CN101337814A - Low temperature sintering lithium antimonite doped quinary system piezoelectric ceramics material and method for preparing same - Google Patents

Abstract

The invention provides low-temperature sintering lithium antimoniate mixed quinary system piezoelectric ceramics, which consists of the materials expressed with the following general expression: 0.02Pb(Mg1/2W1/2)O3-yPb(Sb1/2Nb1/2)O3-(0.39-y)Pb(Ni1/3Nb2/3)O3-Pb0.59(Zr0.38Ti0.21)O3+xLiSbO3. In the general expression, x is more than 0 percent by weight, but less than 0.40 percent by weight; y is more than or equal to 0 percent by weight, but less than or equal to 0.030mol. The preparation method of the lower-pressure sintering lithium antimoniate mixed quinary system peizoelectric ceramics comprises the processing steps of preparing lithium antimoniate, synthesizing ingredients, pre-burning, granulation, tabletting, batching-out, sintering, burning silver and polarization. According to the laboratory investigation result, the piezoelectric constant and the planar electromechanical coupling factor of the quinary system piezoelectric ceramics prepared are high; the low-temperature sintering performance is good. By comparing the low-temperature sintering antimoniate mixed quinary system with similar piezoelectric ceramics reported in literatures, the mechanical quality factor Qm and the dielectric loss tan Delta are significantly reduced; the piezoelectric constant d33 and the planar electromechanical coupling factor Kp are significantly improved; the sintering temperature is significantly reduced from 1200 DEG C to 900 DEG C; and the preparation process is simple with high repetitiveness, yield and low cost.

Description

Five one-component system piezoelectric ceramics materials of low-temperature sintering metaantimmonic acid lithium doping and preparation method thereof

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.Since it have high piezoelectric property, easily be processed into complex character, cheap, be easy to advantage such as batch process, be widely used in the electron device.But existing piezoceramic material still can not satisfy the composite request of practical application to material property.For improving the performance of piezoceramic material, often adopt two kinds of approach: the one, by in body material, adding ternary or quaternary to form the purpose that novel material reaches modification; The 2nd, different with Effect on Performance according to different dopant ions to material structure, current material is carried out doping vario-property.In addition, the lead base piezoelectric ceramics is when high temperature sintering, because plumbous volatilization, feasible composition departs from, degradation and to technical problems such as environment pollute, especially silver replaces the interior electrode of precious metal palladium as the multilayer piezoelectric ceramic device in order to adopt cheaply, is necessary piezoelectric ceramics is carried out low-temperature sintering research.

This unique function of piezoelectric makes it have more wide application prospect in the intelligent material system.But, under the high temperature sintering plumbous volatilization can cause that stoichiometric ratio departs from, degradation, contaminate environment.Sealing sintering process, atmospheric pellet method at present commonly used, bury powder method, plumbous overflow method, can not fundamentally solve plumbous volatilization, suppress plumbous volatilization actively and effective means is the low-temperature sintering that realizes piezoelectric ceramics.The exploitation low-temperature melt piezoelectric ceramic material is the important research direction of development high-performance, high reliability, low-cost multilayer piezoelectric ceramic device.

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 study five yuan be and the system of high piezoelectric constant, high planar electromechanical coupling factor and low sintering temperature, low mechanical quality factor, low dynamo-electric loss of obtaining simultaneously 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 LiSbO 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 low sintering temperature 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 electromechanical coupling factor, low-temperature sintering and temperature range is wide, performance is good, practical, five one-component system piezoelectric ceramics materials of the low-temperature sintering metaantimmonic acid lithium doping of easy production.

Another technical problem to be solved by this invention is to provide a kind of five one-component system piezoelectric ceramics preparation methods of low-temperature sintering metaantimmonic acid lithium doping.

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+ xLi SbO ₃, 0.00wt.%＜x in the formula≤0.40wt.%, 0.000≤y≤0.030mol.

Five one-component system piezoelectric ceramics preparation methods of above-mentioned low-temperature sintering metaantimmonic acid lithium doping comprise that step is as follows:

1, preparation metaantimmonic acid lithium

Earlier with Li ₂CO ₃, Sb ₂O ₅Be to mix at 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: 1.5～2.5, with ball mill ball milling 12 hours, rotating speed was 400 rev/mins, separation of oxygenated zirconium ball, compound is put into the oven dry in 10 hours of 80 ℃ of dryings of loft drier, put into mortar again and ground 30 minutes, cross 80 mesh sieves, the material after sieving places in the alumina crucible, with the compacting of agate rod, loose density is 1.2～1.5g/cm ³, add a cover 2～4 hours synthetic LiSbO of 570～730 ℃ of pre-burning insulations in resistance furnace 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

Then with synthetic LiSbO 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, 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 ℃ of dryings of loft drier 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, 800～850 ℃ 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, the weight ratio of dehydrated alcohol and raw material is 1: 2, uses ball mill ball milling 6～12 hours, carries out secondary ball milling, rotating speed is 300 rev/mins, separation of oxygenated zirconium ball was put into 80 ℃ of dryings of loft drier 5～10 hours with compound, crossed 80 mesh sieves.

4, granulation

The burning piece of pre-burning is crossed 160 mesh sieves with the mortar porphyrize, the adding mass concentration is 5% polyvinyl alcohol solution and glycerol solution, raw material 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

Spherical powder 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 880～950 ℃ 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, 80 ℃ of oven dry in the baking oven, 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 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 metaantimmonic acid lithium processing step 1 of the present invention, the Li after grinding is sieved ₂CO ₃, Sb ₂O ₅Compound, 2～3 hours synthetic LiSbO of preferred 570～700 ℃ of pre-burnings in resistance furnace 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 880～930 ℃ of sintering 3～4.5 hours.

In preparation metaantimmonic acid lithium processing step 1 of the present invention, the Li after grinding is sieved ₂CO ₃, Sb ₂O ₅Compound, 3 hours synthetic LiSbO of best 610 ℃ of pre-burnings in resistance furnace 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 900 ℃ of sintering 4 hours.

The present invention shows through results of laboratory, five prepared one-component system piezoelectric ceramics materials, and piezoelectric constant height, planar electromechanical coupling factor high and low temperature sintering character are good, compare mechanical quality factor Q with the similar piezoceramic material 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 900 ℃ 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 low-temperature melt piezoelectric ceramic 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.Help multilayer device and adopt the Ag-Pd slurry of the low palladium content that conductivity is good, price is lower or pure Ag entoplasm in process of production, lowered the production cost of device as interior electrode.With the piezoelectric ceramic actuator that this piezoceramic material is made, the displacement power output greatly, do not generate heat, sensitive high, stablize, advantage such as precision height, compact construction, controllability are good.

Description of drawings

Fig. 1 is Different L iSbO ₃The X ray collection of illustrative plates of 900 ℃ of sintered ceramics of doping.

Fig. 2 is 0.06wt.%LiSbO ₃The X ray collection of illustrative plates of doping differing temps sintered ceramic.

Fig. 3 is Different L iSbO ₃The stereoscan photograph of 900 ℃ of sintered ceramics of doping.

Fig. 4 is 0.06wt.%LiSbO ₃The stereoscan photograph of doping differing temps sintered ceramic.

Fig. 5 is different Pb (Sb _1/2Nb _1/2) O ₃The X ray collection of illustrative plates of 900 ℃ of sintered 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 sintered ceramic.

Fig. 7 is different Pb (Sb _1/2Nb _1/2) O ₃The stereoscan photograph of 900 ℃ of sintered ceramics of content.

Fig. 8 is 0.10wt.%Pb (Sb _1/2Nb _1/2) O ₃The stereoscan photograph of content differing temps sintered ceramic.

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 0.2, y is 0.01 o'clock, 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+ 0.2wt%LiSbO ₃The raw material and the weight proportion thereof of expression are:

Pb ₃O ₄ 67.06g

ZrO ₂ 13.75g

TiO ₂ 4.92g

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

LiSbO ₃ 0.20g

Its preparation method is as follows:

1, preparation metaantimmonic acid lithium

Earlier with Li ₂CO ₃, Sb ₂O ₅Be to mix at 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, with ball mill ball milling 12 hours, rotating speed was 400 rev/mins, separation of oxygenated zirconium ball, compound is put into the oven dry in 10 hours of 80 ℃ of dryings of loft drier, put into mortar again and ground 30 minutes, cross 80 mesh sieves, the material after sieving places in the alumina crucible, with the compacting of agate rod, loose density is 1.2～1.5g/cm ³, add a cover 3 hours synthetic Li SbO of 610 ℃ of pre-burning insulations in resistance furnace 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

Then with synthetic Li SbO 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, 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, the weight ratio of dehydrated alcohol and raw material is 1: 2, uses ball mill ball milling 6～12 hours, carries out secondary ball milling, rotating speed is 300 rev/mins, separation of oxygenated zirconium ball was put into 80 ℃ of dryings of loft drier 5～10 hours with compound, 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 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 900 ℃ 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, 80 ℃ of oven dry in the baking oven, 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 4kV/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

LiSbO ₃ 0g

Its preparation method is as follows:

In preparation metaantimmonic acid lithium processing step 1, with Li ₂CO ₃, Sb ₂O ₅Be mixing in 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 LiSbO of 570 ℃ of pre-burning insulations in resistance furnace 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%LiSbO 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

LiSbO ₃ 0.4g

Its preparation method is as follows:

In preparation metaantimmonic acid lithium processing step 1, with Li ₂CO ₃, Sb ₂O ₅Be mixing in 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 LiSbO of 730 ℃ of pre-burnings in resistance furnace 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 950 ℃ 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 0.06, 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+ 0.06wt%LiSbO ₃The raw material and the weight proportion thereof of expression are:

Pb ₃O ₄ 67.20g

ZrO ₂ 13.76g

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

LiSbO ₃ 0.06g

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, LiSbO ₃Content is to the ceramic electrical Effect on Performance

Earlier with Li ₂CO ₃, Sb ₂O ₅Be to mix at 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, with ball mill ball milling 12 hours, rotating speed was 400 rev/mins, separation of oxygenated zirconium ball, compound is put into the oven dry in 10 hours of 80 ℃ of dryings of loft drier, put into mortar again and ground 30 minutes, cross 80 mesh sieves, the material after sieving places in the alumina crucible, with the compacting of agate rod, loose density is 1.2～1.5g/cm ³, add a cover 3 hours synthetic LiSbO of 610 ℃ of pre-burning insulations in resistance furnace 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.

Again raw material is placed in the loft drier 120 ℃ of dryings 5 hours, and pressed 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+ x LiSbO ₃Prepare burden, y is 0.010 in the formula, and x is respectively 0.00wt.%, 0.03wt.%, 0.06wt.%, 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 3 hours.Powder after the pre-burning carried out secondary ball milling 10 hours under the same conditions; discharging; oven dry in 80 ℃, 8 hours; crossed 160 mesh sieves in 1 hour with the mortar mill; the interpolation weight concentration is 5% polyvinyl alcohol granulation; addition is 7% of a preburning powdered material weight; it is that 15 ± 0.05mm, thickness are the disk of 1.5 ± 0.02mm that material after the granulation is pressed into diameter with mould; 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, 880～950 ℃ of sintering 4 hours in lead protection atmosphere naturally cool to room temperature with stove.With agglomerating ceramic disks sanding and polishing to diameter is that 13.5mm, thickness are 1.2mm, with ultrasonic cleaning, 80 ℃ of oven dry, at coated on both sides silver slurry, in 850 ℃ of burning infiltration silver electrodes 30 minutes.The sample that will burn electrode then places 150 ℃ silicone oil with the high direct voltage polarization of 4kV/mm 25 minutes, obtains the piezoelectric ceramics finished product.After leaving standstill 24 hours under the room temperature, test piezoelectric property.The capacitor C and the dielectric loss tan δ of the sample of electrode burnt in test.Calculate specific inductivity with following formula:

ε _r＝4Ct/(πε ₀d ²) (1)

In the formula, t is the thickness of ceramic plate, ε ₀Be permittivity of vacuum (8.85 * 10 ^-12F/m), d is the diameter of ceramic plate.

Measure the piezoelectric constant d of piezoelectric ceramics finished product with the quasi static test instrument ₃₃

Adopt Archimedes's method to measure the density p (g/cm of ceramics sample 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, putting into water boiled 40 minutes, soaked again 5～10 minutes, and weighed up the quality B (unit be g) of sample in distilled water.Be calculated as follows its volume density:

$\mathrm{\ρ}=\frac{A}{A-B}\×({\mathrm{\ρ}}_o-{\mathrm{\ρ}}_L)+{\mathrm{\ρ}}_L---\left(2\right)$

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:

$K_p=\sqrt{\frac{2.51\×(f_a-f_r)}{f_r}}---\left(3\right)$

F in the formula _rBe resonant frequency, f _A,Be anti-resonance frequency, by (4) formula calculating machine quality factor Q _m:

$Q_m={f_a}^2{\left[2\mathrm{\πr}{C}^T{f}_r({f_a}^2-{f_r}^2)\right]}^{-1}---\left(4\right)$

F in the formula _rBe resonant frequency, f _A,Be 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 1 y is 4 hours different sintering temperature LiSbO of 0.010mol sintering ₃Content is to the ceramic electrical Effect on Performance

By table 1 as seen, in 880～950 ℃ of sintering ranges, when x was 0.00～0.40wt.%, every performance index of piezoelectric ceramics were all better, wherein when x is 0.06wt.%, when sintering temperature is 900 ℃, every performance the best of piezoelectric ceramics.

Y is 0.010mol, LiSbO ₃Content is that the X ray collection of illustrative plates of 0.00～0.40wt.%, 4 hours prepared piezoelectric ceramics of 900 ℃ of sintering is seen Fig. 1.As seen from Figure 1, when x＜0.40wt.%, all components are the pure perovskite phase structure all, and the Jiao Lvshi that does not have a degrade performance mutually and second appearance of dephasign mutually.And, be 43 °～47 ° unimodal (200) located by 2 θ _RCan illustrate that this material system is water chestnut side's phase structure.

Y is 0.010mol, LiSbO ₃Content is that the X ray collection of illustrative plates of the prepared piezoelectric ceramics of 0.06wt.%, different sintering temperature is seen Fig. 2.As seen from Figure 2, all components all are the pure perovskite phase structure, and 880 ℃ second phase occurs, and along with the increase of temperature, second disappears mutually.And, 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 0.010mol, LiSbO ₃Content is that the electronic scanning electromicroscopic photograph of 0.00～0.40wt.%, 4 hours prepared piezoelectric ceramics sections of 900 ℃ of sintering is seen Fig. 3.In Fig. 3, a is LiSbO ₃Content is the electronic scanning electromicroscopic photograph of the ceramic section of 900 ℃ of 0.00wt.% sintering, and b is LiSbO ₃Content is the electronic scanning electromicroscopic photograph of the ceramic section of 900 ℃ of 0.03wt.% sintering, and c is LiSbO ₃Content is the electronic scanning electromicroscopic photograph of the ceramic section of 900 ℃ of 0.06wt.% sintering, and d is LiSbO ₃Content is the electronic scanning electromicroscopic photograph of the ceramic section of 900 ℃ of 0.10wt.% sintering, and e is LiSbO ₃Content is the electronic scanning electromicroscopic photograph of the ceramic section of 900 ℃ of 0.20wt.% sintering, and f is LiSbO ₃Content is the electronic scanning electromicroscopic photograph of the ceramic section of 900 ℃ of 0.40wt.% sintering.As can be seen from Figure 3, LiSbO in piezoelectric ceramics ₃Content when being 0.03wt.%～0.06wt.%, the crystal boundary of piezoelectric ceramics is clear, full grains, grain growth and growth are evenly.

Y is 0.010mol, LiSbO ₃Content is that the electronic scanning electromicroscopic photograph of the prepared piezoelectric ceramics section of 0.06wt.%, different sintering temperature is seen Fig. 4.In Fig. 4, a is 0.06wt.%LiSbO ₃The electronic scanning electromicroscopic photograph of doped sintered 880 ℃ ceramic section, b is 0.06wt.%LiSbO ₃The electronic scanning electromicroscopic photograph of doped sintered 900 ℃ ceramic section, c is 0.06wt.%LiSbO ₃The electronic scanning electromicroscopic photograph of doped sintered 930 ℃ ceramic section, d is 0.06wt.%LiSbO ₃The electronic scanning electromicroscopic photograph of doped sintered 950 ℃ ceramic section.As can be seen from Figure 4, when sintering temperature was 900 ℃, the crystal boundary of piezoelectric ceramics was clear, full grains, and grain growing is even.

2.Pb (Sb _1/2Nb _1/2) O ₃Content is to the ceramic electrical Effect on Performance

In experiment 1, x is 0.06wt.%, Pb (Sb _1/2Nb _1/2) O ₃Content is value in 0.000～0.030mol, presses 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+ 0.06wt.%LiSbO ₃Prepare burden, experimentation is identical with experiment 1.The capacitor C and the dielectric loss tan δ of the sample of electrode burnt in test.Measure the piezoelectric constant d of piezoelectric ceramics finished product with the quasi static test instrument ₃₃, by formula (1) calculates DIELECTRIC CONSTANT _r, (2) bulk density by formula, by formula (3) calculate planar electromechanical coupling factor K _p, (4) calculating machine quality factor Q by formula _mTest and calculation result see Table 2.

Different Pb (Sb under the different sintering temperatures of table 2 _1/2Nb _1/2) O ₃The electrical property of the pottery of content

By table 2 as seen, sintering temperature is 880～950 ℃, and every performance index of piezoelectric ceramics are all better, wherein at Pb (Sb _1/2Nb _1/2) O ₃Content is that 0.010mol, sintering temperature are every performance the best of 900 ℃ of piezoelectric ceramics.

X is 0.06wt.%, Pb (Sb _1/2Nb _1/2) O ₃Content is 0.000～0.030mol, and the X ray collection of illustrative plates of 4 hours pottery of 900 ℃ of sintering is seen Fig. 5.As can be seen from Figure 5, all components all are the pure perovskite phase structure, and when content during from 0.000mol to 0.010mol, the Jiao Lvshi that does not have a degrade performance mutually and second appearance of dephasign mutually.And, be 43 °～47 ° unimodal (002) located by 2 θ _RCan illustrate that this system is water chestnut side's phase.

X is 0.06wt.%, Pb (Sb _1/2Nb _1/2) O ₃Content is 0.010mol, and the X ray collection of illustrative plates of differing temps sintered ceramic is seen Fig. 6.As can be seen from Figure 6, all components all are the pure perovskite phase structure, when temperature is 880～950 ℃, do not have the Jiao Lvshi phase and second appearance of dephasign mutually of degrade performance.And, be 43 °～47 ° unimodal (002) located by 2 θ _RCan illustrate that this system is water chestnut side's phase.

X is 0.06wt.%, Pb (Sb _1/2Nb _1/2) O ₃Content is 0.000～0.030mol, different Pb (Sb _1/2Nb _1/2) O ₃The electronic scanning electromicroscopic photograph of 4 hours prepared piezoelectric ceramics sections of 900 ℃ of sintering of content is seen Fig. 7.In Fig. 7, a is that content is the Pb (Sb of 0.000mol _1/2Nb _1/2) O ₃, the electronic scanning electromicroscopic photograph of 4 hours piezoelectric ceramics section of 900 ℃ of sintering, b are that content is the Pb (Sb of 0.006mol _1/2Nb _1/2) O ₃, the electronic scanning electromicroscopic photograph of 4 hours piezoelectric ceramics section of 900 ℃ of sintering, c are that content is the Pb (Sb of 0.010mol _1/2Nb _1/2) O ₃, the electronic scanning electromicroscopic photograph of 4 hours piezoelectric ceramics section of 900 ℃ of sintering, d are that content is the Pb (Sb of 0.015mol _1/2Nb _1/2) O ₃, the electronic scanning electromicroscopic photograph of 4 hours piezoelectric ceramics section of 900 ℃ of sintering, e are that content is the Pb (Sb of 0.030mol _1/2Nb _1/2) O ₃, the electronic scanning electromicroscopic photograph of 4 hours piezoelectric ceramics section of 900 ℃ of sintering.From Fig. 7 as seen, as Pb (Sb _1/2Nb _1/2) O ₃When content was 0.006～0.010mol, crystal grain was more even, and crystal boundary is clear, and compactness is good.

X is 0.06wt.%, Pb (Sb _1/2Nb _1/2) O ₃Content is 0.010mol, and the electronic scanning electromicroscopic photograph of differing temps sintered ceramic section is seen Fig. 8.In Fig. 8, a is that content is the Pb (Sb of 0.010mol _1/2Nb _1/2) O ₃, the electronic scanning electromicroscopic photograph of 4 hours piezoelectric ceramics section of 880 ℃ of sintering, b are that content is the Pb (Sb of 0.010mol _1/2Nb _1/2) O ₃, the electronic scanning electromicroscopic photograph of 4 hours piezoelectric ceramics section of 900 ℃ of sintering, c are that content is the Pb (Sb of 0.010mol _1/2Nb _1/2) O ₃, the electronic scanning electromicroscopic photograph of 4 hours piezoelectric ceramics section of 930 ℃ of sintering, d are that content is the Pb (Sb of 0.010mol _1/2Nb _1/2) O ₃, the electronic scanning electromicroscopic photograph of 4 hours piezoelectric ceramics section of 950 ℃ of sintering.Can see that from Fig. 8 when sintering temperature was 900 ℃, the crystal grain of pottery was bigger, and relatively evenly, crystal boundary is clear, compactness is good.

Claims (4)

1, a kind of five one-component system piezoelectric ceramics materials of low-temperature sintering metaantimmonic acid lithium doping is characterized in that: use general formula 0.02Pb (Mg down _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+ xLi SbO ₃

The material of expression is formed, 0.00wt.%＜x in the formula≤0.40wt.%, 0.000≤y≤0.030mol.

2, a kind of five one-component system piezoelectric ceramics preparation methods of claim 1 low-temperature sintering metaantimmonic acid lithium doping is characterized in that this method comprises the steps:

(1) preparation metaantimmonic acid lithium

Earlier with Li ₂CO ₃, Sb ₂O ₅Be to mix at 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: 1.5～2.5, with ball mill ball milling 12 hours, rotating speed was 400 rev/mins, separation of oxygenated zirconium ball, compound is put into the oven dry in 10 hours of 80 ℃ of dryings of loft drier, put into mortar again and ground 30 minutes, cross 80 mesh sieves, the material after sieving places in the alumina crucible, with the compacting of agate rod, loose density is 1.2～1.5g/cm ³, add a cover 2～4 hours synthetic LiSbO of 570～730 ℃ of pre-burning insulations in resistance furnace 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

Then with synthetic LiSbO 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, 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 ℃ of dryings of loft drier 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, 800～850 ℃ 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, the weight ratio of dehydrated alcohol and raw material is 1: 2, uses ball mill ball milling 6～12 hours, carries out secondary ball milling, rotating speed is 300 rev/mins, separation of oxygenated zirconium ball was put into 80 ℃ of dryings of loft drier 5～10 hours with compound, crossed 80 mesh sieves;

(4) granulation

The burning piece of pre-burning is crossed 160 mesh sieves with the mortar porphyrize, the adding mass concentration is 5% polyvinyl alcohol solution and glycerol solution, raw material 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

Spherical powder 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 880～950 ℃ 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, 80 ℃ of oven dry in the baking oven, 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 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 five one-component system piezoelectric ceramics preparation methods of the described low-temperature sintering metaantimmonic acid of claim 2 lithium doping, it is characterized in that: in preparation metaantimmonic acid lithium processing step of the present invention (1), the Li after grinding is sieved ₂CO ₃, Sb ₂O ₅Compound, 2～3 hours synthetic LiSbO of 570～700 ℃ of pre-burnings in resistance furnace 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 alumina crucible lid and seal, 2～5 ℃/minute of heat-up rates, 880～930 ℃ of sintering 3～4.5 hours.

4, according to five one-component system piezoelectric ceramics preparation methods of the described low-temperature sintering metaantimmonic acid of claim 2 lithium doping, it is characterized in that: in preparation metaantimmonic acid lithium processing step of the present invention (1), the Li after grinding is sieved ₂CO ₃, Sb ₂O ₅Compound, 3 hours synthetic LiSbO of 610 ℃ of pre-burnings in resistance furnace 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, 900 ℃ of sintering 4 hours.

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