CN104761260B - Preparation method of (Ba＜x＞Ca＜1-x＞)(Ti＜y＞M＜1-y＞)O3 system piezoelectric ceramic material - Google Patents
Preparation method of (Ba＜x＞Ca＜1-x＞)(Ti＜y＞M＜1-y＞)O3 system piezoelectric ceramic material Download PDFInfo
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Abstract
The invention relates a (Ba＜x＞Ca＜1-x＞)(Ti＜y＞M＜1-y＞)O3 system piezoelectric ceramic material and a preparation method thereof. The piezoelectric ceramic material can be represented by the following general formula: (Ba＜x＞Ca＜1-x＞)(Ti＜y＞M＜1-y＞)O3, wherein M is one of Zr or Sn, 0≤x≤1 and 0≤y≤1. In the invention, a ceramic sample is prepared through a method of combination of liquid-phase mixing and solid-phase sintering. By means of the method, the raw materials can be mixed more uniformly. The prepared ceramic sample is more uniform in crystal grain size, is clear in crystal boundary and is uniform and compact in structure. The ceramic sample is better in piezoelectric performances and electrostrictive strain than those of a sample prepared through a conventional solid phase method.
Description
Technical field
A kind of (ba is providedxca1-x)(tiym1-y)o3The preparation method of system piezoceramic material, belongs to piezoceramic material
Field.
Background technology
Piezoelectric ceramics, as modern and its important high-tech functional material, its application throughout military, civilian etc. each
The fields such as field, particularly ultrasonic transduction, sensor, Non-Destructive Testing and mechanics of communication.In recent years, along with the mankind, environmental protection is anticipated
Know enhancing and own health is given more sustained attention, as leading position lead titanate piezoelectric ceramics Europe disabling.Phase
In the near future, lead piezoelectric ceramics can disable letter in the world.So, in the urgent need to finding leadless piezoelectric material material generation
For traditional lead base piezoceramic material.
At present, the more leadless piezoelectric ceramics of research mainly has perovskite structure, bismuth laminated and tungsten bronze structure.One
As for, bismuth laminated leadless piezoelectric ceramic Curie temperature is higher, and anisotropy is big and piezoelectric activity is relatively low.Tungsten bronze structure
System piezoelectric ceramics has that spontaneous polarization strength is big, Curie temperature is high, the low feature of dielectric constant, and its composition and structure are to its ferrum
Electrical property has a major impact.
Perovskite system piezoelectric ceramics has higher piezoelectric constant, potassium-sodium niobate system particularly document " lead-free
Piezoceramics, y.saito, et al.nature, 432 (2004) " it is prepared for using the method for conventional solid sintering in having
There is the potassium-sodium niobate lithium tantalum antimony leadless piezoelectric ceramics of of a relatively high piezoelectric property, the piezoelectric ceramics sintering temperature of the method preparation is low
In 1100 DEG C, but containing volatile elements such as substantial amounts of lithium, potassium and sodium, sintering process is more difficult fine and close and sintering character is unstable.
Barium calcium zirconate titanate and stannum barium titanate calcium are the piezoceramic materials with very high piezoelectric property of discovered in recent years, but existing
Research in the preparation method of ceramic material be single solid phase method or sol-gal process.
Solid phase method is the traditional method preparing electric function ceramic.Its basic technology be by raw material based on required chemistry
Amount ratio prepares, and then through ball milling mixing dispersion, pre-burning, obtains ceramic powder.The advantage of this method is technology maturation, process is simple,
With low cost, therefore current industrial production still adopts this method.But this method there is also many inevitably shortcomings: in (1) raw material
Each component is difficult to be mixed into preferable uniform state；(2) calcining heat is high；(3) high-temperature lower part divides raw material volatile, thus is difficult to
Obtain the sintered body in strict conformity with stoichiometric proportion；(4) easily mix in whole technical process, cannot get the high powder body of purity, will
The final performance affecting material.
The ultimate principle of liquid phase method is to select one or more soluble metallic salt, and according to target the chemical composition of material is made into
Solution, makes each element be in lewis' acid state, the handss such as a kind of suitable precipitant of reselection or selection evaporation, distillation, hydrolysis
Section, by metal ion homogeneous precipitation or crystallize out, gained precipitation or crystal can be prepared by ultra micro through dehydration or heat resolve
Powder.Each component mixes on a molecular scale, and material is uniformly dispersed, and preparation temperature has substantial degradation than traditional method, easily
In doping.But, the change of ceramic material because different metal salt dissolubility in the solution is different, can be affected to a certain extent
Learn the homogeneity with structure, and be very difficult to avoid completely the generation of side reaction.
So, the present invention prepares ceramics sample using the method that liquid-phase mixing is combined with solid-phase sintering, by the method
The mixing of raw material can be made more uniform, prepared ceramics sample grain size is more uniform, crystal boundary is clear, even structure causes
Close.Piezoelectric property and electric field induced strain are better than sample prepared by conventional solid-state method.
Content of the invention
It is an object of the invention to provide a kind of (baxca1-x)(tiym1-y)o3The preparation method of system piezoceramic material,
The method prepares ceramics sample using the method that liquid-phase mixing is combined with solid-phase sintering, can make the mixed of raw material by the method
Close more uniform, prepared ceramics sample grain size is more uniform, and crystal boundary is clear, even structure is fine and close.Piezoelectric property and electricity
Cause the sample that strain is better than conventional solid-state method preparation.
The invention provides a kind of (baxca1-x)(tiym1-y)o3System piezoceramic material, its composition is by below general formula table
Show: (baxca1-x)(tiym1-y)o3, in formula, m is one of zr and sn element, and the value of x is 0≤x≤1, and the value of y is 0
≤y≤1.
The invention provides above-mentioned (baxca1-x)(tiym1-y)o3The preparation method of system piezoceramic material, including following
Step:
Step one: according to formula (baxca1-x)(tiym1-y)o3In stoichiometric proportion accurately weigh raw material ba
(ch3coo)2、ca(ch3coo)2、tio2And mo2.
Step 2: by load weighted ba (ch3coo)2And ca (ch3coo)2Be formulated as settled solution respectively in beaker and
After mix, stirring keep its clarification；Tio is sequentially added in settled solution2、mo2, monohydrate potassium.
Step 3: mixed solution is placed in heated and stirred on magnetic agitation platform until evaporating water, is then positioned over
Heating, drying in baking oven, the partially carbonized variable color of compound；Use spoon and brush by compound after taking out from baking oven from beaker
Carefully scrape, grind levigate in mortar.
Step 4: compound is placed in alumina crucible, remaining Organic substance is removed in pre-burning.
Step 5: the compound after heat treatment is taken out from crucible and is placed in finely ground in mortar, then put crucible again into
In, start second pre-burning.
Step 6: the powder after second pre-burning is added dehydrated alcohol to carry out ball milling.
Step 7: carry out third time pre-burning after the compound after ball milling is dried.
Step 8: the powder after third time pre-burning is added dehydrated alcohol to carry out ball milling, then the compound obtaining is dried
Sieve after dry；Add binding agent regrinding in compound after sizing, after so that the two is sufficiently uniformly mixed, carry out second
Secondary sieve.
Step 9: the compound after the completion of sieving is carried out ripening more than 12 hours, makes binding agent abundant with powder body
Mixing, is pressed into ceramic green sheet, and carries out plastic removal process.
Step 10: the ceramic green sheet after plastic removal is processed is calcined, and is then cooled to room temperature.
Step 11: the ceramic green sheet after cooling is carried out polishing both surfaces, drapes over one's shoulders silver electrode and polarize in silicone oil, obtains
(baxca1-x)(tiym1-y)o3System piezoceramic material.
Brief description
Fig. 1 show preparation (ba in the specific embodiment of the inventionxca1-x)(tiym1-y)o3System piezoceramic material
Process chart.
Fig. 2 show (ba in the specific embodiment of the invention0.85ca0.15)(ti0.9zr0.1)o3Pottery is incubated 2 at 1540 DEG C
X-ray diffraction collection of illustrative plates after -24 hours for the hour.It can be seen that sample is all pure phase under each temperature retention time, thing phase
For Tetragonal.
Fig. 3 show liquid-phase mixing and solid-phase sintering combined techniqueses in conventional solid-state method (a) and the specific embodiment of the invention
(ba prepared by (b)0.85ca0.15)(ti0.9zr0.1)o3Pottery 1540 DEG C insulation 2 hours after surface sem figure.Permissible from figure
Find out, the sample grain size of method provided by the present invention preparation is more more uniform than prepare by conventional solid-state method, crystal boundary clearly,
Even structure is fine and close.
Fig. 4 show (ba in the specific embodiment of the invention0.85ca0.15)(ti0.9zr0.1)o3Pottery is incubated 2 at 1540 DEG C
Dielectric constant and dielectric loss variation with temperature curve chart after hour.It can be seen that the Curie temperature of sample is 89
DEG C, and loss value very little.
Fig. 5 show (ba in the specific embodiment of the invention0.85ca0.15)(ti0.9zr0.1)o3Pottery is incubated 2 at 1540 DEG C
The change curve to electric field intensity for the ferroelectric hysteresis loop and switching current of test after hour.
Fig. 6 show (ba in the specific embodiment of the invention0.85ca0.15)(ti0.9zr0.1)o3Pottery is incubated 2 at 1540 DEG C
The electric field induced strain curve chart of test after hour.
Fig. 7 show (ba in the specific embodiment of the invention0.85ca0.15)(ti0.9zr0.1)o3Pottery is incubated at 1540 DEG C
The electric field induced strain curve chart tested at different temperatures after 24 hours.It can be seen that raising with temperature, the electricity of sample
Strain is caused to be gradually reduced.So for the application of this piezoelectric ceramics, operating temperature is unsuitable too high.
Specific embodiment
For making the object, technical solutions and advantages of the present invention clearer, illustrate the present invention below in conjunction with accompanying drawing
Technical scheme and effect.
Embodiment 1
This example provides a kind of (baxca1-x)(tiym1-y)o3System piezoceramic material, its composition such as following formula represents:
(ba0.85ca0.15)(ti0.9zr0.1)o3, wherein m is zr, and the value of x is the value of 0.85, y is 0.90.
(ba in the present embodimentxca1-x)(tiym1-y)o3The preparation method of system piezoceramic material, referring to Fig. 1, concrete step
Suddenly as follows:
Step one: with analyze pure be more than 98% ba (ch3coo)2、ca(ch3coo)2、tio2And zro2As raw material,
According to formula (ba0.85ca0.15)(ti0.9zr0.1)o3Stoichiometric proportion accurately calculate and precise.
Step 2: by load weighted ba (ch3coo)2And ca (ch3coo)2Be formulated as settled solution respectively in beaker and
After mix, stirring keep its clarification；Tio is sequentially added in settled solution2、zro2, monohydrate potassium.
Step 3: mixed solution is placed on magnetic agitation platform at 80 DEG C of temperature heated and stirred until being evaporated water
Point, then it is positioned in baking oven 250 DEG C of heating, dryings 8 hours, the partially carbonized variable color of compound；Spoon is used after taking out from baking oven
With brush, compound is carefully scraped from beaker, grind levigate in mortar.
Step 4: compound is placed in alumina crucible, rises to 750 DEG C with the heating rate of 3 DEG C/min and to be incubated 4 little
When, remove remaining Organic substance.
Step 5: the compound after pre-burning is taken out from crucible and is placed in finely ground in mortar, then put into again in crucible,
Rise to 1300 DEG C with the heating rate of 5 DEG C/min, keep this temperature calcination after 8 hours, be naturally cooling to room temperature with stove.
Step 6: the powder after second pre-burning is added dehydrated alcohol, is ball milling under 400r/min 10 in ball milling speed
Hour.
Step 7: the compound after ball milling is placed in 80 DEG C of drying of temperature in baking oven, then with the intensification speed of 5 DEG C/min
Rate rises to 1350 DEG C, keeps this temperature calcination after 10 hours, is naturally cooling to room temperature with stove.
Step 8: the powder after third time pre-burning is added dehydrated alcohol, is ball milling under 400r/min 10 in ball milling speed
Hour, cross 300 mesh dusting covers after then the compound obtaining being dried at 80 DEG C；Appropriate gluing is added in compound after sizing
Knot agent regrinding, after so that the two is sufficiently uniformly mixed, after 100 mesh sieves.Wherein, binding agent is that weight percentage is
5% polyvinyl alcohol water solution, its consumption is the 7% of mixed powder gross weight.
Step 9: the compound after the completion of sieving is carried out ripening more than 12 hours, makes binding agent abundant with powder body
Mixing, is pressed into ceramic green sheet, and carries out plastic removal process.
Step 10: the ceramic green sheet after plastic removal is processed rises to 1540 DEG C with the heating rate of 5 DEG C/min, keeps respectively
This temperature calcination 2 hours, 5 hours, 8 hours, after 12 hours and 24 hours, is then cooled to room temperature.
Step 11: the ceramic green sheet after cooling is carried out polishing both surfaces, drapes over one's shoulders in silver electrode silicone oil at room temperature
Impose the DC voltage polarization 30min of 6kv/mm, obtain barium zirconium phthalate calcium ceramic material.
Learn after tested: the piezoceramic material that the present embodiment prepares performance parameter at room temperature is as follows:
1540 DEG C/2h:d33=380pc/n, kp=0.351, ε=3436, tan δ=0.0322, qm=213
1540 DEG C/5h:d33=430pc/n, kp=0.366, ε=3527, tan δ=0.0298, qm=185
1540 DEG C/8h:d33=455pc/n, kp=0.388, ε=3845, tan δ=0.0311, qm=243
1540 DEG C/12h:d33=475pc/n, kp=0.422, ε=4137, tan δ=0.0249, qm=125
1540 DEG C/24h:d33=540pc/n, kp=0.48, ε=3316, tan δ=0.0208, qm=161
Fig. 2 show (ba in the specific embodiment of the invention0.85ca0.15)(ti0.9zr0.1)o3Pottery is incubated 2 at 1540 DEG C
X-ray diffraction collection of illustrative plates after -24 hours for the hour.It can be seen that sample is all pure phase under each temperature retention time, thing phase
For Tetragonal.
Fig. 3 show liquid-phase mixing and solid-phase sintering combined techniqueses in conventional solid-state method (a) and the specific embodiment of the invention
(ba prepared by (b)0.85ca0.15)(ti0.9zr0.1)o3Pottery 1540 DEG C insulation 2 hours after surface sem figure.Can from figure
To find out, the sample grain size of method preparation provided by the present invention is more more uniform than prepared by conventional solid-state method, and crystal boundary is clear
Clear, even structure is fine and close.
Fig. 4 show (ba in the specific embodiment of the invention0.85ca0.15)(ti0.9zr0.1)o3Pottery is incubated 2 at 1540 DEG C
Dielectric constant and dielectric loss variation with temperature curve chart after hour.It can be seen that the Curie temperature of sample is 89
DEG C, and loss value very little.
Fig. 5 show (ba in the specific embodiment of the invention0.85ca0.15)(ti0.9zr0.1)o3Pottery is incubated 2 at 1540 DEG C
The change curve to electric field intensity for the ferroelectric hysteresis loop and switching current of test after hour.
Fig. 6 show (ba in the specific embodiment of the invention0.85ca0.15)(ti0.9zr0.1)o3Pottery is incubated 2 at 1540 DEG C
The electric field induced strain curve chart of test after hour.
Fig. 7 show (ba in the specific embodiment of the invention0.85ca0.15)(ti0.9zr0.1)o3Pottery is incubated at 1540 DEG C
The electric field induced strain curve chart tested at different temperatures after 24 hours.It can be seen that raising with temperature, the electricity of sample
Strain is caused to be gradually reduced.So for the application of this piezoelectric ceramics, operating temperature is unsuitable too high.
Embodiment 2
This example provides a kind of (baxca1-x)(tiym1-y)o3System piezoceramic material, its composition such as following formula represents:
(ba0.85ca0.15)(ti0.95zr0.05)o3, wherein m is zr, and the value of x is the value of 0.85, y is 0.95.
(ba in the present embodimentxca1-x)(tiym1-y)o3The preparation method of system piezoceramic material, referring to Fig. 1, concrete step
Suddenly as follows:
Step one: with analyze pure be more than 98% ba (ch3coo)2、ca(ch3coo)2、tio2And zro2As raw material,
According to formula (ba0.85ca0.15)(ti0.95zr0.05)o3Stoichiometric proportion accurately calculate and precise.
Step 2: by load weighted ba (ch3coo)2And ca (ch3coo)2Be formulated as settled solution respectively in beaker and
After mix, stirring keep its clarification；Tio is sequentially added in settled solution2、zro2, monohydrate potassium.
Step 3: mixed solution is placed on magnetic agitation platform at 80 DEG C of temperature heated and stirred until being evaporated water
Point, then it is positioned in baking oven 250 DEG C of heating, dryings 8 hours, the partially carbonized variable color of compound；Spoon is used after taking out from baking oven
With brush, compound is carefully scraped from beaker, grind levigate in mortar.
Step 4: compound is placed in alumina crucible, rises to 750 DEG C with the heating rate of 3 DEG C/min and to be incubated 4 little
When, remove remaining Organic substance.
Step 5: the compound after pre-burning is taken out from crucible and is placed in finely ground in mortar, then put into again in crucible,
Rise to 1300 DEG C with the heating rate of 5 DEG C/min, keep this temperature calcination after 8 hours, be naturally cooling to room temperature with stove.
Step 6: the powder after second pre-burning is added dehydrated alcohol, is ball milling under 400r/min 10 in ball milling speed
Hour.
Step 7: the compound after ball milling is placed in 80 DEG C of drying of temperature in baking oven, then with the intensification speed of 5 DEG C/min
Rate rises to 1350 DEG C, keeps this temperature calcination after 10 hours, is naturally cooling to room temperature with stove.
Step 8: the powder after third time pre-burning is added dehydrated alcohol, is ball milling under 400r/min 10 in ball milling speed
Hour, cross 300 mesh dusting covers after then the compound obtaining being dried at 80 DEG C；Appropriate gluing is added in compound after sizing
Knot agent regrinding, after so that the two is sufficiently uniformly mixed, after 100 mesh sieves.Wherein, binding agent is that weight percentage is
5% polyvinyl alcohol water solution, its consumption is the 7% of mixed powder gross weight.
Step 9: the compound after the completion of sieving is carried out ripening more than 12 hours, makes binding agent abundant with powder body
Mixing, is pressed into ceramic green sheet, and carries out plastic removal process.
Step 10: the ceramic green sheet after plastic removal is processed rises to 1540 DEG C with the heating rate of 5 DEG C/min, keeps this temperature
After degree calcining 24 hours, it is then cooled to room temperature.
Step 11: the ceramic green sheet after cooling is carried out polishing both surfaces, drapes over one's shoulders in silver electrode silicone oil at room temperature
Impose the DC voltage polarization 30min of 5kv/mm, obtain barium zirconium phthalate calcium ceramic material.
Learn after tested: the piezoceramic material that the present embodiment prepares performance parameter at room temperature is as follows: d33=
244pc/n, kp=0.368, ε=1441, tan δ=0.0113, qm=224
Embodiment 3
This example provides a kind of (baxca1-x)(tiym1-y)o3System piezoceramic material, its composition such as following formula represents:
ba(ti0.9sn0.1)o3, wherein m is sn, and the value of x is the value of 1, y is 0.9.
(ba in the present embodimentxca1-x)(tiym1-y)o3The preparation method of system piezoceramic material, referring to Fig. 1, concrete step
Suddenly as follows:
Step one: with analyze pure be more than 98% ba (ch3coo)2、tio2And sno2As raw material, according to formula ba
(ti0.9sn0.1)o3Stoichiometric proportion accurately calculate and precise.
Step 2: by load weighted ba (ch3coo)2It is formulated as settled solution in beaker, add successively in settled solution
Enter tio2、sno2, monohydrate potassium.
Step 3: mixed solution is placed on magnetic agitation platform at 80 DEG C of temperature heated and stirred until being evaporated water
Point, then it is positioned in baking oven 250 DEG C of heating, dryings 8 hours, the partially carbonized variable color of compound；Spoon is used after taking out from baking oven
With brush, compound is carefully scraped from beaker, grind levigate in mortar.
Step 4: compound is placed in alumina crucible, rises to 750 DEG C with the heating rate of 3 DEG C/min and to be incubated 4 little
When, remove remaining Organic substance.
Step 5: the compound after pre-burning is taken out from crucible and is placed in finely ground in mortar, then put into again in crucible,
Rise to 1200 DEG C with the heating rate of 5 DEG C/min, keep this temperature calcination after 8 hours, be naturally cooling to room temperature with stove.
Step 6: the powder after second pre-burning is added dehydrated alcohol, is ball milling under 400r/min 12 in ball milling speed
Hour.
Step 7: the compound after ball milling is placed in 80 DEG C of drying of temperature in baking oven, then with the intensification speed of 5 DEG C/min
Rate rises to 1250 DEG C, keeps this temperature calcination after 8 hours, is naturally cooling to room temperature with stove.
Step 8: the powder after third time pre-burning is added dehydrated alcohol, is ball milling under 400r/min 12 in ball milling speed
Hour, cross 300 mesh dusting covers after then the compound obtaining being dried at 80 DEG C；Add appropriate in compound after sizing
Binding agent regrinding, after so that the two is sufficiently uniformly mixed, after 200 mesh sieves.Wherein, binding agent is that weight percentage is
5% polyvinyl alcohol water solution, its consumption is the 7% of mixed powder gross weight.
Step 9: the compound after the completion of sieving is carried out ripening more than 12 hours, makes binding agent abundant with powder body
Mixing, is pressed into ceramic green sheet, and carries out plastic removal process.
Step 10: the ceramic green sheet after plastic removal is processed rises to 1400 DEG C with the heating rate of 5 DEG C/min, keeps this temperature
After degree calcining 4 hours, it is then cooled to room temperature.
Step 11: the ceramic green sheet after cooling is carried out polishing both surfaces, drapes over one's shoulders in silver electrode silicone oil at room temperature
Impose the DC voltage polarization 30min of 5kv/mm, obtain stannum barium titanate calcium ceramic material.
Learn after tested: the piezoceramic material that the present embodiment prepares performance parameter at room temperature is as follows: d33=
400pc/n, ε=6876, tan δ=0.131.
Embodiment 4
This example provides a kind of (baxca1-x)(tiym1-y)o3System piezoceramic material, its composition such as following formula represents:
(ba0.95ca0.05)(ti0.9sn0.1)o3, wherein m is sn, and the value of x is the value of 0.95, y is 0.9.
(ba in the present embodimentxca1-x)(tiym1-y)o3The preparation method of system piezoceramic material, referring to Fig. 1, concrete step
Suddenly as follows:
Step one: with analyze pure be more than 98% ba (ch3coo)2、ca(ch3coo)2、tio2And sno2As raw material,
According to formula (ba0.85ca0.15)(ti0.95sn0.05)o3Stoichiometric proportion accurately calculate and precise.
Step 2: by load weighted ba (ch3coo)2And ca (ch3coo)2Be formulated as settled solution respectively in beaker and
After mix, stirring keep its clarification；Tio is sequentially added in settled solution2、sno2, monohydrate potassium.
Step 3: mixed solution is placed on magnetic agitation platform at 80 DEG C of temperature heated and stirred until being evaporated water
Point, then it is positioned in baking oven 250 DEG C of heating, dryings 8 hours, the partially carbonized variable color of compound；Spoon is used after taking out from baking oven
With brush, compound is carefully scraped from beaker, grind levigate in mortar.
Step 4: compound is placed in alumina crucible, rises to 750 DEG C with the heating rate of 3 DEG C/min and to be incubated 4 little
When, remove remaining Organic substance.
Step 5: the compound after pre-burning is taken out from crucible and is placed in finely ground in mortar, then put into again in crucible,
Rise to 1200 DEG C with the heating rate of 5 DEG C/min, keep this temperature calcination after 8 hours, be naturally cooling to room temperature with stove.
Step 6: the powder after second pre-burning is added dehydrated alcohol, is ball milling under 400r/min 12 in ball milling speed
Hour.
Step 7: the compound after ball milling is placed in 80 DEG C of drying of temperature in baking oven, then with the intensification speed of 5 DEG C/min
Rate rises to 1250 DEG C, keeps this temperature calcination after 8 hours, is naturally cooling to room temperature with stove.
Step 8: the powder after third time pre-burning is added dehydrated alcohol, is ball milling under 400r/min 12 in ball milling speed
Hour, cross 300 mesh dusting covers after then the compound obtaining being dried at 80 DEG C；Appropriate gluing is added in compound after sizing
Knot agent regrinding, after so that the two is sufficiently uniformly mixed, after 200 mesh sieves.Wherein, binding agent is that weight percentage is
5% polyvinyl alcohol water solution, its consumption is the 7% of mixed powder gross weight.
Step 9: the compound after the completion of sieving is carried out ripening more than 12 hours, makes binding agent abundant with powder body
Mixing, is pressed into ceramic green sheet, and carries out plastic removal process.
Step 10: the ceramic green sheet after plastic removal is processed rises to 1400 DEG C with the heating rate of 5 DEG C/min, keeps this temperature
After degree calcining 4 hours, it is then cooled to room temperature.
Step 11: the ceramic green sheet after cooling is carried out polishing both surfaces, drapes over one's shoulders in silver electrode silicone oil at room temperature
Impose the DC voltage polarization 30min of 5kv/mm, obtain stannum barium titanate calcium ceramic material.
Learn after tested: the piezoceramic material that the present embodiment prepares performance parameter at room temperature is as follows: d33=
548pc/n, kp=0.37, ε=13027, tan δ=0.051, qm=81.2.
Claims (3)
1. a kind of (baxca1-x)(tiym1-y)o3The preparation of (m=zr, sn) (0≤x≤1,0≤y≤1) system piezoceramic material
Method is it is characterised in that comprise the following steps:
Step one: according to formula (baxca1-x)(tiym1-y)o3In stoichiometric proportion accurately calculate and weigh raw material；
Step 2: by load weighted ba (ch3coo)2And ca (ch3coo)2It is formulated as settled solution respectively then to mix in beaker
Close, stirring keeps its clarification；Tio is sequentially added in settled solution2、mo2, monohydrate potassium；
Step 3: mixed solution is placed in heated and stirred on magnetic agitation platform until evaporating water, is then positioned over baking oven
Middle heating, drying, the partially carbonized variable color of compound；With spoon and brush, compound is careful from beaker after taking out from baking oven
Scrape, grind levigate in mortar；
Step 4: compound is placed in alumina crucible, remaining Organic substance is removed in pre-burning；
Step 5: the compound after heat treatment is taken out from crucible and is placed in finely ground in mortar, then put into again in crucible, open
Begin second pre-burning；
Step 6: the powder after second pre-burning is added dehydrated alcohol to carry out ball milling；
Step 7: carry out third time pre-burning after the compound after ball milling is dried；
Step 8: the powder after third time pre-burning is added dehydrated alcohol to carry out ball milling, then by after the compound obtaining drying
Sieve；Add binding agent regrinding in compound after sizing, after so that the two is sufficiently uniformly mixed, carry out second mistake
Sieve；
Step 9: the compound after the completion of sieving is carried out ripening more than 12 hours, allows binding agent to be sufficiently mixed with powder body,
It is pressed into ceramic green sheet, and carry out plastic removal process；
Step 10: the ceramic green sheet after plastic removal is processed is calcined, and is then cooled to room temperature；
Step 11: the ceramic green sheet after cooling is carried out polishing both surfaces, drapes over one's shoulders silver electrode and polarize in silicone oil, obtains pottery
Material.
2. one kind (ba according to claim 1xca1-x)(tiym1-y)o3The preparation method of system piezoceramic material, its
It is characterised by, in step 2, the amount of addition monohydrate potassium material is 1-3 times of the amount of metal ion species；
In step 3, on magnetic agitation platform, the temperature of heating is 70-90 DEG C, and the temperature of heating, drying is 200- in an oven
250 DEG C, the time is 8-10 hour；
In step 4, first time calcined temperature is 700-750 DEG C, and temperature retention time is 4-6 hour；
In step 5, (baxca1-x)(tiyzr1-y)o3Second calcined temperature of system compound is 1250-1300 DEG C, insulation
Time is 8-10 hour；(baxca1-x)(tiysn1-y)o3Second calcined temperature of system compound is 1150-1200 DEG C, insulation
Time is 8-10 hour；
In step 5 and step 8, the speed of described ball milling is 200-400r/min, and Ball-milling Time is 10-12 hour；
In step 7, the drying temperature of described compound is 70-90 DEG C, (baxca1-x)(tiyzr1-y)o3System compound
Three times calcined temperature is 1300-1350 DEG C, and temperature retention time is 8-10 hour；(baxca1-x)(tiysn1-y)o3System compound
Three times calcined temperature is 1200-1250 DEG C, and temperature retention time is 8-10 hour；
In step 8, the mesh number sieved for the first time is 300 mesh, and the mesh number sieved for the second time is 100-300 mesh；
In step 8, the polyvinyl alcohol water solution that described binding agent is 5% for weight percentage, the consumption of described binding agent
It is about the 6-8% of mixed powder gross weight；
In step 9, tablet machine pressure is set to 8-10mpa；
In step 9, the temperature of described plastic removal is 700-750 DEG C, and temperature retention time is 4-6 hour；
In step 10, described (baxca1-x)(tiyzr1-y)o3The calcining heat of system is 1400-1550 DEG C, and heating rate is
3-5℃/min；(baxca1-x)(tiysn1-y)o3The calcining heat of system is 1300-1450 DEG C, and heating rate is 3-5 DEG C/min；
In step 11, the temperature of described polarization is room temperature, and polarizing voltage is 3-6kv/mm, and the polarization time is 20-30min.
3. (the ba being obtained according to one of claim 1 or 2 methods describedxca1-x)(tiym1-y)o3(m=zr, sn) system piezoelectricity
Ceramic material, its d33At least above 500pc/n, tan δ is at least below 0.03.
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| CN105645953A (en) * | 2015-12-31 | 2016-06-08 | 中国科学院声学研究所 | Preparation method of lead-free piezoelectric ceramic and preparation method of lead-free piezoelectric ceramic thin film |
| CN106409509A (en) * | 2016-03-23 | 2017-02-15 | 东莞理工学院 | Transparent film varactor and preparation method thereof |
| CN106478095A (en) * | 2016-09-28 | 2017-03-08 | 陕西科技大学 | Ba0.9Ca0.1Ti0.9Zr0.1O3/CoFe2O4Layered electromagnetic composite and preparation method thereof |
| CN106431398A (en) * | 2016-09-28 | 2017-02-22 | 陕西科技大学 | Ba0.9Ca0.1Ti0.9Zr0.1O3/Co0.8Ni0.1Zn0.1Fe2O4 layered magnetoelectric composite and preparation method thereof |
| CN107324803A (en) * | 2017-07-17 | 2017-11-07 | 陕西师范大学 | A kind of method that co-precipitation prepares barium calcium zirconate titanate lead-free piezoceramic material |
| CN108383525B (en) * | 2018-04-09 | 2022-02-18 | 聊城大学 | Potassium sodium niobate-based ceramic material and preparation method thereof |
| CN110642621B (en) * | 2019-10-21 | 2021-12-21 | 湖南云天雾化科技有限公司 | High-performance piezoelectric ceramic for electronic cigarette oil atomization and manufacturing method thereof |
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