses ball mill ball milling 6～12 hours, rotating speed is 400 rev/mins, separation of oxygenated zirconium ball is put into loft drier with compound, 80 ℃ of dryings 5～10 hours, put into mortar again and ground 30 minutes, cross 80 mesh sieves.
3, pre-burning
Material after grinding is placed in the alumina crucible, and being densified to loose density with the agate rod is 1.5g/cm
3, add a cover, 800～850 ℃ of pre-burnings are incubated 2～4 hours in resistance furnace, naturally cool to room temperature, come out of the stove.Smash the pre-burning powder to pieces grinding 1 hour, pack in the nylon jar, adding dehydrated alcohol is that dispersion agent and zirconia ball are ball-milling medium, and the mass ratio of dehydrated alcohol and pre-burning powder is 1: 2, uses ball mill ball milling 6～12 hours, carry out secondary ball milling, rotating speed is 300 rev/mins, and separation of oxygenated zirconium ball is put into loft drier with compound, 80 ℃ of dryings 5～10 hours are crossed 80 mesh sieves.
4, granulation
The burning piece of pre-burning is crossed 160 mesh sieves with the mortar porphyrize, adding glycerol and mass concentration are 5% polyvinyl alcohol solution, pre-burning powder and 5% polyvinyl alcohol solution, the mass ratio of glycerol are 1: 0.068～0.072: 0.0097～0.013, fully stir, seasoning, cross 120 purposes sieve, make spherical powder.
5, compressing tablet
Powder after the granulation is put into the stainless steel mould that diameter is 15mm, depress to the cylindric blank of 1.5mm at 100Mpa pressure.
6, binder removal
Blank is put into resistance furnace, and 500 ℃ of insulations were carried out organism in 1 hour and are got rid of.
7, sintering
The binder removal blank is put into alumina crucible, cover alumina crucible lid and seal, 2～5 ℃/minute of heat-up rates, 880～1000 ℃ of sintering 3～5 hours naturally cool to room temperature with stove.
8, silver ink firing
With the ceramic surface polishing that sinters, it is thick to be polished to 0.8～1.2mm, with power is the Ultrasonic Cleaners of 100w, ultrasonic cleaning that frequency is 50kHz 30 minutes, the interior 80 ℃ of dryings of baking oven 5～10 hours, the lower surface coating thickness is the silver slurry of 0.01～0.03mm thereon, place resistance furnace, 850 ℃ are incubated 30 minutes, naturally cool to room temperature.
9, polarization
Place methyl-silicone oil to be heated to 120～180 ℃ on the sample of burned silver, apply the high direct voltage of 3kV/mm～5kV/mm, continue 15～30 minutes, be prepared into piezoelectric ceramics.
10, test piezoelectric property
The testing plate that polarized leaves standstill under the room temperature after 24 hours and tests piezoelectric property.
In preparation tungsten barium cuprate processing step 1 of the present invention, the BaCO after grinding is sieved
3, CuO, WO
3Compound, 2～3 hours synthetic Ba (Cu of preferred 700～750 ℃ of pre-burnings in resistance furnace
1/2W
1/2) O
3In pre-sinter process step 3, the material after grinding is placed in the alumina crucible, being densified to loose density with the agate rod is 1.5g/cm
3, add a cover, preferred 800～830 ℃ of pre-burnings insulation is 2～3 hours in resistance furnace.In sintering process step 7, the binder removal blank is put into alumina crucible, cover the alumina crucible lid and seal 2～5 ℃/minute of heat-up rates, preferred 900～950 ℃ of sintering 3～4.5 hours.
In preparation tungsten barium cuprate processing step 1 of the present invention, the BaCO after grinding is sieved
3, CuO, WO
3Compound, 3 hours synthetic Ba (Cu of best 730 ℃ of pre-burnings in resistance furnace
1/2W
1/2) O
3In pre-sinter process step 3, the material after grinding is placed in the alumina crucible, being densified to loose density with the agate rod is 1.5g/cm
3, add a cover, best 800 ℃ of pre-burnings insulation is 3 hours in resistance furnace.In sintering process step 7, the binder removal blank is put into alumina crucible, cover the alumina crucible lid and seal, 2～5 ℃/minute of heat-up rates, best 930 ℃ of sintering 4 hours.
The present invention is through a large amount of laboratory study experiments, and the result shows that the performance of prepared high piezoelectric constant, high plane piezoelectric constant, low-temperature sintering five one-component system piezoelectric ceramics materials is compared mechanical quality factor Q with the similar stupalith of bibliographical information
mObviously reduce piezoelectric constant d with dielectric loss tan δ
33With planar electromechanical coupling factor K
pObviously improve, and sintering temperature obviously drops to 930 ℃ from 1200 ℃, preparation technology is simple, good reproducibility, and the yield rate height, cost is low.Piezoelectric ceramics of the present invention can be used for preparing the housing of the built-in vibration transducer of automobile, controller, the dynamic piezoceramic material of devices such as fuel injection nozzle, large power supersonic device, high temperature high-frequency vibration meter, high temperature under meter, high temperature resistant minute hummer and pyrostat.The reduction greatly of piezoceramic material sintering temperature helps multilayer device and uses aborning, and the Ag-Pd slurry of the low palladium content that the employing conductivity is good, price is lower or pure Ag entoplasm have lowered the production cost of device greatly as interior electrode.With the piezoelectric ceramic actuator that this piezoceramic material is made, have the displacement power output greatly, do not generate heat, highly sensitive, good stability, precision advantages of higher.
Description of drawings
Fig. 1 is different B a (Cu
1/2W
1/2) O
3The X ray collection of illustrative plates of 930 ℃ of agglomerating piezoelectric ceramics of doping.
Fig. 2 is 0.10wt.%Ba (Cu
1/2W
1/2) O
3The X ray collection of illustrative plates of doping differing temps agglomerating piezoelectric ceramics.
Fig. 3 is different B a (Cu
1/2W
1/2) O
3The stereoscan photograph of 930 ℃ of agglomerating piezoelectric ceramics of doping.
Fig. 4 is 0.10wt.%Ba (Cu
1/2W
1/2) O
3The stereoscan photograph of doping differing temps agglomerating piezoelectric ceramics.
Fig. 5 is different Pb (Sb
1/2Nb
1/2) O
3The X ray collection of illustrative plates of 930 ℃ of agglomerating piezoelectric ceramics of content.
Fig. 6 is 0.10wt.%Pb (Sb
1/2Nb
1/2) O
3The X ray collection of illustrative plates of content differing temps agglomerating piezoelectric ceramics.
Fig. 7 is different Pb (Sb
1/2Nb
1/2) O
3The stereoscan photograph of 930 ℃ of agglomerating piezoelectric ceramics of content.
Fig. 8 is 0.10wt.%Pb (Sb
1/2Nb
1/2) O
3The stereoscan photograph of content differing temps agglomerating piezoelectric ceramics.
Embodiment
The present invention is further described below in conjunction with drawings and Examples, but the invention is not restricted to these embodiment.
Embodiment 1
Raw materials used 100g is an example with production product of the present invention, and x is 0.10, y is 0.01 o'clock, with general formula 0.02Pb (Mg
1/2W
1/2) O
3-yPb (Sb
1/2Nb
1/2)] O
3-(0.39-y) Pb (Ni
1/3Nb
2/3) O
3-Pb
0.59(Zr
0.38Ti
0.21) O
3+ 0.10wt%Ba (Cu
1/2W
1/2) O
3The raw material and the weight proportion thereof of expression are:
Pb
3O
46 7.14g
ZrO
2 13.76g
TiO
2 4.93g
Mg(OH)
2·MgCO
3·6H
2O 0.3g
WO
3 0.68g
Sb
2O
5 0.22g
Nb
2O
5 10.09g
NiO 2.78g
Ba(Cu
1/2W
1/2)O
3 0.10g
Its preparation method is as follows:
1, preparation tungsten barium cuprate
Earlier with BaCO
3With CuO, WO
3Mixed in 2: 1: 1 in molar ratio, pack in the nylon jar, adding dehydrated alcohol is that dispersion agent and zirconia ball are ball-milling medium, the weight ratio of dehydrated alcohol and raw material is 1: 2, uses ball mill ball milling 12 hours, and rotating speed is 400 rev/mins, separation of oxygenated zirconium ball, compound is put into 80 ℃ in loft drier, oven dry in 10 hours, put into mortar again and ground 30 minutes, cross 80 mesh sieves.Material after sieving is placed in the alumina crucible, and being densified to loose density with the agate rod is 1.2～1.5g/cm
3, add a cover 3 hours synthetic Ba (Cu of 730 ℃ of pre-burning insulations in resistance furnace
1/2W
1/2) O
3, naturally cool to room temperature, come out of the stove.Smash the pre-burning powder to pieces grinding 1 hour, in the nylon jar of packing into, the same technology is carried out the ball milling dry for standby.
2, batching is synthetic
To synthesize Ba (Cu then
1/2W
1/2) O
3And Pb
3O
4, ZrO
2, TiO
2, Mg (OH)
2MgCO
36H
2O, WO
3, Sb
2O
5, Nb
2O
5, NiO mixes by the stoichiometric ratio of general formula, pack in the nylon jar, adding dehydrated alcohol is that dispersion agent and zirconia ball are ball-milling medium, the weight ratio of dehydrated alcohol and raw material is 1: 2, uses ball mill ball milling 6～12 hours, and rotating speed is 400 rev/mins, separation of oxygenated zirconium ball, compound is put into 80 ℃ in loft drier, oven dry in 5～10 hours, put into mortar again and ground 30 minutes, cross 80 mesh sieves.
3, pre-burning
Material after grinding is placed in the alumina crucible,, make its loose density reach 1.5g/cm with the compacting of agate rod
3, add a cover, 800 ℃ of pre-burnings are incubated 3 hours in resistance furnace, naturally cool to room temperature, come out of the stove.Smash the pre-burning powder to pieces grinding 1 hour, pack in the nylon jar, adding dehydrated alcohol is that dispersion agent and zirconia ball are ball-milling medium, and the mass ratio of dehydrated alcohol and pre-burning powder is 1: 2, uses ball mill ball milling 6～12 hours, carry out secondary ball milling, rotating speed is 300 rev/mins, and separation of oxygenated zirconium ball is put into loft drier with compound, 80 ℃ of dryings 5～10 hours are crossed 80 mesh sieves.
4, granulation
The burning piece of pre-burning is crossed 160 mesh sieves with the mortar porphyrize, the adding weight concentration is 5% polyvinyl alcohol solution 7g and glycerol solution 0.1g, raw material and 5% polyvinyl alcohol solution, the weight ratio of glycerol are 1: 0.7: 0.01, fully stir, seasoning, cross 120 purposes sieve, make spherical powder.
5, compressing tablet
Powder after the granulation is put into the stainless steel mould that diameter is 15mm, depress to the cylindric blank of 1.5mm at 100Mpa pressure.
6, binder removal
Blank is put into resistance furnace, and 500 ℃ of insulations were carried out organism in 1 hour and are got rid of.
7, sintering
The binder removal blank is put into alumina crucible, cover alumina crucible lid and seal, 4 ℃/minute of heat-up rates 930 ℃ of sintering 4 hours, naturally cool to room temperature with stove.
8, silver ink firing
With the ceramic surface polishing that sinters, it is thick to be polished to 0.8～1.2mm, with power is the Ultrasonic Cleaners of 100w, ultrasonic cleaning that frequency is 50kHz 30 minutes, the interior 80 ℃ of dryings of baking oven 5～10 hours, the lower surface coating thickness is the silver slurry of 0.01～0.03mm thereon, place 850 ℃ of insulations of resistance furnace 30 minutes, naturally cool to room temperature.
9, polarization
Place methyl-silicone oil to be heated to 150 ℃ on the sample of burned silver, apply the high direct voltage of 3.5kV/mm, continue 25 minutes, be prepared into piezoelectric ceramics.
10, test piezoelectric property
Leave standstill under the room temperature after 24 hours and test piezoelectric property.
Embodiment 2
Raw materials used 100g is an example with production product of the present invention, and x is 0.0, y is 0.01, with general formula 0.02Pb (Mg
1/2W
1/2) O
3-0.01Pb (Sb
1/2Nb
1/2)] O
3-0.38Pb (Ni
1/3Nb
2/3) O
3-Pb
0.59(Zr
0.38Ti
0.21) O
3, the raw material of expression and weight proportion thereof are:
Pb
3O
4 67.22g
ZrO
2 13.77g
TiO
2 4.93g
Mg(OH)
2·MgCO
3·6H
2O 0.3g
WO
3 0.68g
Sb
2O
5 0.22g
Nb
2O
5 10.10g
NiO 2.78g
Ba(Cu
1/2W
1/2)O
3 0g
Its preparation method is as follows:
In preparation tungsten barium cuprate processing step 1, with BaCO
3With CuO, WO
3Be mixing in 2: 1: 1 in molar ratio, in the nylon jar of packing into, adding dehydrated alcohol is that dispersion agent and zirconia ball are ball-milling medium, the weight ratio of dehydrated alcohol and raw material is 1: 1.5, uses the ball mill ball milling, oven dry, grind again, sieve, 4 hours synthetic Ba (Cu of 680 ℃ of pre-burning insulations in resistance furnace
1/2W
1/2) O
3, other step of processing step is identical with embodiment 1.In batching synthesis technique step 2, raw material is pressed the general formula batching, add dehydrated alcohol 50g, zirconia ball is a ball-milling medium, other step of this processing step is identical with embodiment 1.In pre-sinter process step 3, the material after grinding is placed in the alumina crucible, with the compacting of agate rod, make its loose density reach 1.5g/cm
3, add a cover, 800 ℃ of pre-burnings are incubated 4 hours in resistance furnace, naturally cool to room temperature, come out of the stove, and other step of this processing step is identical with embodiment 1.In granulation process step 4, the burning piece of pre-burning is crossed 160 mesh sieves with the mortar porphyrize, the adding weight concentration is 5% polyvinyl alcohol solution 6.8g and glycerol solution 0.97g, raw material and 5% polyvinyl alcohol solution, the weight ratio of glycerol are 1: 0.068: 0.0097, fully stir, 120 purposes sieve is crossed in seasoning, makes spherical powder.In sintering process step 7, the binder removal blank is put into alumina crucible, cover alumina crucible lid and seal, 2 ℃/minute of heat-up rates 880 ℃ of sintering 5 hours, naturally cool to room temperature with stove.In polarization process step 9, place methyl-silicone oil to be heated to 120 ℃ on the sample of burned silver, apply the high direct voltage of 5kV/mm, continue 15 minutes, be prepared into piezoelectric ceramics.Other processing step is identical with embodiment 1.
Embodiment 3
Raw materials used 100g is an example with production product of the present invention, and x is 0.40, y is 0.03 o'clock, with general formula 0.02Pb (Mg
1/2W
1/2) O
3-0.03Pb (Sb
1/2Nb
1/2)] O
3-0.36Pb (Ni
1/3Nb
2/3) O
3-Pb
0.59(Zr
0.38Ti
0.21) O
3+ 0.40wt%Ba (Cu
1/2W
1/2) O
3The raw material and the weight proportion thereof of expression are:
Pb
3O
4 66.84g
ZrO
2 13.69g
TiO
2 4.91g
Mg(OH)
2·MgCO
3·6H
2O 0.3g
WO
3 0.68g
Sb
2O
5 0.64g
Nb
2O
5 9.91g
NiO 2.63g
Ba(Cu
1/2W
1/2)O
3 0.4g
Its preparation method is as follows:
In preparation tungsten barium cuprate processing step 1, with BaCO
3With CuO, WO
3Be mixing in 2: 1: 1 in molar ratio, in the nylon jar of packing into, adding dehydrated alcohol is that dispersion agent and zirconia ball are ball-milling medium, the weight ratio of dehydrated alcohol and raw material is 1: 2.5, uses the ball mill ball milling, oven dry, grind again, sieve 2 hours synthetic Ba (Cu of 760 ℃ of pre-burnings in resistance furnace
1/2W
1/2) O
3, other step of processing step is identical with embodiment 1.In batching synthesis technique step 2, raw material is packed in the nylon jar, adding dehydrated alcohol 50g is dispersion agent, is ball-milling medium, other step of this processing step is identical with embodiment 1.In pre-sinter process step 3, the material after grinding is placed in the alumina crucible, with the compacting of agate rod, make its loose density reach 1.5g/cm
3, add a cover, 850 ℃ of pre-burnings are incubated 2 hours in resistance furnace, naturally cool to room temperature, come out of the stove, and other step of this processing step is identical with embodiment 1.In granulation process step 4, the burning piece of pre-burning is crossed 160 mesh sieves with the mortar porphyrize, the adding weight concentration is 5% polyvinyl alcohol solution 7.2g and glycerol solution 1.3g, raw material and 5% polyvinyl alcohol solution, the weight ratio of glycerol are 1: 0.072: 0.013, fully stir, 120 purposes sieve is crossed in seasoning, makes spherical powder.In sintering process step 7, the binder removal blank is put into alumina crucible, cover alumina crucible lid and seal, 5 ℃/minute of heat-up rates 1000 ℃ of sintering 3 hours, naturally cool to room temperature with stove.In polarization process step 8, place methyl-silicone oil to be heated to 180 ℃ on the sample of burned silver, apply the high direct voltage of 3kV/mm, continue 30 minutes, be prepared into piezoelectric ceramics.Other processing step is identical with embodiment 1.
Embodiment 4
Raw materials used 100g is an example with production product of the present invention, and x is 0.10, y is 0.006 o'clock, with general formula 0.02Pb (Mg
1/2W
1/2) O
3-0.006Pb (Sb
1/2Nb
1/2)] O
3-0.384Pb (Ni
1/3Nb
2/3) O
3-Pb
0.59(Zr
0.38Ti
0.21) O
3+ 0.1wt%Ba (Cu
1/2W
1/2) O
3The raw material and the weight proportion thereof of expression are:
Pb
3O
4 67.17g
ZrO
2 13.75g
TiO
2 4.93g
Mg(OH)
2·MgCO
3·6H
2O 0.30g
WO
3 0.68g
Sb
2O
5 0.13g
Nb
2O
5 10.13g
NiO 2.81g
Ba(Cu
1/2W
1/2)O
3 0.10g
Its preparation method is identical with embodiment 1.
In order to determine best proportioning of the present invention and optimised process step, the contriver has carried out a large amount of laboratory study experiments, and various experiment situations are as follows:
Testing tool: accurate LCR bridge test instrument, model is HP4294A, is produced by Anjelen Sci. ﹠ Tech. Inc; Quasistatic d
33Tester is produced by Acoustical Inst., Chinese Academy of Sciences; Accurate electric impedance analyzer, model is HP4294A, is produced by Anjelen Sci. ﹠ Tech. Inc; X-ray diffractometer, model are D/max-2200, are produced by Japan company of science; The scanning electron microscope model is Quanta 200, is produced by Dutch Philips FEI Co..
1.Ba (Cu
1/2W
1/2) O
3Content is to the ceramic electrical Effect on Performance
Earlier with BaCO
3, CuO, WO
3Mixed in 2: 1: 1 in molar ratio, pack in the nylon jar, adding dehydrated alcohol is that dispersion agent and zirconia ball are ball-milling medium, the weight ratio of dehydrated alcohol and raw material is 1: 2, uses ball mill ball milling 12 hours, and rotating speed is 400 rev/mins, separation of oxygenated zirconium ball, compound is put into 80 ℃ in loft drier, oven dry in 10 hours, put into mortar again and ground 30 minutes, cross 80 mesh sieves.Material after sieving is placed in the alumina crucible, and being densified to loose density with the agate rod is 1.2～1.5g/cm
3, add a cover 3 hours synthetic Ba (Cu of 730 ℃ of pre-burning insulations in resistance furnace
1/2W
1/2) O
3, naturally cool to room temperature, come out of the stove.Smash the pre-burning powder to pieces grinding 1 hour, in the nylon jar of packing into, the same technology is carried out the ball milling dry for standby.
Ba (Cu with the adulterated five-membered low-temperature melt piezoelectric ceramic of preparation
1/2W
1/2) O
3And other raw material places in the loft drier, 120 ℃ of dryings 5 hours, presses general formula 0.02Pb (Mg
1/2W
1/2) O
3-0.01Pb (Sb
1/2Nb
1/2) O
3-0.38Pb (Ni
1/3Nb
2/3) O
3-Pb
0.59(Zr
0.38Ti
0.21) O
3+ xBa (Cu
1/2W
1/2) O
3Prepare burden, y is 0.010 in the formula, and x is respectively 0.00wt.%, 0.025wt.%, 0.05wt.%, 0.075wt.%, 0.10wt.%, 0.15wt.%, 0.20wt.%, 0.30wt.%, 0.40wt.%, wet ball grinding 12 hours, discharging, wet feed oven dry back was 800 ℃ of following pre-burnings 2 hours.Powder after the pre-burning carried out secondary ball milling 30 minutes under the same conditions; discharging; 80 ℃ of dryings 8 hours; crossed 120 mesh sieves in 20 minutes with the mortar mill; the adding weight concentration is 5% polyvinyl alcohol solution 7g and glycerol solution 0.1g; raw material and 5% polyvinyl alcohol solution; the weight ratio of glycerol is 1: 0.7: 0.01; it is 15+0.05mm that material after the granulation is pressed into diameter with mould; thickness is the disk of 1.5 ± 0.02mm; make type in the axial compression that places an order of 100Mpa pressure; binder removal was carried out in 500 ℃ of insulations in 1 hour; 1.5 ℃/minute of heat-up rates, 880～1000 ℃ of sintering are 4 hours in the lead protection atmosphere, naturally cool to room temperature with stove.Agglomerating ceramic disks sanding and polishing to diameter is that 13.5mm, thickness are 1.2mm, with power is the ultrasonication 30 minutes of 50Hz for the 100W frequency, 80 ℃ of dryings 5～10 hours, at coated on both sides silver slurry, 850 ℃ of burning infiltration silver electrodes 30 minutes, the sample that burnt electrode place 150 ℃ silicone oil with the high direct voltage electropolarization 30min of 4kV/mm, obtain piezoelectric ceramics, room temperature left standstill 24 hours, the test piezoelectric property.The capacitor C and the dielectric loss tan δ of the sample of electrode burnt in test.
Calculate specific inductivity by following formula:
ε
r＝4Ct/(πε
0d
2) (1)
T is the thickness of ceramic plate in the formula, ε
0Be permittivity of vacuum (8.85 * 10
-12F/m), d is the diameter of ceramic plate.
Piezoelectric constant d with quasi static test instrument test piezoelectric ceramics
33
Adopt Archimedes's method to measure the density p (g/cm of pottery
3).Concrete grammar is: sample is cleaned up, put into thermostatic drying chamber, the oven dry back is taken out and is weighed up sample quality A (unit is g) in air with plum Teller-Tuo benefit electronic balance, then sample is put into water and boiled 40 minutes, soak again and weigh up the quality B (unit be g) of sample in distilled water after 5～10 minutes.Be calculated as follows its volume density:
A is solid to be measured quality in air in the formula, and B is solid to be measured quality in auxiliary liq water, ρ
0Be auxiliary liq density, ρ
LBe density of air (0.0012g/cm
3)
With accurate electric impedance analyzer test, obtain resonant frequency and anti-resonance frequency, calculate planar electromechanical coupling factor K by (3) formula
p:
F in the formula
rBe resonant frequency, f
a, be anti-resonance frequency, by (4) formula calculating machine quality factor Q
m:
Q
m＝f
a 2[2πrC
Tf
r(f
a 2-f
r 2)]
-1(4)
F in the formula
rBe resonant frequency, f
a, being anti-resonance frequency, r is a resonant resistance, C
TDirect capacitance amount for sample under the 1kHz.Test and calculation result see Table 1.
Table 1y is Ba (Cu under 4 hours different sintering temperatures of 0.010mol sintering
1/2W
1/2) O
3Content is to the influence of piezoelectric ceramics electrical property
By table 1 as seen, in 880～1000 ℃ of sintering ranges, when x was 0.00～0.40wt.%, every performance index of piezoelectric ceramics were all better, wherein when x is 0.10wt.%, and piezoelectric constant d
33All greater than 390pC/N, in every performance the best of 930 ℃ of agglomerating piezoelectric ceramics.
Y is 0.010mol, Ba (Cu
1/2W
1/2) O
3Content is that the X ray collection of illustrative plates of 0.00～0.40wt.%, 4 hours prepared piezoelectric ceramics of 930 ℃ of sintering is seen Fig. 1.As seen from Figure 1, all components is the pure perovskite phase structure all, does not have the Jiao Lvshi phase and second appearance of dephasign mutually of degrade performance.And, along with Ba (Cu
1/2W
1/2) O
3The increase of content is 43 °～47 ° unimodal (200) located by 2 θ
RSplit into division peak (002) gradually
T(200)
T, illustrate that this material system is transformed into tetragonal phase structure mutually by water chestnut side.
Y is 0.010mol, Ba (Cu
1/2W
1/2) O
3Content is that the X ray collection of illustrative plates of the prepared piezoelectric ceramics of 0.10wt.%, different sintering temperature is seen Fig. 2.As seen from Figure 2, all components all are the pure perovskite phase structure, and 880 ℃ burnt green stone phase occurs, and along with the increase of temperature, Jiao Lvshi disappears mutually and do not have the appearance of the second phase dephasign.Along with the increase of sintering temperature, be 43 °～47 ° unimodal (200) located by 2 θ
RAs can be seen, this material system is water chestnut side's phase structure.
Y is 0.01mol, Ba (Cu
1/2W
1/2) O
3Content is that the electronic scanning electromicroscopic photograph on 0.00～0.40wt.%, 4 hours prepared piezoelectric ceramics surfaces of 930 ℃ of sintering is seen Fig. 3.In Fig. 3, a is 0.00wt.%Ba (Cu
1/2W
1/2) O
3The electronic scanning electromicroscopic photograph on doped sintered 930 ℃ piezoelectric ceramics surface, b are 0.025wt.%Ba (Cu
1/2W
1/2) O
3The electronic scanning electromicroscopic photograph on doped sintered 930 ℃ piezoelectric ceramics surface, c are 0.075wt.%Ba (Cu
1/2W
1/2) O
3The electronic scanning electromicroscopic photograph on doped sintered 930 ℃ piezoelectric ceramics surface, d are 0.10wt.%Ba (Cu
1/2W
1/2) O
3The electronic scanning electromicroscopic photograph on doped sintered 930 ℃ piezoelectric ceramics surface, e are 0.20wt.%Ba (Cu
1/2W
1/2) O
3The electronic scanning electromicroscopic photograph on doped sintered 930 ℃ piezoelectric ceramics surface, f are 0.40wt.%Ba (Cu
1/2W
1/2) O
3The electronic scanning electromicroscopic photograph on doped sintered 930 ℃ piezoelectric ceramics surface.As seen from Figure 3, in system, contain a small amount of Ba (Cu
1/2W
1/2) O
3The time, piezoelectric ceramics is not fine and close, and crystal grain is inhomogeneous, and the more crystal boundary of pore is fuzzy; Along with Ba (Cu
1/2W
1/2) O
3The increase of content, the crystal boundary of system is clear, full grains, grain growth and growth are evenly; Ba (Cu
1/2W
1/2) O
3Content is many more, and ceramic pore is many more, and grain size differs.
Y is 0.010mol, Ba (Cu
1/2W
1/2) O
3Content is that the electronic scanning electromicroscopic photograph on the prepared piezoelectric ceramics surface of 0.10wt.%, different sintering temperature is seen Fig. 4.In Fig. 4, a is 0.10wt.%Ba (Cu
1/2W
1/2) O
3The mix electronic scanning electromicroscopic photograph on 880 ℃ of agglomerating piezoelectric ceramics surfaces, b is 0.10wt.%Ba (Cu
1/2W
1/2) O
3The electronic scanning electromicroscopic photograph on doped sintered 900 ℃ piezoelectric ceramics surface, c are 0.10wt.%Ba (Cu
1/2W
1/2) O
3The electronic scanning electromicroscopic photograph on doped sintered 930 ℃ piezoelectric ceramics surface, d are 0.10wt.%Ba (Cu
1/2W
1/2) O
3The electronic scanning electromicroscopic photograph on doped sintered 950 ℃ piezoelectric ceramics surface, e are 0.10wt.%Ba (Cu
1/2W
1/2) O
3The electronic scanning electromicroscopic photograph on doped sintered 1000 ℃ piezoelectric ceramics surface.As can be seen from Figure 4, when sintering temperature was low, pottery was not fine and close, and crystal grain is inhomogeneous, and pore is more; Along with the increase of sintering temperature, the crystal boundary of system is clear, full grains, and grain growing is even; And along with the increase of sintering temperature, the piezoelectric ceramics pore increases, and the grain size growth is inhomogeneous.
2.Pb (Sb
1/2Nb
1/2) O
3Content is to the influence of piezoelectric ceramics electrical property
Ba (Cu with the adulterated five-membered low-temperature melt piezoelectric ceramic of preparation
1/2W
1/2) O
3And other raw material places in the loft drier, and 120 ℃ of dryings 5 hours are pressed general formula 0.02Pb (Mg
1/2W
1/2) O
3-yPb (Sb
1/2Nb
1/2) O
3-(0.39-y) Pb (Ni
1/3Nb
2/3) O
3-Pb
0.59(Zr
0.38Ti
0.21) O
3+ 0.10wt.%Ba (Cu
1/2W
1/2) O
3Prepare burden, experimentation is identical with 1,4 hours sintered heat insulating time, the sample that burnt electrode is carried out electric capacity and dielectric loss tan δ test.Measure the piezoelectric constant d of piezoelectric ceramics finished product with the quasi static test instrument
33, calculate DIELECTRIC CONSTANT by (1) formula
r, (2) formula bulk density, (3) calculate planar electromechanical coupling factor K
p, (4) formula calculating machine quality factor Q
mTest and calculation result see Table 2.
Different Pb (the Sb of the different sintering temperatures of table 2
1/2Nb
1/2) O
3The electrical property that contains piezoelectric ceramics
Table 2 as seen, in 880～1000 ℃ of sintering ranges, every performance index of piezoelectric ceramics are all better, wherein at Pb (Sb
1/2Nb
1/2) O
3Content is every performance the best of 0.010mol, 930 ℃ of agglomerating piezoelectric ceramics.
X is 0.10wt.%, Pb (Sb
1/2Nb
1/2) O
3Content is 0.000～0.030mol, and the X ray collection of illustrative plates of 4 hours piezoelectric ceramics of 930 ℃ of sintering is seen Fig. 5.As can be seen from Figure 5, all components all are the pure perovskite phase structure, as Pb (Sb
1/2Nb
1/2) O
3Content is during from 0.000mol to 0.010mol, and the Jiao Lvshi that does not have a degrade performance mutually and second appearance of dephasign mutually.By 2 θ is 43 °～47 ° unimodal (002) located
RCan illustrate that this system is water chestnut side's phase.
X is 0.10wt.%, Pb (Sb
1/2Nb
1/2) O
3Content is 0.010mol, and the X ray collection of illustrative plates of the piezoelectric ceramics of different sintering temperature preparations is seen Fig. 6.As can be seen from Figure 6, all components all is the pure perovskite phase structure, when sintering temperature is 880～1000 ℃, does not have the Jiao Lvshi phase and second appearance of dephasign mutually of degrade performance.By 2 θ is 43 °～47 ° unimodal (002) located
RIllustrate that this system is water chestnut side's phase.
X is 0.10wt.%, Pb (Sb
1/2Nb
1/2) O
3Content is 0.000～0.030mol, 4 hours different Pb (Sb of 930 ℃ of sintering
1/2Nb
1/2) O
3The electronic scanning electromicroscopic photograph on content piezoelectric ceramics surface is seen Fig. 7.In Fig. 7, a is 0.000mol Pb (Sb
1/2Nb
1/2) O
3The electronic scanning electromicroscopic photograph on the piezoelectric ceramics surface that the content sintering is 930 ℃, b are 0.006mol Pb (Sb
1/2Nb
1/2) O
3The electronic scanning electromicroscopic photograph on the piezoelectric ceramics surface that the content sintering is 930 ℃, c are 0.010mol Pb (Sb
1/2Nb
1/2) O
3The electronic scanning electromicroscopic photograph on the piezoelectric ceramics surface that the content sintering is 930 ℃, d are 0.015mol Pb (Sb
1/2Nb
1/2) O
3The electronic scanning electromicroscopic photograph on the piezoelectric ceramics surface that the content sintering is 930 ℃, e are 0.030mol Pb (Sb
1/2Nb
1/2) O
3The electronic scanning electromicroscopic photograph on the piezoelectric ceramics surface that the content sintering is 930 ℃.As can be seen from Figure 7, Pb (Sb
1/2Nb
1/2) O
3When content was 0.006～0.010mol, grain-size was about 3.2～4.4 μ m, and crystal grain is more even, and crystal boundary is clear, and compactness is good.
X is 0.10wt.%, Pb (Sb
1/2Nb
1/2) O
3Content is 0.010mol, and the electronic scanning electromicroscopic photograph of differing temps sintered piezoelectric ceramics table is seen Fig. 8.In Fig. 8, a is 0.010mol Pb (Sb
1/2Nb
1/2) O
3The electronic scanning electromicroscopic photograph on the piezoelectric ceramics surface that the content sintering is 880 ℃, b are 0.010mol Pb (Sb
1/2Nb
1/2) O
3The electronic scanning electromicroscopic photograph on the piezoelectric ceramics surface that the content sintering is 900 ℃, c are 0.010mol Pb (Sb
1/2Nb
1/2) O
3The electronic scanning electromicroscopic photograph on the piezoelectric ceramics surface that the content sintering is 930 ℃, d are 0.010mol Pb (Sb
1/2Nb
1/2) O
3The electronic scanning electromicroscopic photograph on the piezoelectric ceramics surface that the content sintering is 950 ℃, e are 0.010mol Pb (Sb
1/2Nb
1/2) O
3The electronic scanning electromicroscopic photograph on the piezoelectric ceramics surface that the content sintering is 1000 ℃.As can be seen from Figure 8, when sintering temperature is 900～950 ℃, compare evenly, grain-size is about 3.2～4.4 μ m, and crystal grain is more even, and crystal boundary is clear, and compactness is good.Along with the increase of temperature, the grain growing size of pottery is inhomogeneous.
Claims (4)
1. an adulterated five-membered low-temperature melt piezoelectric ceramic material is characterized in that: with following general formula 0.02Pb (Mg
1/2W
1/2) O
3-yPb (Sb
1/2Nb
1/2)]
3-(0.39-y) Pb (Ni
1/3Nb
2/3) O
3-Pb
0.59(Zr
0.38Ti
0.21) O
3+ xBa (Cu
1/2W
1/2) O
3The material of expression is formed, 0.10wt.%≤x in the formula≤0.40wt.%, 0.000＜y≤0.030mol.
2. the preparation method of the adulterated five-membered low-temperature melt piezoelectric ceramic material of claim 1 is characterized in that this method comprises the steps:
(1) preparation tungsten barium cuprate
With BaCO
3With CuO, WO
3Be mixing in 2: 1: 1 in molar ratio, pack in the nylon jar, adding dehydrated alcohol is that dispersion agent and zirconia ball are ball-milling medium, and the weight ratio of dehydrated alcohol and raw material is 1: 1.5～2.5, uses ball mill ball milling 12 hours, rotating speed is 400 rev/mins, separation of oxygenated zirconium ball is put into loft drier with compound, 80 ℃ of dryings 10 hours, put into mortar again and ground 30 minutes, cross 80 mesh sieves; Material after sieving places in the alumina crucible, and being densified to loose density with the agate rod is 1.2～1.5g/cm
3, add a cover 2～4 hours synthetic Ba (Cu of 680～760 ℃ of pre-burnings in resistance furnace
1/2W
1/2) O
3, naturally cool to room temperature, come out of the stove, the pre-burning powder to be smashed to pieces ground 1 hour, in the nylon jar of packing into, the same technology is carried out the ball milling dry for standby;
(2) batching is synthetic
With Ba (Cu
1/2W
1/2) O
3, Pb
3O
4, ZrO
2, TiO
2, Mg (OH)
2MgCO
36H
2O, WO
3, Sb
2O
5, Nb
2O
5, NiO mixes by the stoichiometric ratio of general formula, pack in the nylon jar, adding dehydrated alcohol is that dispersion agent and zirconia ball are ball-milling medium, and the mass ratio of dehydrated alcohol and compound is 1: 2, uses ball mill ball milling 6～12 hours, rotating speed is 400 rev/mins, separation of oxygenated zirconium ball is put into loft drier with compound, 80 ℃ of dryings 5～10 hours, put into mortar again and ground 30 minutes, cross 80 mesh sieves;
(3) pre-burning
Material after grinding is placed in the alumina crucible, and being densified to loose density with the agate rod is 1.5g/cm
3, add a cover, 800～850 ℃ of pre-burnings are incubated 2～4 hours in resistance furnace, naturally cool to room temperature, come out of the stove; Smash the pre-burning powder to pieces grinding 1 hour, pack in the nylon jar, adding dehydrated alcohol is that dispersion agent and zirconia ball are ball-milling medium, and the mass ratio of dehydrated alcohol and pre-burning powder is 1: 2, uses ball mill ball milling 6～12 hours, carry out secondary ball milling, rotating speed is 300 rev/mins, and separation of oxygenated zirconium ball is put into loft drier with compound, 80 ℃ of dryings 5～10 hours are crossed 80 mesh sieves;
(4) granulation
The burning piece of pre-burning is crossed 160 mesh sieves with the mortar porphyrize, adding glycerol and mass concentration are 5% polyvinyl alcohol solution, pre-burning powder and 5% polyvinyl alcohol solution, the mass ratio of glycerol are 1: 0.068～0.072: 0.0097～0.013, fully stir, seasoning, cross 120 purposes sieve, make spherical powder;
(5) compressing tablet
Powder after the granulation is put into the stainless steel mould that diameter is 15mm, depress to the cylindric blank of 1.5mm at 100Mpa pressure;
(6) binder removal
Blank is put into resistance furnace, and 500 ℃ of insulations were carried out organism in 1 hour and are got rid of;
(7) sintering
The binder removal blank is put into alumina crucible, cover alumina crucible lid and seal, 2～5 ℃/minute of heat-up rates, 8801000 ℃ of sintering 3～5 hours naturally cool to room temperature with stove;
(8) silver ink firing
With the ceramic surface polishing that sinters, it is thick to be polished to 0.8～1.2mm, with power is the Ultrasonic Cleaners of 100w, ultrasonic cleaning that frequency is 50kHz 30 minutes, the interior 80 ℃ of dryings of baking oven 5～10 hours, the lower surface coating thickness is the silver slurry of 0.01～0.03mm thereon, place resistance furnace, 850 ℃ are incubated 30 minutes, naturally cool to room temperature;
(9) polarization
Place methyl-silicone oil to be heated to 120～180 ℃ on the sample of burned silver, apply the high direct voltage of 3kV/mm～5kV/mm, continue 15～30 minutes, be prepared into piezoelectric ceramics.
3. according to the preparation method of the described adulterated five-membered low-temperature melt piezoelectric ceramic material of claim 2, it is characterized in that: in preparation tungsten barium cuprate processing step (1), the BaCO after grinding is sieved
3, CuO, WO
3Compound, 2～3 hours synthetic Ba (Cu of 700～750 ℃ of pre-burnings in resistance furnace
1/2W
1/2) O
3In pre-sinter process step (3), the material after grinding is placed in the alumina crucible, being densified to loose density with the agate rod is 1.5g/cm
3, add a cover, 800～830 ℃ of pre-burnings are incubated 2～3 hours in resistance furnace; In sintering process step (7), the binder removal blank is put into alumina crucible, cover that alumina crucible is smoked to be sealed, 2～5 ℃/minute of heat-up rates, 900～950 ℃ of sintering 3～4.5 hours.
4. according to the preparation method of the described adulterated five-membered low-temperature melt piezoelectric ceramic material of claim 2, it is characterized in that: in preparation tungsten barium cuprate processing step (1), the BaCO after grinding is sieved
3, CuO, WO
3Compound, 3 hours synthetic Ba (Cu of 730 ℃ of pre-burnings in resistance furnace
1/2W
1/2) O
3In pre-sinter process step (3), the material after grinding is placed in the alumina crucible, being densified to loose density with the agate rod is 1.5g/cm
3, add a cover, 800 ℃ of pre-burnings are incubated 3 hours in resistance furnace; In sintering process step (7), the binder removal blank is put into alumina crucible, cover alumina crucible lid and seal, 2～5 ℃/minute of heat-up rates, 930 ℃ of sintering 4 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101507446A CN101343182B (en) | 2008-08-28 | 2008-08-28 | Doped five-membered low-temperature melt piezoelectric ceramic material and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101507446A CN101343182B (en) | 2008-08-28 | 2008-08-28 | Doped five-membered low-temperature melt piezoelectric ceramic material and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101343182A CN101343182A (en) | 2009-01-14 |
| CN101343182B true CN101343182B (en) | 2011-05-04 |
Family
ID=40245320
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101507446A Expired - Fee Related CN101343182B (en) | 2008-08-28 | 2008-08-28 | Doped five-membered low-temperature melt piezoelectric ceramic material and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101343182B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731091A (en) * | 2011-03-30 | 2012-10-17 | 中国科学院上海硅酸盐研究所 | Piezoceramic material and its preparation method |
| CN102718482B (en) * | 2012-05-24 | 2013-09-25 | 成都汇通西电电子有限公司 | Piezoceramic material and preparation method thereof, and piezoelectric generating oscillator |
| CN102826845A (en) * | 2012-08-29 | 2012-12-19 | 苏州金桨节能与环保科技有限公司 | Preparation method of electric shock/piezoelectric material and application of electric-shock/piezoelectric material |
| CN103214240B (en) * | 2013-03-20 | 2014-12-17 | 瑞声精密制造科技(常州)有限公司 | Piezoceramic material, sintered body, preparation method thereof, and piezoceramic device |
| CN106588008B (en) * | 2016-12-07 | 2019-07-23 | 西安理工大学 | The barium tungsten-cuprum ceramic material and preparation method thereof for having giant dielectric performance |
| CN107337452B (en) * | 2017-07-14 | 2019-10-25 | 陕西师范大学 | The Sm of high transparency and luminous thermal stability3+Adulterate luminous ferroelectric ceramic material of tungsten bronze and preparation method thereof |
| CN107935591B (en) * | 2017-12-01 | 2021-03-23 | 广东工业大学 | Modified lead zirconate titanate powder, preparation method thereof and piezoelectric ceramic molding blank |
| CN109837442B (en) * | 2019-03-28 | 2020-09-25 | 北京工业大学 | Preparation method of nanocrystalline tungsten-copper-based composite material co-doped with metal element Ti/Cr and hard phase WC in situ |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803708A (en) * | 2006-01-19 | 2006-07-19 | 湖北大学 | Low temperature sintered PMMSN titanic acid piezoelectric ceramic material and preparation method thereof |
-
2008
- 2008-08-28 CN CN2008101507446A patent/CN101343182B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803708A (en) * | 2006-01-19 | 2006-07-19 | 湖北大学 | Low temperature sintered PMMSN titanic acid piezoelectric ceramic material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 晁小练.低温烧结PZT-PFW-PMN系压电陶瓷电性能的研究.《硕士论文级》.2007,(第11期),全文. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101343182A (en) | 2009-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101343182B (en) | Doped five-membered low-temperature melt piezoelectric ceramic material and preparation thereof | |
| CN101337814B (en) | Low temperature sintering lithium antimonite doped quinary system piezoelectric ceramics material and method for preparing same | |
| CN101302105B (en) | Lead niobium antimonite-containing five-element piezoelectric ceramics material for driver and preparation thereof | |
| JP4100847B2 (en) | Piezoelectric ceramic composition | |
| CN106554202B (en) | A kind of bismuth laminated bismuth-sodium titanate high temperature piezoceramics and preparation method thereof | |
| JPS62202576A (en) | Piezoelectric ceramics and manufacture of the same | |
| CN103636018A (en) | Piezoelectric material | |
| CN105198417B (en) | A kind of preparation method of zirconic acid bismuth sodium lithium cerium dopping potassium-sodium niobate base ceramic material | |
| CN111302797A (en) | Potassium-sodium niobate-based leadless piezoelectric ceramic and preparation method thereof | |
| CN102167585B (en) | Multielement-doped bismuth titanate group lead-free piezoceramic material and preparation method thereof | |
| CN101302106A (en) | Potassium-sodium niobate-based leadless piezoelectric material and preparation thereof | |
| CN101786880B (en) | Sodium potassium niobate-potassium lithium niobate piezoelectric ceramics and preparation method thereof | |
| JP4995412B2 (en) | Piezoelectric ceramic composition and piezoelectric element using the same | |
| CN110981469A (en) | Preparation method of sodium bismuth titanate-based high-temperature piezoelectric ceramic | |
| CN114133243A (en) | High-dielectric-constant high-voltage electric strain emission type piezoelectric ceramic material and preparation method thereof | |
| CN106588011A (en) | Potassium sodium niobate-based leadless transparent ferroelectric ceramic with high remanent polarization and high Curie temperature, and production method thereof | |
| CN101337815A (en) | Leadless piezoelectric ceramics and method for preparing the same | |
| CN102584228A (en) | Cerium-oxide-doped niobium-stibium lead-zirconate-titanate piezoelectric ceramic | |
| CN105218090B (en) | Obvious anisotropic high-performance lead zirconates based piezoelectric ceramic materials of a kind of electromechanical coupling factor and preparation method thereof | |
| JP4247936B2 (en) | Piezoelectric ceramic composition | |
| CN101265093A (en) | Tungsten bronze structure lead lanthanum niobate titanate high-temperature piezoelectric ceramic and preparation method thereof | |
| CN107311643B (en) | lead-free electronic ceramic material with wide working temperature region and high dielectric property and preparation method thereof | |
| CN101265092A (en) | Oxide modifying lead barium niobate high-temperature piezoelectric ceramic and preparation method thereof | |
| CN111606707B (en) | Temperature-holding stable piezoelectric ceramic material and preparation method thereof | |
| CN107021754A (en) | Dispersant is modified relaxation type niobium nickel lead titanate piezoelectric ceramics and preparation method thereof |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110504 Termination date: 20130828 |