CN116120053A - Bismuth sodium titanate-based leadless antiferroelectric ceramic material and preparation method thereof - Google Patents
Bismuth sodium titanate-based leadless antiferroelectric ceramic material and preparation method thereof Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 66
- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 239000011734 sodium Substances 0.000 claims abstract description 137
- 238000007873 sieving Methods 0.000 claims abstract description 85
- 238000000498 ball milling Methods 0.000 claims abstract description 82
- 239000000463 material Substances 0.000 claims abstract description 68
- 238000002156 mixing Methods 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000008367 deionised water Substances 0.000 claims abstract description 49
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 49
- 238000001816 cooling Methods 0.000 claims abstract description 42
- 229910002115 bismuth titanate Inorganic materials 0.000 claims abstract description 38
- 239000004575 stone Substances 0.000 claims abstract description 35
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 27
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 26
- 239000011267 electrode slurry Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000000643 oven drying Methods 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 52
- 239000000203 mixture Substances 0.000 claims description 49
- 229910052845 zircon Inorganic materials 0.000 claims description 46
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 46
- 238000001035 drying Methods 0.000 claims description 45
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 42
- 238000005245 sintering Methods 0.000 claims description 27
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 22
- 238000004140 cleaning Methods 0.000 claims description 22
- 239000011248 coating agent Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 22
- 238000005498 polishing Methods 0.000 claims description 22
- 229910052709 silver Inorganic materials 0.000 claims description 22
- 239000004332 silver Substances 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 21
- 239000004615 ingredient Substances 0.000 claims description 20
- 229910002112 ferroelectric ceramic material Inorganic materials 0.000 claims description 7
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 abstract description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000003825 pressing Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 45
- 238000005303 weighing Methods 0.000 description 35
- 229910002367 SrTiO Inorganic materials 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 19
- 238000004146 energy storage Methods 0.000 description 11
- 239000000919 ceramic Substances 0.000 description 8
- 239000003985 ceramic capacitor Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 229910052797 bismuth Inorganic materials 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- XPXCLKDJWMSNJG-UHFFFAOYSA-N [Na].[Bi].[Sr] Chemical compound [Na].[Bi].[Sr] XPXCLKDJWMSNJG-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Abstract
The invention discloses a bismuth sodium titanate-based lead-free antiferroelectric ceramic material and a preparation method thereof, and belongs to the field of material preparation. The raw material of the ceramic material is Bi 2 O 3 、Na 2 CO 3 、TiO 2 、SrCO 3 、MgO、SnO 2 Bi is mixed with 2 O 3 、Na 2 CO 3 、TiO 2 、SrCO 3 、MgO、SnO 2 Mixing with zirconium ball stone and deionized water, ball milling, oven drying, sieving, pressing to obtain sample, maintaining temperature in air for 3 hr, cooling with furnace, and grindingFinally, the electrode slurry is coated, and the bismuth sodium titanate-based leadless antiferroelectric ceramic material is prepared. The sodium bismuth titanate-based lead-free antiferroelectric ceramic material prepared by the method has obvious relaxation phenomenon, simple preparation process, environment friendliness, low manufacturing cost, large dielectric constant, small dielectric loss, excellent high-temperature stability and obvious frequency dispersion, is widely applied, and has excellent application in a pulse power system.
Description
Technical Field
The invention belongs to the field of material preparation, and relates to a sodium bismuth titanate-based leadless antiferroelectric ceramic material and a preparation method thereof.
Background
The ceramic-based dielectric capacitor can meet the conditions of high power density, wide temperature and frequency range, and the like. It has a stronger temperature resistance than polymer film capacitors and thus has a wider application. In dielectric materials, temperature stability, frequency stability and fatigue resistance are equally important as energy storage density and energy storage efficiency. BNT-based leadless energy storage ceramics have wide application prospect in the aspects of energy storage performance and high pulse performance, and are leadless ferroelectric ceramic materials with excellent performance, and have high saturation polarization intensity so that the BNT-based leadless energy storage ceramics have potential to be main dielectric materials in dielectric ceramic capacitors. In the aspect of energy storage, the reduction of dielectric loss in the equipment is beneficial to improving energy storage efficiency and prolonging the cycle service life of components and parts, and is beneficial to long-term operation of the equipment. However, the BNT-based ceramic still has the problems to be solved, the breakdown field strength is low, the remnant polarization strength is high, and the improvement of the energy storage density is limited.
Disclosure of Invention
The invention aims to solve the problems of low breakdown field intensity, high remnant polarization intensity and limitation of energy storage density improvement of BNT-based ceramics in the prior art, and provides a sodium bismuth titanate-based leadless antiferroelectric ceramic material and a preparation method thereof.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme:
the chemical formula of the sodium bismuth titanate based leadless antiferroelectric ceramic material is (1-x) (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 -xBi(Mg 0.5 Sn 0.5 )O 3 Wherein x is mole percent, and the value range of x is 0-0.2.
Preferably, the mole percentage x=0, 0.04, 0.08, 0.12, 0.16 or 0.20.
The invention provides a preparation method of a sodium bismuth titanate-based leadless antiferroelectric ceramic material, which comprises the following steps:
step one: bi is mixed with 2 O 3 、Na 2 CO 3 、TiO 2 And SrCO 3 Mixing to form a mixture A;
step two: mixing the mixture A, zircon and deionized water, sequentially ball milling, oven drying, sieving, and maintaining the temperature to form a main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Powder;
step three: bi is mixed with 2 O 3 MgO and SnO 2 Added to the main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Forming a full-batch by powder;
step four: mixing the full ingredients, the zircon ball stone and the deionized water, and then sequentially performing ball milling, drying and sieving to form a sieving material;
step five: preparing the screened material into a sample, cooling to room temperature after sintering, and polishing and cleaning to obtain a pretreated sample;
step six: and uniformly coating silver electrode slurry on the front and back surfaces of the pretreated sample, and sintering to obtain the sodium bismuth titanate-based lead-free relaxation ferroelectric ceramic material sample.
Preferably, in the second step, the mixture A, the zircon ball stone and the deionized water are mixed according to the mass ratio of 1:4:1.3, ball-milled, dried and sieved in sequence, and then are placed in a muffle furnace to be insulated for 2-4 hours at 800-900 ℃ to form a main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 And (3) powder.
Preferably, in the second step and the fourth step, the ball milling time is 11.5-12.5 h.
Preferably, in the second step, the screen is sieved by a 75-85-mesh screen.
Preferably, in the third step, 4mol% to 20mol% of Bi is respectively weighed according to the mole percentage 2 O 3 MgO and SnO 2 。
Preferably, in the fourth step, the screen is a 115-125 mesh screen.
Preferably, in the fifth step, the screened material is prepared into a sample under the pressure of 115MPa to 125MPa, then the sample is placed in an alumina sagger taking alumina as a base plate and placed in a high-temperature box-type furnace, the temperature is kept for 2 to 4 hours when the temperature is increased to 1150 to 1200 ℃ at 4 to 6 ℃ per minute, and then the temperature is reduced to 450 to 550 ℃ at 4 to 6 ℃ per minute, and then the sample is cooled to room temperature along with the furnace.
Preferably, in the step six, sintering is carried out at 650-750 ℃ for 15-25 min to obtain the bismuth sodium titanate based lead-free relaxor ferroelectric ceramic material sample.
Compared with the prior art, the invention has the following beneficial effects:
the sodium bismuth titanate-based lead-free antiferroelectric ceramic material provided by the invention has the advantages of obvious relaxation phenomenon, large dielectric constant, small dielectric loss, excellent high-temperature stability and obvious frequency dispersion, and can be applied to a multilayer ceramic capacitor.
The invention provides a preparation method of a bismuth sodium titanate-based leadless antiferroelectric ceramic material, which comprises the steps of mixing Bi with a ceramic material 2 O 3 、Na 2 CO 3 、TiO 2 And SrCO 3 Mixing to form a mixture A, and mixing the mixture A, the zircon ball and deionized water to obtain a main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Powder of Bi 2 O 3 MgO and SnO 2 Added to the main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Forming a full-batching material by the powder, and then mixing the full-batching material, the zircon ball stone and deionized water for post-treatment to form a screened material; and then the screened material is treated to obtain a sodium bismuth titanate-based lead-free relaxor ferroelectric ceramic material sample. The preparation method adopts a solid phase method for preparation, and is suitable for industrialized production. Bi is mixed with 2 O 3 MgO and SnO 2 Added to the main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 The powder is doped, which is beneficial to improving the energy storage efficiency and the relaxation of the strontium bismuth sodium titanate ceramic. Simple preparation process, low material cost, higher dielectric constant, low dielectric loss and excellent high performanceThe temperature stability and obvious relaxation phenomenon are important candidate materials for replacing lead-based relaxation ferroelectrics to be used as multilayer ceramic capacitors in technical and economical aspects. Therefore, the preparation method provided by the invention can solve the problems existing in the prior art.
Drawings
For a clearer description of the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a flow chart of a method for preparing the sodium bismuth titanate-based leadless antiferroelectric ceramic material of the present invention.
FIG. 2 is a graph of the dielectric constant and dielectric loss versus temperature for a mole percent 0 of the present invention.
FIG. 3 is a graph showing the dielectric constant and dielectric loss characteristics of the present invention as a function of temperature at a mole percent of 0.04.
FIG. 4 is a graph showing the dielectric constant and dielectric loss characteristics of the present invention as a function of temperature at a mole percent of 0.08.
FIG. 5 is a graph showing the dielectric constant and dielectric loss characteristics of the present invention as a function of temperature at a mole percent of 0.12.
FIG. 6 is a graph of the dielectric constant and dielectric loss versus temperature for a mole percent of 0.16 of the present invention.
FIG. 7 is a graph showing the dielectric constant and dielectric loss characteristics of the present invention as a function of temperature at a mole percent of 0.20.
FIG. 8 is a graph showing the dielectric constant and dielectric loss versus temperature for a sample of the present invention at 1 MHz.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that: like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further definition or explanation thereof is necessary in the following figures.
In the description of the embodiments of the present invention, it should be noted that, if the terms "upper," "lower," "horizontal," "inner," and the like indicate an azimuth or a positional relationship based on the azimuth or the positional relationship shown in the drawings, or the azimuth or the positional relationship in which the inventive product is conventionally put in use, it is merely for convenience of describing the present invention and simplifying the description, and does not indicate or imply that the apparatus or element to be referred to must have a specific azimuth, be configured and operated in a specific azimuth, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like, are used merely to distinguish between descriptions and should not be construed as indicating or implying relative importance.
Furthermore, the term "horizontal" if present does not mean that the component is required to be absolutely horizontal, but may be slightly inclined. As "horizontal" merely means that its direction is more horizontal than "vertical", and does not mean that the structure must be perfectly horizontal, but may be slightly inclined.
In the description of the embodiments of the present invention, it should also be noted that, unless explicitly specified and limited otherwise, the terms "disposed," "mounted," "connected," and "connected" should be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
The invention is described in further detail below with reference to the attached drawing figures:
the chemical formula of the sodium bismuth titanate based leadless antiferroelectric ceramic material is (1-x) (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 -xBi(Mg 0.5 Sn 0.5 )O 3 Wherein x is mole percent, and the value range of the mole percent x is 0-0.2. The main material is Bi 2 O 3 、Na 2 CO 3 、TiO 2 、SrCO 3 The doping material is Bi 2 O 3 MgO and SnO 2 Wherein, the doping material Bi is calculated according to mole percent 2 O 3 MgO and SnO 2 Accounting for 4mol percent to 20mol percent of the total ingredients.
Specifically, the mole percentage x=0, 0.04, 0.08, 0.12, 0.16, or 0.20.
The invention provides a preparation method of a sodium bismuth titanate-based leadless antiferroelectric ceramic material, which is shown in figure 1 and comprises the following steps:
step one: bi is mixed with 2 O 3 、Na 2 CO 3 、TiO 2 And SrCO 3 Mixing to form a mixture A;
step two: mixing the mixture A, zircon and deionized water, sequentially ball milling, oven drying, sieving, and maintaining the temperature to form a main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Powder;
step three: bi is mixed with 2 O 3 MgO and SnO 2 Added to the main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Forming a full-batch by powder;
step four: mixing the full ingredients, the zircon ball stone and the deionized water, and then sequentially performing ball milling, drying and sieving to form a sieving material;
step five: preparing the screened material into a sample, cooling to room temperature after sintering, and polishing and cleaning to obtain a pretreated sample;
step six: and uniformly coating silver electrode slurry on the front and back surfaces of the pretreated sample, and sintering to obtain the sodium bismuth titanate-based lead-free relaxation ferroelectric ceramic material sample.
The method comprises the following specific steps:
step one: according to Bi 0.5 Na 0.5 TiO 3 With SrTiO 3 Respectively weighing Bi according to the stoichiometric ratio of 0.7:0.3 2 O 3 、Na 2 CO 3 、TiO 2 、SrCO 3 Mixing to form a mixture A;
step two: respectively taking the mixture A, the zircon ball stone and the deionized water, mixing according to the mass ratio of 1:4:1.3, sequentially performing ball milling, drying and sieving, and then placing in a muffle furnace to keep the temperature at 800-900 ℃ for 2-4 hours to form a main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Powder for standby; wherein, ball milling is carried out for 11.5h to 12.5h, and sieving is carried out for 75-85 mesh.
Step three: respectively weighing 4mol% to 20mol% of Bi according to the mol percentage 2 O 3 MgO and SnO 2 Added to the main phase (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Forming a full-batch by powder;
step four: respectively taking the full ingredients, the zircon ball stone and the deionized water obtained in the step three, mixing according to the mass ratio of 1:4:1.3, and then sequentially performing ball milling, drying and sieving to form a sieving material; wherein, ball milling is carried out for 11.5h to 12.5h, and sieving is carried out by a 115-125-mesh sieve.
Step five: preparing the screened material obtained in the step four into a sample under the pressure of 115-125 MPa, then placing the sample in an alumina sagger taking alumina as a base plate, heating to 1100-1120 ℃ at 4-6 ℃ per minute, preserving heat for 2-4 hours, cooling to 450-550 ℃ at 4-6 ℃ per minute, and cooling to room temperature along with the furnace;
step six: after polishing and cleaning the sample sintered in the fifth step, uniformly coating silver electrode slurry on the front and back sides of the sample, and sintering at 650-750 ℃ for 15-25 min to obtain a sodium bismuth titanate-based lead-free antiferroelectric ceramic material sample.
Example 1:
bi in this example 0.5 Na 0.5 TiO 3 The chemical formula of the lead-free-based antiferroelectric ceramic material is (1-x) (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 -xBi(Mg 0.5 Sn 0.5 )O 3 Wherein x=0;
step one: according to Bi 0.5 Na 0.5 TiO 3 With SrTiO 3 Respectively weighing Bi according to the stoichiometric ratio of 0.7:0.3 2 O 3 、Na 2 CO 3 、TiO 2 、SrCO 3 Mixing to form a mixture A;
step two: respectively taking a mixture A, zircon and deionized water, mixing according to the mass ratio of 1:4:1.3, sequentially performing ball milling, drying and sieving, and placing in a muffle furnace to keep the temperature at 850 ℃ for 3 hours to form a main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Powder for standby; wherein, ball milling is carried out for 12 hours, and sieving is carried out by a 80-mesh sieve.
Step three: the main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Grinding the powder, mixing the ground powder, the zirconium ball stone and deionized water according to the mass ratio of 1:4:1.3, ball milling for 12 hours, drying to obtain a drying material, and sieving the drying material with a 120-mesh sieve;
step four: preparing the screened material obtained in the step three into a sample under the pressure of 120MPa, then placing the sample in an alumina sagger taking alumina as a base plate in a high-temperature box type furnace, heating to 1150 ℃ at 5 ℃/min, preserving heat for 3 hours, cooling to 500 ℃ at 5 ℃/min, and cooling to room temperature along with the furnace;
step six: after polishing and cleaning the sintered sample, uniformly coating silver electrode slurry on the front and back sides of the sample, and sintering at 700 ℃ for 20min to obtain Bi 0.5 Na 0.5 TiO 3 Basic lead-free ironSamples of electroceramic material.
Example 2:
bi in this example 0.5 Na 0.5 TiO 3 The chemical formula of the lead-free-based antiferroelectric ceramic material is (1-x) (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 -xBi(Mg 0.5 Sn 0.5 )O 3 Wherein x=0.04;
step one: according to Bi 0.5 Na 0.5 TiO 3 With SrTiO 3 Respectively weighing Bi according to the stoichiometric ratio of 0.7:0.3 2 O 3 、Na 2 CO 3 、TiO 2 、SrCO 3 Mixing to form a mixture A;
step two: respectively taking a mixture A, zircon and deionized water, mixing according to the mass ratio of 1:4:1.3, sequentially performing ball milling, drying and sieving, and placing in a muffle furnace to keep the temperature at 850 ℃ for 3 hours to form a main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Powder for standby; wherein, ball milling is carried out for 12 hours, and sieving is carried out by a 80-mesh sieve.
Step three: respectively weighing 4mol% of Bi according to the mol percentage 2 O 3 MgO and SnO 2 Added to the main phase (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Forming a full-batch by powder;
step four: respectively taking the full ingredients, the zircon ball stone and the deionized water obtained in the step three, mixing according to the mass ratio of 1:4:1.3, and then sequentially performing ball milling, drying and sieving to form a sieving material; wherein, ball milling is carried out for 12 hours, and a 120-mesh sieve is sieved.
Step five: preparing a sample from the screened material obtained in the step four under the pressure of 120MPa, placing the sample in an alumina sagger taking alumina as a base plate in a high-temperature box type furnace, heating to 1150 ℃ at 5 ℃/min, preserving heat for 3 hours, cooling to 500 ℃ at 5 ℃/min, and cooling to room temperature along with the furnace;
step six: and after polishing and cleaning the sample sintered in the fifth step, uniformly coating silver electrode slurry on the front and back sides of the sample, and sintering at 700 ℃ for 20min to obtain a sodium bismuth titanate-based lead-free antiferroelectric ceramic material sample.
Example 3:
bi of this example 0.5 Na 0.5 TiO 3 The chemical formula of the lead-free-based antiferroelectric ceramic material is (1-x) (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 -xBi(Mg 0.5 Sn 0.5 )O 3 Wherein x=0.08;
step one: according to Bi 0.5 Na 0.5 TiO 3 With SrTiO 3 Respectively weighing Bi according to the stoichiometric ratio of 0.7:0.3 2 O 3 、Na 2 CO 3 、TiO 2 、SrCO 3 Mixing to form a mixture A;
step two: respectively taking a mixture A, zircon and deionized water, mixing according to the mass ratio of 1:4:1.3, sequentially performing ball milling, drying and sieving, and placing in a muffle furnace to keep the temperature at 850 ℃ for 3 hours to form a main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Powder for standby; wherein, ball milling is carried out for 12 hours, and sieving is carried out by a 80-mesh sieve.
Step three: respectively weighing 8mol% of Bi according to the mol percentage 2 O 3 MgO and SnO 2 Added to the main phase (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Forming a full-batch by powder;
step four: respectively taking the full ingredients, the zircon ball stone and the deionized water obtained in the step three, mixing according to the mass ratio of 1:4:1.3, and then sequentially performing ball milling, drying and sieving to form a sieving material; wherein, ball milling is carried out for 12 hours, and a 120-mesh sieve is sieved.
Step five: preparing a sample from the screened material obtained in the step four under the pressure of 120MPa, placing the sample in an alumina sagger taking alumina as a base plate in a high-temperature box type furnace, heating to 1150 ℃ at 5 ℃/min, preserving heat for 3 hours, cooling to 500 ℃ at 5 ℃/min, and cooling to room temperature along with the furnace;
step six: and after polishing and cleaning the sample sintered in the fifth step, uniformly coating silver electrode slurry on the front and back sides of the sample, and sintering at 700 ℃ for 20min to obtain a sodium bismuth titanate-based lead-free antiferroelectric ceramic material sample.
Example 4:
bi of this example 0.5 Na 0.5 TiO 3 The chemical formula of the lead-free-based antiferroelectric ceramic material is (1-x) (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 -xBi(Mg 0.5 Sn 0.5 )O 3 Wherein x=0.12;
step one: according to Bi 0.5 Na 0.5 TiO 3 With SrTiO 3 Respectively weighing Bi according to the stoichiometric ratio of 0.7:0.3 2 O 3 、Na 2 CO 3 、TiO 2 、SrCO 3 Mixing to form a mixture A;
step two: respectively taking a mixture A, zircon and deionized water, mixing according to the mass ratio of 1:4:1.3, sequentially performing ball milling, drying and sieving, and placing in a muffle furnace to keep the temperature at 850 ℃ for 3 hours to form a main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Powder for standby; wherein, ball milling is carried out for 12 hours, and sieving is carried out by a 80-mesh sieve.
Step three: respectively weighing 12mol percent of Bi according to the mol percent 2 O 3 MgO and SnO 2 Added to the main phase (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Forming a full-batch by powder;
step four: respectively taking the full ingredients, the zircon ball stone and the deionized water obtained in the step three, mixing according to the mass ratio of 1:4:1.3, and then sequentially performing ball milling, drying and sieving to form a sieving material; wherein, ball milling is carried out for 12 hours, and a 120-mesh sieve is sieved.
Step five: preparing a sample from the screened material obtained in the step four under the pressure of 120MPa, placing the sample in an alumina sagger taking alumina as a base plate in a high-temperature box type furnace, heating to 1150 ℃ at 5 ℃/min, preserving heat for 3 hours, cooling to 500 ℃ at 5 ℃/min, and cooling to room temperature along with the furnace;
step six: and after polishing and cleaning the sample sintered in the fifth step, uniformly coating silver electrode slurry on the front and back sides of the sample, and sintering at 700 ℃ for 20min to obtain a sodium bismuth titanate-based lead-free antiferroelectric ceramic material sample.
Example 5:
this practice isExample Bi 0.5 Na 0.5 TiO 3 The chemical formula of the lead-free-based antiferroelectric ceramic material is (1-x) (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 -xBi(Mg 0.5 Sn 0.5 )O 3 Wherein x=0.16;
step one: according to Bi 0.5 Na 0.5 TiO 3 With SrTiO 3 Respectively weighing Bi according to the stoichiometric ratio of 0.7:0.3 2 O 3 、Na 2 CO 3 、TiO 2 、SrCO 3 Mixing to form a mixture A;
step two: respectively taking a mixture A, zircon and deionized water, mixing according to the mass ratio of 1:4:1.3, sequentially performing ball milling, drying and sieving, and placing in a muffle furnace to keep the temperature at 850 ℃ for 3 hours to form a main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Powder for standby; wherein, ball milling is carried out for 12 hours, and sieving is carried out by a 80-mesh sieve.
Step three: respectively weighing 16mol% of Bi according to the mol percentage 2 O 3 MgO and SnO 2 Added to the main phase (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Forming a full-batch by powder;
step four: respectively taking the full ingredients, the zircon ball stone and the deionized water obtained in the step three, mixing according to the mass ratio of 1:4:1.3, and then sequentially performing ball milling, drying and sieving to form a sieving material; wherein, ball milling is carried out for 12 hours, and a 120-mesh sieve is sieved.
Step five: preparing a sample from the screened material obtained in the step four under the pressure of 120MPa, placing the sample in an alumina sagger taking alumina as a base plate in a high-temperature box type furnace, heating to 1150 ℃ at 5 ℃/min, preserving heat for 3 hours, cooling to 500 ℃ at 5 ℃/min, and cooling to room temperature along with the furnace;
step six: and after polishing and cleaning the sample sintered in the fifth step, uniformly coating silver electrode slurry on the front and back sides of the sample, and sintering at 700 ℃ for 20min to obtain a sodium bismuth titanate-based lead-free antiferroelectric ceramic material sample.
Example 6:
bi of this example 0.5 Na 0.5 TiO 3 The chemical formula of the lead-free-based antiferroelectric ceramic material is (1-x) (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 -xBi(Mg 0.5 Sn 0.5 )O 3 Wherein x=0.20;
step one: according to Bi 0.5 Na 0.5 TiO 3 With SrTiO 3 Respectively weighing Bi according to the stoichiometric ratio of 0.7:0.3 2 O 3 、Na 2 CO 3 、TiO 2 、SrCO 3 Mixing to form a mixture A;
step two: respectively taking a mixture A, zircon and deionized water, mixing according to the mass ratio of 1:4:1.3, sequentially performing ball milling, drying and sieving, and placing in a muffle furnace to keep the temperature at 850 ℃ for 3 hours to form a main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Powder for standby; wherein, ball milling is carried out for 12 hours, and sieving is carried out by a 80-mesh sieve.
Step three: respectively weighing 20mol% of Bi according to the mol percentage 2 O 3 MgO and SnO 2 Added to the main phase (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Forming a full-batch by powder;
step four: respectively taking the full ingredients, the zircon ball stone and the deionized water obtained in the step three, mixing according to the mass ratio of 1:4:1.3, and then sequentially performing ball milling, drying and sieving to form a sieving material; wherein, ball milling is carried out for 12 hours, and a 120-mesh sieve is sieved.
Step five: preparing a sample from the screened material obtained in the step four under the pressure of 120MPa, placing the sample in an alumina sagger taking alumina as a base plate in a high-temperature box type furnace, heating to 1150 ℃ at 5 ℃/min, preserving heat for 3 hours, cooling to 500 ℃ at 5 ℃/min, and cooling to room temperature along with the furnace;
step six: and after polishing and cleaning the sample sintered in the fifth step, uniformly coating silver electrode slurry on the front and back sides of the sample, and sintering at 700 ℃ for 20min to obtain a sodium bismuth titanate-based lead-free antiferroelectric ceramic material sample.
Example 7:
bi in this example 0.5 Na 0.5 TiO 3 Basic leadless antiferroelectric ceramicThe chemical formula of the porcelain material is (1-x) (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 -xBi(Mg 0.5 Sn 0.5 )O 3 Wherein x=0;
step one: according to Bi 0.5 Na 0.5 TiO 3 With SrTiO 3 Respectively weighing Bi according to the stoichiometric ratio of 0.7:0.3 2 O 3 、Na 2 CO 3 、TiO 2 、SrCO 3 Mixing to form a mixture A;
step two: respectively taking a mixture A, zircon and deionized water, mixing according to the mass ratio of 1:4:1.3, sequentially performing ball milling, drying and sieving, and placing in a muffle furnace to keep the temperature at 850 ℃ for 3 hours to form a main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Powder for standby; wherein, ball milling is carried out for 11.5 hours, and sieving is carried out by a 75-mesh sieve.
Step three: the main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Grinding the powder, mixing the ground powder, the zirconium ball stone and deionized water according to the mass ratio of 1:4:1.3, ball milling for 11.5 hours, drying to obtain a drying material, and sieving the drying material with a 115-mesh sieve;
step four: preparing the screened material obtained in the step three into a sample under the pressure of 115MPa, then placing the sample in an alumina sagger taking alumina as a base plate in a high-temperature box type furnace, heating to 1100 ℃ at 4 ℃/min, preserving heat for 2 hours, cooling to 450 ℃ at 4 ℃/min, and cooling to room temperature along with the furnace;
step six: after polishing and cleaning the sintered sample, uniformly coating silver electrode slurry on the front and back sides of the sample, and sintering at 650 ℃ for 15min to obtain Bi 0.5 Na 0.5 TiO 3 A sample of a lead-free antiferroelectric ceramic material.
Example 8:
bi in this example 0.5 Na 0.5 TiO 3 The chemical formula of the lead-free-based antiferroelectric ceramic material is (1-x) (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 -xBi(Mg 0.5 Sn 0.5 )O 3 Wherein x=0;
step one: according to Bi 0.5 Na 0.5 TiO 3 With SrTiO 3 Respectively weighing Bi according to the stoichiometric ratio of 0.7:0.3 2 O 3 、Na 2 CO 3 、TiO 2 、SrCO 3 Mixing to form a mixture A;
step two: respectively taking the mixture A, the zircon ball stone and the deionized water, mixing according to the mass ratio of 1:4:1.3, sequentially performing ball milling, drying and sieving, and then placing in a muffle furnace to keep the temperature at 900 ℃ for 3.5h to form a main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Powder for standby; wherein, ball milling is carried out for 12.5 hours, and a sieve with 85 meshes is sieved.
Step three: the main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Grinding the powder, mixing the ground powder, the zirconium ball stone and deionized water according to the mass ratio of 1:4:1.3, ball milling for 12.5 hours, drying to obtain a drying material, and sieving the drying material with a 125-mesh sieve;
step four: preparing the screened material obtained in the step three into a sample under the pressure of 125MPa, then placing the sample in an alumina sagger taking alumina as a base plate in a high-temperature box type furnace, heating to 1200 ℃ at 5 ℃/min, preserving heat for 4 hours, cooling to 550 ℃ at 5 ℃/min, and cooling to room temperature along with the furnace;
step six: after polishing and cleaning the sintered sample, uniformly coating silver electrode slurry on the front and back sides of the sample, and sintering at 750 ℃ for 25min to obtain Bi 0.5 Na 0.5 TiO 3 A sample of a lead-free antiferroelectric ceramic material.
Example 9:
bi in this example 0.5 Na 0.5 TiO 3 The chemical formula of the lead-free-based antiferroelectric ceramic material is (1-x) (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 -xBi(Mg 0.5 Sn 0.5 )O 3 Wherein x=0.04;
step one: according to Bi 0.5 Na 0.5 TiO 3 With SrTiO 3 Respectively weighing Bi according to the stoichiometric ratio of 0.7:0.3 2 O 3 、Na 2 CO 3 、TiO 2 、SrCO 3 Mixing to form a mixture A;
step two: respectively taking the mixture A, the zircon ball stone and the deionized water, mixing according to the mass ratio of 1:4:1.3, sequentially performing ball milling, drying and sieving, and then placing in a muffle furnace to keep the temperature at 800 ℃ for 2.5h to form a main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Powder for standby; wherein, ball milling is carried out for 11.5 hours, and sieving is carried out by a 75-mesh sieve.
Step three: respectively weighing 4mol% of Bi according to the mol percentage 2 O 3 MgO and SnO 2 Added to the main phase (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Forming a full-batch by powder;
step four: respectively taking the full ingredients, the zircon ball stone and the deionized water obtained in the step three, mixing according to the mass ratio of 1:4:1.3, and then sequentially performing ball milling, drying and sieving to form a sieving material; wherein, ball milling is carried out for 11.5 hours, and sieving is carried out by a 115-mesh sieve.
Step five: preparing a sample from the screened material obtained in the step four under the pressure of 115MPa, placing the sample in an alumina sagger taking alumina as a base plate in a high-temperature box type furnace, heating to 1100 ℃ at 4 ℃/min, preserving heat for 2 hours, cooling to 450 ℃ at 4 ℃/min, and cooling to room temperature along with the furnace;
step six: and (3) after polishing and cleaning the sample sintered in the fifth step, uniformly coating silver electrode slurry on the front and back sides of the sample, and sintering at 650 ℃ for 15min to obtain a sodium bismuth titanate-based lead-free antiferroelectric ceramic material sample.
Example 10:
bi in this example 0.5 Na 0.5 TiO 3 The chemical formula of the lead-free-based antiferroelectric ceramic material is (1-x) (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 -xBi(Mg 0.5 Sn 0.5 )O 3 Wherein x=0.04;
step one: according to Bi 0.5 Na 0.5 TiO 3 With SrTiO 3 Respectively weighing Bi according to the stoichiometric ratio of 0.7:0.3 2 O 3 、Na 2 CO 3 、TiO 2 、SrCO 3 Mixing to form a mixtureAn article A;
step two: respectively taking the mixture A, the zircon ball stone and the deionized water, mixing according to the mass ratio of 1:4:1.3, sequentially performing ball milling, drying and sieving, and then placing in a muffle furnace to keep the temperature at 900 ℃ for 3.5h to form a main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Powder for standby; wherein, ball milling is carried out for 12.5 hours, and a sieve with 85 meshes is sieved.
Step three: respectively weighing 4mol% of Bi according to the mol percentage 2 O 3 MgO and SnO 2 Added to the main phase (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Forming a full-batch by powder;
step four: respectively taking the full ingredients, the zircon ball stone and the deionized water obtained in the step three, mixing according to the mass ratio of 1:4:1.3, and then sequentially performing ball milling, drying and sieving to form a sieving material; wherein, ball milling is carried out for 12.5 hours, and a 125-mesh sieve is sieved.
Step five: preparing a sample from the screened material obtained in the step four under the pressure of 125MPa, placing the sample in an alumina sagger taking alumina as a base plate in a high-temperature box type furnace, heating to 1200 ℃ at a speed of 6 ℃/min, preserving heat for 4 hours, cooling to 550 ℃ at a speed of 6 ℃/min, and cooling to room temperature along with the furnace;
step six: and after polishing and cleaning the sample sintered in the fifth step, uniformly coating silver electrode slurry on the front and back sides of the sample, and sintering at 700 ℃ for 20min to obtain a sodium bismuth titanate-based lead-free antiferroelectric ceramic material sample.
Example 11:
bi of this example 0.5 Na 0.5 TiO 3 The chemical formula of the lead-free-based antiferroelectric ceramic material is (1-x) (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 -xBi(Mg 0.5 Sn 0.5 )O 3 Wherein x=0.08;
step one: according to Bi 0.5 Na 0.5 TiO 3 With SrTiO 3 Respectively weighing Bi according to the stoichiometric ratio of 0.7:0.3 2 O 3 、Na 2 CO 3 、TiO 2 、SrCO 3 Mixing to form a mixture A;
step two: respectively taking the mixture A, the zircon ball stone and the deionized water, mixing according to the mass ratio of 1:4:1.3, sequentially performing ball milling, drying and sieving, and then placing in a muffle furnace to keep the temperature at 800 ℃ for 2.5h to form a main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Powder for standby; wherein, ball milling is carried out for 11.5 hours, and sieving is carried out by a 75-mesh sieve.
Step three: respectively weighing 8mol% of Bi according to the mol percentage 2 O 3 MgO and SnO 2 Added to the main phase (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Forming a full-batch by powder;
step four: respectively taking the full ingredients, the zircon ball stone and the deionized water obtained in the step three, mixing according to the mass ratio of 1:4:1.3, and then sequentially performing ball milling, drying and sieving to form a sieving material; wherein, ball milling is carried out for 11.5 hours, and sieving is carried out by a 115-mesh sieve.
Step five: preparing a sample from the screened material obtained in the step four under the pressure of 115MPa, placing the sample in an alumina sagger taking alumina as a base plate in a high-temperature box type furnace, heating to 1100 ℃ at 4 ℃/min, preserving heat for 2 hours, cooling to 450 ℃ at 4 ℃/min, and cooling to room temperature along with the furnace;
step six: and (3) after polishing and cleaning the sample sintered in the fifth step, uniformly coating silver electrode slurry on the front and back sides of the sample, and sintering at 650 ℃ for 15min to obtain a sodium bismuth titanate-based lead-free antiferroelectric ceramic material sample.
Example 12:
bi of this example 0.5 Na 0.5 TiO 3 The chemical formula of the lead-free-based antiferroelectric ceramic material is (1-x) (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 -xBi(Mg 0.5 Sn 0.5 )O 3 Wherein x=0.08;
step one: according to Bi 0.5 Na 0.5 TiO 3 With SrTiO 3 Respectively weighing Bi according to the stoichiometric ratio of 0.7:0.3 2 O 3 、Na 2 CO 3 、TiO 2 、SrCO 3 Mixing to form a mixture A;
step two: respectively take outMixing the mixture A, the zircon ball stone and the deionized water according to the mass ratio of 1:4:1.3, sequentially performing ball milling, drying and sieving, and then placing the mixture A, the zircon ball stone and the deionized water in a muffle furnace to keep the temperature at 900 ℃ for 3.5h to form a main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Powder for standby; wherein, ball milling is carried out for 12.5 hours, and a sieve with 85 meshes is sieved.
Step three: respectively weighing 8mol% of Bi according to the mol percentage 2 O 3 MgO and SnO 2 Added to the main phase (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Forming a full-batch by powder;
step four: respectively taking the full ingredients, the zircon ball stone and the deionized water obtained in the step three, mixing according to the mass ratio of 1:4:1.3, and then sequentially performing ball milling, drying and sieving to form a sieving material; wherein, ball milling is carried out for 12.5 hours, and a 125-mesh sieve is sieved.
Step five: preparing a sample from the screened material obtained in the step four under the pressure of 125MPa, placing the sample in an alumina sagger taking alumina as a base plate in a high-temperature box type furnace, heating to 1200 ℃ at a speed of 6 ℃/min, preserving heat for 4 hours, cooling to 550 ℃ at a speed of 6 ℃/min, and cooling to room temperature along with the furnace;
step six: after polishing and cleaning the sample sintered in the fifth step, uniformly coating silver electrode slurry on the front and back sides of the sample, and sintering at 750 ℃ for 25min to obtain a sodium bismuth titanate-based lead-free antiferroelectric ceramic material sample.
Example 13:
bi of this example 0.5 Na 0.5 TiO 3 The chemical formula of the lead-free-based antiferroelectric ceramic material is (1-x) (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 -xBi(Mg 0.5 Sn 0.5 )O 3 Wherein x=0.12;
step one: according to Bi 0.5 Na 0.5 TiO 3 With SrTiO 3 Respectively weighing Bi according to the stoichiometric ratio of 0.7:0.3 2 O 3 、Na 2 CO 3 、TiO 2 、SrCO 3 Mixing to form a mixture A;
step two: respectively taking the mixture A, the zircon ball and deionizedMixing water according to the mass ratio of 1:4:1.3, sequentially performing ball milling, drying and sieving, and placing in a muffle furnace to keep the temperature at 800 ℃ for 2.5h to form a main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Powder for standby; wherein, ball milling is carried out for 11.5 hours, and sieving is carried out by a 75-mesh sieve.
Step three: respectively weighing 12mol percent of Bi according to the mol percent 2 O 3 MgO and SnO 2 Added to the main phase (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Forming a full-batch by powder;
step four: respectively taking the full ingredients, the zircon ball stone and the deionized water obtained in the step three, mixing according to the mass ratio of 1:4:1.3, and then sequentially performing ball milling, drying and sieving to form a sieving material; wherein, ball milling is carried out for 11.5 hours, and sieving is carried out by a 115-mesh sieve.
Step five: preparing a sample from the screened material obtained in the step four under the pressure of 115MPa, placing the sample in an alumina sagger taking alumina as a base plate in a high-temperature box type furnace, heating to 1100 ℃ at 4 ℃/min, preserving heat for 2 hours, cooling to 450 ℃ at 4 ℃/min, and cooling to room temperature along with the furnace;
step six: and (3) after polishing and cleaning the sample sintered in the fifth step, uniformly coating silver electrode slurry on the front and back sides of the sample, and sintering at 650 ℃ for 15min to obtain a sodium bismuth titanate-based lead-free antiferroelectric ceramic material sample.
Example 14:
bi of this example 0.5 Na 0.5 TiO 3 The chemical formula of the lead-free-based antiferroelectric ceramic material is (1-x) (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 -xBi(Mg 0.5 Sn 0.5 )O 3 Wherein x=0.12;
step one: according to Bi 0.5 Na 0.5 TiO 3 With SrTiO 3 Respectively weighing Bi according to the stoichiometric ratio of 0.7:0.3 2 O 3 、Na 2 CO 3 、TiO 2 、SrCO 3 Mixing to form a mixture A;
step two: respectively taking the mixture A, the zircon ball and the deionized water according to the mass ratio of 1:4:1.3Mixing, ball milling, oven drying, sieving, placing in a muffle furnace, and maintaining at 900deg.C for 3.5 hr to form main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Powder for standby; wherein, ball milling is carried out for 12.5 hours, and a sieve with 85 meshes is sieved.
Step three: respectively weighing 12mol percent of Bi according to the mol percent 2 O 3 MgO and SnO 2 Added to the main phase (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Forming a full-batch by powder;
step four: respectively taking the full ingredients, the zircon ball stone and the deionized water obtained in the step three, mixing according to the mass ratio of 1:4:1.3, and then sequentially performing ball milling, drying and sieving to form a sieving material; wherein, ball milling is carried out for 12.5 hours, and a 125-mesh sieve is sieved.
Step five: preparing a sample from the screened material obtained in the step four under the pressure of 125MPa, placing the sample in an alumina sagger taking alumina as a base plate in a high-temperature box type furnace, heating to 1200 ℃ at a speed of 6 ℃/min, preserving heat for 4 hours, cooling to 550 ℃ at a speed of 6 ℃/min, and cooling to room temperature along with the furnace;
step six: after polishing and cleaning the sample sintered in the fifth step, uniformly coating silver electrode slurry on the front and back sides of the sample, and sintering at 750 ℃ for 25min to obtain a sodium bismuth titanate-based lead-free antiferroelectric ceramic material sample.
Example 15:
bi of this example 0.5 Na 0.5 TiO 3 The chemical formula of the lead-free-based antiferroelectric ceramic material is (1-x) (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 -xBi(Mg 0.5 Sn 0.5 )O 3 Wherein x=0.16;
step one: according to Bi 0.5 Na 0.5 TiO 3 With SrTiO 3 Respectively weighing Bi according to the stoichiometric ratio of 0.7:0.3 2 O 3 、Na 2 CO 3 、TiO 2 、SrCO 3 Mixing to form a mixture A;
step two: respectively taking the mixture A, the zircon ball stone and the deionized water, mixing according to the mass ratio of 1:4:1.3, and then sequentially performing ball milling and bakingDrying, sieving, placing in muffle furnace, maintaining at 800 deg.C for 2.5 hr to form main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Powder for standby; wherein, ball milling is carried out for 11.5 hours, and sieving is carried out by a 75-mesh sieve.
Step three: respectively weighing 16mol% of Bi according to the mol percentage 2 O 3 MgO and SnO 2 Added to the main phase (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Forming a full-batch by powder;
step four: respectively taking the full ingredients, the zircon ball stone and the deionized water obtained in the step three, mixing according to the mass ratio of 1:4:1.3, and then sequentially performing ball milling, drying and sieving to form a sieving material; wherein, ball milling is carried out for 11.5 hours, and sieving is carried out by a 115-mesh sieve.
Step five: preparing a sample from the screened material obtained in the step four under the pressure of 115MPa, placing the sample in an alumina sagger taking alumina as a base plate in a high-temperature box type furnace, heating to 1100 ℃ at 4 ℃/min, preserving heat for 2 hours, cooling to 450 ℃ at 4 ℃/min, and cooling to room temperature along with the furnace;
step six: and (3) after polishing and cleaning the sample sintered in the fifth step, uniformly coating silver electrode slurry on the front and back sides of the sample, and sintering at 650 ℃ for 15min to obtain a sodium bismuth titanate-based lead-free antiferroelectric ceramic material sample.
Example 16:
bi of this example 0.5 Na 0.5 TiO 3 The chemical formula of the lead-free-based antiferroelectric ceramic material is (1-x) (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 -xBi(Mg 0.5 Sn 0.5 )O 3 Wherein x=0.16;
step one: according to Bi 0.5 Na 0.5 TiO 3 With SrTiO 3 Respectively weighing Bi according to the stoichiometric ratio of 0.7:0.3 2 O 3 、Na 2 CO 3 、TiO 2 、SrCO 3 Mixing to form a mixture A;
step two: respectively taking a mixture A, zircon and deionized water, mixing according to the mass ratio of 1:4:1.3, sequentially performing ball milling, drying and sieving, and then placing in a muffle furnaceThe mixture is kept at 900 ℃ for 3.5 hours to form a main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Powder for standby; wherein, ball milling is carried out for 12.5 hours, and a sieve with 85 meshes is sieved.
Step three: respectively weighing 16mol% of Bi according to the mol percentage 2 O 3 MgO and SnO 2 Added to the main phase (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Forming a full-batch by powder;
step four: respectively taking the full ingredients, the zircon ball stone and the deionized water obtained in the step three, mixing according to the mass ratio of 1:4:1.3, and then sequentially performing ball milling, drying and sieving to form a sieving material; wherein, ball milling is carried out for 12.5 hours, and a 125-mesh sieve is sieved.
Step five: preparing a sample from the screened material obtained in the step four under the pressure of 125MPa, placing the sample in an alumina sagger taking alumina as a base plate in a high-temperature box type furnace, heating to 1200 ℃ at a speed of 6 ℃/min, preserving heat for 4 hours, cooling to 550 ℃ at a speed of 6 ℃/min, and cooling to room temperature along with the furnace;
step six: after polishing and cleaning the sample sintered in the fifth step, uniformly coating silver electrode slurry on the front and back sides of the sample, and sintering at 750 ℃ for 25min to obtain a sodium bismuth titanate-based lead-free antiferroelectric ceramic material sample.
Example 17:
bi of this example 0.5 Na 0.5 TiO 3 The chemical formula of the lead-free-based antiferroelectric ceramic material is (1-x) (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 -xBi(Mg 0.5 Sn 0.5 )O 3 Wherein x=0.20;
step one: according to Bi 0.5 Na 0.5 TiO 3 With SrTiO 3 Respectively weighing Bi according to the stoichiometric ratio of 0.7:0.3 2 O 3 、Na 2 CO 3 、TiO 2 、SrCO 3 Mixing to form a mixture A;
step two: respectively taking the mixture A, the zircon ball stone and the deionized water, mixing according to the mass ratio of 1:4:1.3, sequentially performing ball milling, drying and sieving, and then placing in a muffle furnace to keep the temperature at 800 ℃ for 2.5h to form a main bodyPhase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Powder for standby; wherein, ball milling is carried out for 11.5 hours, and sieving is carried out by a 75-mesh sieve.
Step three: respectively weighing 20mol% of Bi according to the mol percentage 2 O 3 MgO and SnO 2 Added to the main phase (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Forming a full-batch by powder;
step four: respectively taking the full ingredients, the zircon ball stone and the deionized water obtained in the step three, mixing according to the mass ratio of 1:4:1.3, and then sequentially performing ball milling, drying and sieving to form a sieving material; wherein, ball milling is carried out for 11.5 hours, and sieving is carried out by a 115-mesh sieve.
Step five: preparing a sample from the screened material obtained in the step four under the pressure of 115MPa, placing the sample in an alumina sagger taking alumina as a base plate in a high-temperature box type furnace, heating to 1100 ℃ at 4 ℃/min, preserving heat for 2 hours, cooling to 450 ℃ at 4 ℃/min, and cooling to room temperature along with the furnace;
step six: and (3) after polishing and cleaning the sample sintered in the fifth step, uniformly coating silver electrode slurry on the front and back sides of the sample, and sintering at 650 ℃ for 15min to obtain a sodium bismuth titanate-based lead-free antiferroelectric ceramic material sample.
Example 18:
bi of this example 0.5 Na 0.5 TiO 3 The chemical formula of the lead-free-based antiferroelectric ceramic material is (1-x) (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 -xBi(Mg 0.5 Sn 0.5 )O 3 Wherein x=0.20;
step one: according to Bi 0.5 Na 0.5 TiO 3 With SrTiO 3 Respectively weighing Bi according to the stoichiometric ratio of 0.7:0.3 2 O 3 、Na 2 CO 3 、TiO 2 、SrCO 3 Mixing to form a mixture A;
step two: respectively taking the mixture A, the zircon ball stone and the deionized water, mixing according to the mass ratio of 1:4:1.3, sequentially performing ball milling, drying and sieving, and then placing in a muffle furnace to keep the temperature at 900 ℃ for 3.5h to form a main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Powder for standby; wherein, ball milling is carried out for 12.5 hours, and a sieve with 85 meshes is sieved.
Step three: respectively weighing 20mol% of Bi according to the mol percentage 2 O 3 MgO and SnO 2 Added to the main phase (Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Forming a full-batch by powder;
step four: respectively taking the full ingredients, the zircon ball stone and the deionized water obtained in the step three, mixing according to the mass ratio of 1:4:1.3, and then sequentially performing ball milling, drying and sieving to form a sieving material; wherein, ball milling is carried out for 12.5 hours, and a 125-mesh sieve is sieved.
Step five: preparing a sample from the screened material obtained in the step four under the pressure of 125MPa, placing the sample in an alumina sagger taking alumina as a base plate in a high-temperature box type furnace, heating to 1200 ℃ at a speed of 6 ℃/min, preserving heat for 4 hours, cooling to 550 ℃ at a speed of 6 ℃/min, and cooling to room temperature along with the furnace;
step six: after polishing and cleaning the sample sintered in the fifth step, uniformly coating silver electrode slurry on the front and back sides of the sample, and sintering at 750 ℃ for 25min to obtain a sodium bismuth titanate-based lead-free antiferroelectric ceramic material sample.
Referring to fig. 2 to 8, fig. 2 is a graph of the dielectric constant and the dielectric loss of x=0 as a function of temperature, fig. 3 is a graph of the dielectric constant and the dielectric loss of x=0.04 as a function of temperature, fig. 4 is a graph of the dielectric constant and the dielectric loss of x=0.08 as a function of temperature, fig. 5 is a graph of the dielectric constant and the dielectric loss of x=0.12 as a function of temperature, fig. 6 is a graph of the dielectric constant and the dielectric loss of x=0.16 as a function of temperature, fig. 7 is a graph of the dielectric constant and the dielectric loss of x=0.20 as a function of temperature, and at T s And T m Double dielectric anomaly peaks can be observed here due to thermal evolution of polar nano-regions (PNRs), all samples have a broad peak of dielectric constant and dielectric loss near Ts and have significant frequency dispersion, which is characteristic of relaxed ferroelectrics. At the same time, the temperature corresponding to the peak value of Ts shifts to a lower value with the increase of the doping content. From the above results, it can be concluded that，(1-x)(Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 -xBi(Mg 0.5 Sn 0.5 )O 3 The ceramic has nano ferroelectric regions, which destroy long ferroelectric order. Further, with Bi (Mg 0.5 Sn 0.5 )O 3 An increase in the amount of addition, T m To higher temperature change, T m The dielectric constant at the location gradually decreases, which is the same as Ti 4+ Is coated with Mg 2+ And Sn (Sn) 4+ Ion substitution is involved, resulting in site disorder and charge fluctuation. The sodium bismuth titanate based lead-free antiferroelectric ceramic material prepared by the method has obvious relaxation phenomenon, simple material preparation process, low material cost, higher dielectric constant, low dielectric loss and excellent high-temperature stability, and becomes one of important candidate materials which are expected to replace lead-based relaxation ferroelectrics to be excellent in both technology and economy of the multilayer ceramic capacitor.
The sodium bismuth titanate-based lead-free antiferroelectric ceramic material and the preparation method thereof provided by the invention have the advantages of obvious relaxation phenomenon, environmental friendliness, simple preparation process, low preparation cost, large dielectric constant, small dielectric loss, excellent high-temperature stability and obvious frequency dispersion, and can be an important candidate material for replacing lead-based relaxor ferroelectric to become a multilayer ceramic capacitor in terms of both technology and economy. The preparation method of the bismuth sodium titanate-based leadless antiferroelectric ceramic material has at least the following advantages: 1) The preparation method adopts the traditional solid phase method, has mature process and is suitable for industrialized production. 2) By Bi (Mg) 0.5 Sn 0.5 )O 3 The doping is beneficial to improving the energy storage efficiency and the relaxation of the strontium bismuth sodium titanate ceramic. 3) The lead-free antiferroelectric ceramic material prepared by the method has the advantages of simple preparation process, low material cost, higher dielectric constant, low dielectric loss, excellent high-temperature stability and obvious relaxation phenomenon, and is an important candidate material for replacing lead-based relaxation ferroelectrics to become a multilayer ceramic capacitor in both technical and economic aspects.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A bismuth sodium titanate based leadless antiferroelectric ceramic material is characterized in that the chemical formula of the bismuth sodium titanate based leadless antiferroelectric ceramic material is (1-x) (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 -xBi(Mg 0.5 Sn 0.5 )O 3 Wherein x is mole percent, and the value range of x is 0-0.2.
2. The bismuth sodium titanate based lead-free antiferroelectric ceramic material according to claim 1, wherein the molar percentage x = 0, 0.04, 0.08, 0.12, 0.16 or 0.20.
3. The method for preparing the sodium bismuth titanate-based lead-free antiferroelectric ceramic material according to claim 1, which is characterized by comprising the following steps:
step one: bi is mixed with 2 O 3 、Na 2 CO 3 、TiO 2 And SrCO 3 Mixing to form a mixture A;
step two: mixing the mixture A, zircon and deionized water, sequentially ball milling, oven drying, sieving, and maintaining the temperature to form a main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Powder;
step three: bi is mixed with 2 O 3 MgO and SnO 2 Added to the main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 Forming a full-batch by powder;
step four: mixing the full ingredients, the zircon ball stone and the deionized water, and then sequentially performing ball milling, drying and sieving to form a sieving material;
step five: preparing the screened material into a sample, cooling to room temperature after sintering, and polishing and cleaning to obtain a pretreated sample;
step six: and uniformly coating silver electrode slurry on the front and back surfaces of the pretreated sample, and sintering to obtain the sodium bismuth titanate-based lead-free relaxation ferroelectric ceramic material sample.
4. The method for preparing the sodium bismuth titanate-based leadless antiferroelectric ceramic material according to claim 3, wherein in the second step, the mixture A, the zircon ball and the deionized water are mixed according to the mass ratio of 1:4:1.3, ball-milled, dried and sieved in sequence, and then placed in a muffle furnace to be insulated for 2-4 hours at 800-900 ℃ to form a main phase (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 And (3) powder.
5. The method for preparing a sodium bismuth titanate based leadless antiferroelectric ceramic material according to claim 3, wherein the ball milling time is 11.5-12.5 h in the second step and the fourth step.
6. The method for preparing a sodium bismuth titanate based leadless antiferroelectric ceramic material according to claim 3, wherein the second step is sieving through a 75-85 mesh sieve.
7. The method for preparing a sodium bismuth titanate based leadless antiferroelectric ceramic material according to claim 3, wherein in the third step, 4mol% to 20mol% of Bi is respectively weighed according to the mole percentage 2 O 3 MgO and SnO 2 。
8. The method for preparing a sodium bismuth titanate based leadless antiferroelectric ceramic material according to claim 3, wherein in the fourth step, the sieving is carried out by a 115-125 mesh sieve.
9. The method for preparing the sodium bismuth titanate-based leadless antiferroelectric ceramic material according to claim 3, wherein in the fifth step, the screened material is prepared into a sample under the pressure of 115-125 MPa, then is placed in an alumina sagger taking alumina as a backing plate, is placed in a high-temperature box-type furnace, is heated to 1150-1200 ℃ at 4-6 ℃ per minute, is kept for 2-4 h, is cooled to 450-550 ℃ at 4-6 ℃ per minute, and is cooled to room temperature along with the furnace.
10. The method for preparing a bismuth sodium titanate based leadless antiferroelectric ceramic material according to claim 3, wherein in the sixth step, the bismuth sodium titanate based leadless relaxor ferroelectric ceramic material sample is obtained by sintering at 650-750 ℃ for 15-25 min.
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| CN116874297A (en) * | 2023-07-10 | 2023-10-13 | 石河子大学 | Bismuth sodium titanate-based energy storage ceramic material |
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| CN116675530A (en) * | 2023-06-06 | 2023-09-01 | 石河子大学 | Lead-free ferroelectric energy storage ceramic material with stable wide frequency and preparation method thereof |
| CN116874297A (en) * | 2023-07-10 | 2023-10-13 | 石河子大学 | Bismuth sodium titanate-based energy storage ceramic material |
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