CN116947488A - Method for regulating ferroelectric property of unfilled barium strontium niobate material by doping ions with different radiuses - Google Patents
Method for regulating ferroelectric property of unfilled barium strontium niobate material by doping ions with different radiuses Download PDFInfo
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- 150000002500 ions Chemical class 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 title claims abstract description 25
- DKDQMLPMKQLBHQ-UHFFFAOYSA-N strontium;barium(2+);oxido(dioxo)niobium Chemical compound [Sr+2].[Ba+2].[O-][Nb](=O)=O.[O-][Nb](=O)=O.[O-][Nb](=O)=O.[O-][Nb](=O)=O DKDQMLPMKQLBHQ-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 10
- 239000000843 powder Substances 0.000 claims description 54
- 238000000498 ball milling Methods 0.000 claims description 29
- 239000000919 ceramic Substances 0.000 claims description 22
- 239000010937 tungsten Substances 0.000 claims description 20
- 229910052721 tungsten Inorganic materials 0.000 claims description 20
- 239000012071 phase Substances 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
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- 238000003825 pressing Methods 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 abstract description 14
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 abstract 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 16
- 230000009467 reduction Effects 0.000 description 8
- 238000003892 spreading Methods 0.000 description 8
- 230000007480 spreading Effects 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000011324 bead Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
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- 230000010287 polarization Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000033228 biological regulation Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000906 Bronze Inorganic materials 0.000 description 3
- 239000010974 bronze Substances 0.000 description 3
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 3
- 230000005621 ferroelectricity Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 239000012153 distilled water Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
The application belongs to the technical field of ceramic material modification, and particularly relates to a method for regulating ferroelectric properties of an unfilled barium strontium niobate (SBN) material by doping ions with different radiuses. The method utilizes the characteristic that the A site (comprising A1 and A2 sites) of 1/6 and all C sites in the SBN structural lattice are not occupied, and introduces a proper amount of alkali metal ions Li + 、Na + 、K + Filling these unoccupied sites and thus achieving tuning of ferroelectric properties. Since these alkali metal ions have different radii, the lattice points they can occupy are different, and this different occupation position results in Li + 、Na + 、K + Ion doping has different regulatory effects on the ferroelectric properties of SBN: experimental results show that Li + Ion doping enhances the relaxor ferroelectric properties of SBN, na + Ion doping significantly enhances the normal ferroelectric properties of SBN, while K + Ion doping marginally enhances the normal ferroelectric properties of SBN.
Description
Technical Field
The application belongs to the technical field of ceramic material modification, and particularly relates to a method for regulating ferroelectric properties of an unfilled barium strontium niobate material by doping ions with different radiuses.
Background
Ferroelectrics include relaxor ferroelectrics and normal ferroelectrics. The general relaxation ferroelectric has the characteristics of slender electric hysteresis loop, smaller residual polarization, smaller coercive field and the like; whereas normal ferroelectrics have the characteristics of saturated hysteresis loops, larger remnant polarization, larger coercive field, etc. The different ferroelectric properties of the different ferroelectrics make them of different applications. Thus, there is a need to tailor the relaxor or normal ferroelectric properties to different application requirements. It is believed that doping will complicate the chemical composition of the material and will disrupt the long Cheng Tiedian order, thereby enhancing the relaxor ferroelectric properties of the ferroelectric material.
Disclosure of Invention
In view of the above, the present application aims to provide a method for obtaining different modulating effects on the relaxation ferroelectric property or the normal ferroelectric property of SBN by doping ions with different radii, aiming at the technical knowledge that the doped modified barium strontium niobate material only enhances the relaxation ferroelectric property in the prior art.
In order to achieve the above purpose, the present application adopts the following technical scheme:
a method for regulating ferroelectric property of unfilled barium strontium niobate material by doping ions with different radiuses, wherein the barium strontium niobate material is an unfilled tungsten bronze structure ferroelectric oxide represented by SBN, and the initial chemical formula of the doped material is (1-x) SBN-0.5xM 2 CO 3 Wherein SBN represents an underfilling tungsten bronze structure relaxor ferroelectric Sr 0.6 Ba 0.4 Nb 2 O 6 ，M + ＝Li + 、Na + Or K + X represents Li + 、Na + Or K + Doping amount of ions.
Further, the value of x is 0-0.2.
It is worth noting that the chemical formula is (A1) 2 (A2) 4 C 4 (B1) 2 (B2) 8 O 30 The tungsten bronze structure oxide of (2) is an important ferroelectric material, takes oxygen octahedron as a basic structural unit, and forms three gaps through oxygen octahedron connected by common peaks: the C position of the triangular prism with the smallest space, the A1 position of the triangular prism with the middle space and the A2 position of the triangular prism with the largest space. The occupation conditions of the A bit (including A1 and A2) and the C bit can be classified into a full-fill type, a full-fill type and a full-fill typeAnd (3) a non-full type. Sr (Sr) 0.6 Ba 0.4 Nb 2 O 6 (SBN) is a typical non-filled tungsten bronze relaxor ferroelectric with an A-bit occupancy of 5/6, i.e., 1/6 of the A-bit (including A1 and A2 bits) and all of the C-bits unoccupied. This means that unoccupied sites in the SBN can be gradually occupied by introducing further doping ions. Further, considering that unoccupied A1, A2 and C sites in the SBN have different space sizes, if doping ions with different radii are introduced, different occupied states can be generated, so that different regulation and control effects on ferroelectricity can be generated.
Therefore, consider Li + 、Na + 、K + The ionic radii of (a) are respectivelyThe different ionic radii make it possible for them to occupy unoccupied a and/or C sites in the SBN, thereby achieving different regulatory effects on the ferroelectricity of the SBN.
The application is characterized in that Li with different ionic radii is doped + 、Na + Or K + Ions such that Li + 、Na + 、K + Ions occupy different unoccupied positions in the SBN, respectively, forming different occupied states: with the smallest radiusThe ion mainly occupies the least space C site and part of the A site, including the A1 site with larger space and the A2 site with the largest space; with medium radius The ion energy occupies the A position, including the A1 position and the A2 position, and the maximum radius +.>Ions can only occupy the A2 position of the a positions.
Surprisingly, doping as considered in the prior art would causeThe chemical composition of the obtained material is more complex, the long Cheng Tiedian sequence is disturbed, thus the relaxation ferroelectric property of the ferroelectric material is enhanced, and the different occupation states in the application lead to Li + 、Na + 、K + Ion doping has different regulation effects on the ferroelectric properties of SBN: li (Li) + Ion doping significantly enhances the relaxor ferroelectric properties of SBN, na + Ion doping significantly enhances the normal ferroelectric properties of SBN, while K + Ion doping marginally enhances the normal ferroelectric properties of SBN.
Still further, the method comprises the steps of:
(1) Firstly, preparing single-phase SBN powder by a solid-phase chemical reaction sintering method; next, SBN-0.5xM according to the formula (1-x) 2 CO 3 Weighing the single-phase SBN powder and M subjected to drying treatment 2 CO 3 Powder, said M 2 CO 3 Is Li 2 CO 3 、Na 2 CO 3 、K 2 CO 3 One of the following;
(2) Uniformly mixing the powder weighed in the step (1) by wet ball milling, drying, pressing into slices, placing in a crucible, sintering at high temperature, and carrying out M 2 CO 3 The C element in the powder is completely volatilized, and M + Ions then enter the lattice of the tungsten bronze structure and occupy unoccupied sites in the SBN, thereby obtaining M + Ion doped SBN ceramics.
Further, the high-temperature sintering temperature in the step (2) is 1200-1350 ℃ and the time is 1-4 hours.
Compared with the prior art, the application has the beneficial effects that:
1. based on the route and method of this patent, single-phase Li with tungsten bronze structure is obtained + 、Na + 、K + Ion doped SBN ceramic samples. The sample preparation process is convenient and efficient, has no complex process, does not involve expensive equipment, has low cost, and can be applied to actual industrial production.
2. Due to Li + 、Na + 、K + The ions have different ionic radii due toThis Li + 、Na + 、K + Ions occupy different unoccupied positions in the SBN, respectively, forming different occupied states: with the smallest radiusThe ion mainly occupies the least space C site and part of the A site, including the A1 site with larger space and the A2 site with the largest space; middle radius +.>The ion occupies the A position, including the A1 position and the A2 position, and the radius is the largest +.>Ions can only occupy the A2 position of the a positions. Different occupancy states lead to Li + 、Na + 、K + Ion doping has different regulation effects on the ferroelectric properties of SBN: li (Li) + Ion doping significantly enhances the relaxor ferroelectric properties of SBN, na + Ion doping significantly enhances the normal ferroelectric properties of SBN, while K + Ion doping marginally enhances the normal ferroelectric properties of SBN.
3. The method for obtaining different modulation effects by doping ions with different radiuses provides a convenient and efficient design idea for regulating and controlling the properties of the tungsten bronze ferroelectric material.
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In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for the description of the embodiments or the prior art will be briefly described below, it will be apparent that the drawings in the following description are only embodiments of the present application, and other drawings can be obtained from the provided drawings without inventive effort for a person skilled in the art
FIG. 1 shows (1-x) SBN-0.5xM obtained by the preparation of examples 1, 3, 5 and 7 of the present application 2 CO 3 ，M＝Li + 、Na + 、K + And x=0 and 0.2 ceramic samples (abbreviated as SBN, SBNL20, SBNN20, SBNK2, respectively)0) X-ray diffraction spectrum of (c).
FIG. 2 shows (1-x) SBN-0.5xM obtained by the preparation of examples 1, 3, 5 and 7 of the present application 2 CO 3 Dielectric constant ε of ceramic sample r (left axis) and dielectric loss tan delta (right axis), wherein the (a), (b), (c), (d) plots correspond to components SBN, SBNL20, SBNN20, SBNK20, respectively.
FIG. 3 shows (1-x) SBN-0.5xM prepared according to examples 1, 3, 5, and 7 of the present application 2 CO 3 Room temperature polarization-electric field curve (P-E) of ceramic sample, wherein the (a), (b), (c), (d) plots correspond to components SBN, SBNL20, SBNN20, SBNK20, respectively.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The word "embodiment" as used herein does not necessarily mean that any embodiment described as "exemplary" is preferred or advantageous over other embodiments. Performance index testing in the examples of the present application, unless otherwise specified, was performed using conventional testing methods in the art. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure.
Unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; other test methods and techniques not specifically mentioned in the present application are those commonly used by those skilled in the art.
Numerous specific details are set forth in the following examples in order to provide a better understanding of the present application. It will be understood by those skilled in the art that the present application may be practiced without some of these specific details. In the examples, some methods, means, instruments, devices, etc. well known to those skilled in the art are not described in detail in order to highlight the gist of the present application. On the premise of no conflict, the technical features disclosed by the embodiment of the application can be combined at will, and the obtained technical scheme belongs to the disclosure of the embodiment of the application.
The application provides a method for regulating and controlling the ferroelectricity of SBN by doping ions with different radiuses. The initial chemical formula of the doping material is (1-x) SBN-0.5xM 2 CO 3 (M＝Li + 、Na + 、K + And x=0-0.2). Due to Li + 、Na + 、K + The ions have different ionic radii, and therefore Li + 、Na + 、K + Ions occupy different unoccupied positions in the SBN, respectively, forming different occupied states: wherein the radius is the smallestThe ion mainly occupies the least space C site and part of the A site, including the A1 site with larger space and the A2 site with the largest space; middle radius +.>The ion occupies the A position, including the A1 position and the A2 position, and the radius is the largest +.>Ions can only occupy the A2 position of the a positions. Different occupancy states lead to Li + 、Na + 、K + Ion doping has different regulation effects on the ferroelectric properties of SBN: li (Li) + Ion doping significantly enhances the relaxor ferroelectric properties of SBN, na + Ion doping significantly enhances the normal ferroelectric properties of SBN, while K + Ion doping marginally enhances the normal ferroelectric properties of SBN.
The present application will be further specifically illustrated by the following examples, which are not to be construed as limiting the application, but rather as falling within the scope of the present application, for some non-essential modifications and adaptations of the application that are apparent to those skilled in the art based on the foregoing disclosure.
Example 1
The barium strontium niobate material is (1-x) SBN-0.5xM 2 CO 3 Where x=0, i.e. SBN.
8.9473 g SrCO is weighed 3 Powder, 7.9733 g BaCO 3 Powder and 26.7146 g Nb 2 O 5 The powder is put into a ball-milling tank with a proper amount of ball-milling beads, distilled water with the volume of about 2/3 of the ball-milling tank is added, and the mixture is ball-milled for 24 hours to be uniformly mixed. After drying the obtained powder, a proper amount of the powder was pressed into a block having a diameter of about 20 mm and a thickness of about 4 mm by a pressure of 10 MPa. At Al 2 O 3 Spreading a thin layer of uniformly mixed powder on the bottom of the crucible cover, putting into a formed block, and using Al 2 O 3 The wafer covers the crucible to make the block in a sealed state. The crucible is placed in a muffle furnace, the temperature is kept for 60 minutes from room temperature to 450 ℃, the temperature is further raised to the sintering temperature (1300 ℃) for 3 hours, the temperature is reduced to 500 ℃, then the crucible is cooled to the room temperature along with the furnace, and the whole-process temperature rise and reduction rate is controlled at 5 ℃/minute. After the ceramic block is obtained, the ceramic block is manually ground and ball-milled for 24 hours by adding distilled water, and the obtained slurry is dried to obtain single-phase SBN powder.
The appropriate amount of powder was then pressed with a pressure of 15MPa into a sheet having a diameter of about 10 mm and a thickness of about 1.5 mm. At Al 2 O 3 Spreading a thin layer of SBN powder on the bottom of the crucible, placing into a formed sheet, covering the sheet with the powder, and finally coating Al 2 O 3 The wafer is covered on the crucible to make the wafer in a sealed state. The crucible sealed with the thin sheet is placed into a muffle furnace and heated, the temperature is kept for 60 minutes from room temperature to 450 ℃, then the temperature is raised to a sintering temperature (1350 ℃) for 3 hours, the temperature is reduced to 500 ℃, then the crucible is cooled to room temperature along with the furnace, and the whole-process temperature rise and reduction rate is controlled at 3 ℃/minute. A single phase SBN ceramic was obtained and its structural properties were characterized.
Example 2
The barium strontium niobate material is (1-x) SBN-0.5xM 2 CO 3 M=li + And x=0.1, i.e. SBNL10.
26.1875 g of single-phase SBN powder, 0.3016 g of Li, are weighed 2 CO 3 Powder, put intoThe ball milling tank with a proper amount of ball milling beads is added with absolute ethyl alcohol with the volume of about 2/3 of the ball milling tank, and the ball milling is carried out for 24 hours to ensure that the absolute ethyl alcohol is uniformly mixed. After the resulting slurry was dried, an appropriate amount of the powder was pressed with a pressure of 15MPa into a sheet having a diameter of about 10 mm and a thickness of about 1.5 mm. At Al 2 O 3 Spreading a thin layer of the component powder on the bottom of the crucible, putting into a formed sheet, covering the sheet with the powder, and finally coating Al 2 O 3 The wafer is covered on the crucible to make the wafer in a sealed state. The crucible sealed with the thin sheet is placed into a muffle furnace and heated, the temperature is kept for 60 minutes from room temperature to 450 ℃, then the temperature is raised to sintering temperature (1300 ℃) for 3 hours, the temperature is reduced to 500 ℃, then the crucible is cooled to room temperature along with the furnace, and the whole-process temperature rise and reduction rate is controlled at 3 ℃/minute. Obtaining Li + The structure and performance of the doped SBN ceramic are characterized.
Example 3
The barium strontium niobate material is (1-x) SBN-0.5xM 2 CO 3 M=li + And x=0.2, i.e. SBNL20.
23.2778 g of single-phase SBN powder, 0.6032 g of Li, are weighed 2 CO 3 The powder is put into a ball milling tank with a proper amount of ball milling beads, absolute ethyl alcohol with the volume of about 2/3 of the ball milling tank is added, and the ball milling is carried out for 24 hours to ensure that the powder is uniformly mixed. After the resulting slurry was dried, an appropriate amount of the powder was pressed with a pressure of 15MPa into a sheet having a diameter of about 10 mm and a thickness of about 1.5 mm. At Al 2 O 3 Spreading a thin layer of the component powder on the bottom of the crucible, putting into a formed sheet, covering the sheet with the powder, and finally coating Al 2 O 3 The wafer is covered on the crucible to make the wafer in a sealed state. The crucible sealed with the thin sheet is placed into a muffle furnace and heated, the temperature is kept for 60 minutes from room temperature to 450 ℃, then the temperature is raised to sintering temperature (1300 ℃) for 3 hours, the temperature is reduced to 500 ℃, then the crucible is cooled to room temperature along with the furnace, and the whole-process temperature rise and reduction rate is controlled at 3 ℃/minute. Obtaining Li + The structure and performance of the doped SBN ceramic are characterized.
Example 4
The barium strontium niobate material is (1-x) SBN-0.5xM 2 CO 3 M=na + And x=0.1, i.e. SBNN10.
26.1875 g of single-phase SBN powder, 0.4248 g of Na are weighed 2 CO 3 The powder is put into a ball milling tank with a proper amount of ball milling beads, absolute ethyl alcohol with the volume of about 2/3 of the ball milling tank is added, and the ball milling is carried out for 24 hours to ensure that the powder is uniformly mixed. After the resulting slurry was dried, an appropriate amount of the powder was pressed with a pressure of 15MPa into a sheet having a diameter of about 10 mm and a thickness of about 1.5 mm. At Al 2 O 3 Spreading a thin layer of the component powder on the bottom of the crucible, putting into a formed sheet, covering the sheet with the powder, and finally coating Al 2 O 3 The wafer is covered on the crucible to make the wafer in a sealed state. The crucible sealed with the thin sheet is placed into a muffle furnace and heated, the temperature is kept for 60 minutes from room temperature to 450 ℃, then the temperature is raised to a sintering temperature (1250 ℃) for 3 hours, the temperature is reduced to 500 ℃, then the crucible is cooled to room temperature along with the furnace, and the whole-process temperature rise and reduction rate is controlled at 3 ℃/minute. Obtaining Na + The structure and performance of the doped SBN ceramic are characterized.
Example 5
The barium strontium niobate material is (1-x) SBN-0.5xM 2 CO 3 M=na + And x=0.2, i.e. SBNN20.
23.2778 g of single-phase SBN powder, 0.8496 g of Na are weighed 2 CO 3 The powder is put into a ball milling tank with a proper amount of ball milling beads, absolute ethyl alcohol with the volume of about 2/3 of the ball milling tank is added, and the ball milling is carried out for 24 hours to ensure that the powder is uniformly mixed. After the resulting slurry was dried, an appropriate amount of the powder was pressed with a pressure of 15MPa into a sheet having a diameter of about 10 mm and a thickness of about 1.5 mm. At Al 2 O 3 Spreading a thin layer of the component powder on the bottom of the crucible, putting into a formed sheet, covering the sheet with the powder, and finally coating Al 2 O 3 The wafer is covered on the crucible to make the wafer in a sealed state. The crucible sealed with the thin sheet is placed into a muffle furnace and heated, the temperature is kept for 60 minutes from room temperature to 450 ℃, then the temperature is raised to a sintering temperature (1250 ℃) for 3 hours, the temperature is reduced to 500 ℃, then the crucible is cooled to room temperature along with the furnace, and the whole-process temperature rise and reduction rate is controlled at 3 ℃/minute. Obtaining Na + The structure and performance of the doped SBN ceramic are characterized.
Example 6
The barium strontium niobate material is (1-x) SBN-0.5xM 2 CO 3 M=k + And x=0.1, i.e., SBNK10.
26.1875 g of single-phase SBN powder, 0.5584 g of K are weighed 2 CO 3 The powder is put into a ball milling tank with a proper amount of ball milling beads, absolute ethyl alcohol with the volume of about 2/3 of the ball milling tank is added, and the ball milling is carried out for 24 hours to ensure that the powder is uniformly mixed. After the resulting slurry was dried, an appropriate amount of the powder was pressed with a pressure of 15MPa into a sheet having a diameter of about 10 mm and a thickness of about 1.5 mm. At Al 2 O 3 Spreading a thin layer of the component powder on the bottom of the crucible, putting into a formed sheet, covering the sheet with the powder, and finally coating Al 2 O 3 The wafer is covered on the crucible to make the wafer in a sealed state. The crucible sealed with the thin sheet is placed into a muffle furnace and heated, the temperature is kept for 60 minutes from room temperature to 450 ℃, then the temperature is raised to sintering temperature (1200 ℃) for 3 hours, the temperature is reduced to 500 ℃, then the crucible is cooled to room temperature along with the furnace, and the whole-process temperature rise and reduction rate is controlled at 3 ℃/minute. Obtaining K + The structure and performance of the doped SBN ceramic are characterized.
Example 7
The barium strontium niobate material is (1-x) SBN-0.5xM 2 CO 3 M=k + And x=0.2, i.e. SBNK20.
23.2778 g of single-phase SBN powder, 1.1168 g of K are weighed 2 CO 3 The powder is put into a ball milling tank with a proper amount of ball milling beads, absolute ethyl alcohol with the volume of about 2/3 of the ball milling tank is added, and the ball milling is carried out for 24 hours to ensure that the powder is uniformly mixed. After the resulting slurry was dried, an appropriate amount of the powder was pressed with a pressure of 15MPa into a sheet having a diameter of about 10 mm and a thickness of about 1.5 mm. At Al 2 O 3 Spreading a thin layer of the component powder on the bottom of the crucible, putting into a formed sheet, covering the sheet with the powder, and finally coating Al 2 O 3 The wafer is covered on the crucible to make the wafer in a sealed state. Placing the crucible sealed with the thin sheet into a muffle furnace, heating, keeping the temperature from room temperature to 450 ℃ for 60 minutes, heating to sintering temperature (1200 ℃) for 3 hours, cooling to 500 ℃, and cooling to room temperature along with the furnaceThe whole-course temperature rise and reduction rate is controlled at 3 ℃/min. Obtaining K + The structure and performance of the doped SBN ceramic are characterized.
Test results:
FIG. 1 shows the X-ray diffraction (XRD) patterns of the SBN, SBNL20, SBNN20 and SBNK20 ceramic samples prepared in examples 1, 3, 5 and 7. All diffraction peaks and ceramic samples derived from the tungsten bronze structure, i.e., 4 examples, had a single phase tungsten bronze structure. This means that, within the designed composition interval, li + 、Na + 、K + The ions enter the tungsten bronze lattice and occupy the original unoccupied sites, thereby obtaining single-phase Li with tungsten bronze structure + 、Na + 、K + Doped SBN ceramic.
FIG. 2 shows the dielectric constants ε of the SBN, SBNL20, SBNN20 and SBNK20 ceramic samples prepared in examples 1, 3, 5 and 7 r And the variation of dielectric loss tan delta with temperature. The following results can be obtained from the graph: first, the permittivity peaks of both the SBN in FIG. (a) and the SBNL20 ceramic in FIG. (b) are dependent on the test frequency, which is typical of relaxor ferroelectric characteristics. Further comparison shows that the permittivity peaks of the SBN of figure (a) are narrower than those of the SBNL20 of figure (b), which means that the SBN is a non-traversing relaxor ferroelectric, whereas the SBNL20 is a relaxor ferroelectric, i.e. the SBNL20 has enhanced relaxor ferroelectric properties. At the same time, the temperature T corresponding to the maximum dielectric constants of SBN and SBNL20 m At a frequency of 1kHz at 36℃and 40℃respectively, i.e.Tt of SBNL20 m A limited improvement is obtained. Second, in graphs (c) and (d), the permittivity peaks are independent of the test frequency, indicating that both are normal ferroelectrics, T for both m 212℃and 148℃at a frequency of 1kHz, respectively.
The reason for the above results is that Li + 、Na + 、K + The ions have different ionic radii and thus occupy different unoccupied positions in the SBN lattice, respectively, forming different occupancy states: first, the radius is the smallestThe ions mainly occupy the least space of the C site and part of the A site, including the larger space of the A1 site and the largest space of the A2 site. In this case, li + Ion doping exacerbates the disorder of cations in the tungsten bronze structure on the one hand and has limited effect on the distortion of oxygen octahedra in the tungsten bronze structure on the other hand, so that SBNL20 exhibits enhanced relaxor ferroelectric properties while T m Is very limited. Second, moderate radius +.>Ions cannot occupy the C-position but only the a-position, including the A1-position and the A2-position. In this case, on the one hand, the oxygen octahedral distortion in the tungsten bronze structure is significantly suppressed, and on the other hand, na + Is doped to cause Sr at A-position in tungsten bronze structure 2+ 、Ba 2+ 、Na 2+ The ions present a certain order, both of which are beneficial to compacting the relaxor ferroelectric properties of SBNN20, enhancing the normal ferroelectric properties thereof, and significantly improving T m . Third, the radius is the largestIons can only occupy the A2 bit of the a bits, while the A1 bit remains unoccupied, and therefore. Oxygen octahedral twisting in the tungsten bronze structure is suppressed to some extent while Sr at A site in the tungsten bronze structure 2+ 、Ba 2+ 、K 2+ The ions assume a somewhat more ordered state, these two factors being such that the SBNK20 assumes normal ferroelectric properties, but T m Is limited.
FIG. 3 shows the hysteresis loop diagrams (polarization-electric field) of the SBN, SBNL20, SBNN20, SBNK20 ceramic samples prepared in examples 1, 3, 5, 7. It can be seen that, first, the hysteresis loops of fig. (a) and (b) each have an elongated character and the remnant polarization at zero electric field is small, since both SBN and SBNL20 are relaxed ferroelectrics; residual polarization of SBN was 0.05. Mu.C/cm 2 Residual polarization of SBNL20 was 0.03 μC/cm 2 The smaller remnant polarization of SBNL20 can be attributed to its enhanced relaxation relative to SBNFerroelectric properties. Second, the hysteresis loops of both (c) and (d) are more saturated, since both are normal ferroelectrics. It should be noted that the hysteresis loop of SBNK20 has a certain leakage characteristic due to K + The ionic radius is the largest and therefore, possibly a small fraction of K + Ions do not enter the crystal lattice and volatilize at high temperature to form pores, reducing the resistance of the ceramic.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (4)
1. A method for regulating ferroelectric property of unfilled barium strontium niobate material by doping ions with different radiuses, wherein the barium strontium niobate material is an unfilled tungsten bronze structure ferroelectric oxide represented by SBN, and is characterized in that the initial chemical formula of the doped barium strontium niobate material is (1-x) SBN-0.5xM 2 CO 3 Wherein SBN represents an underfilling tungsten bronze structure relaxor ferroelectric Sr 0.6 Ba 0.4 Nb 2 O 6 ，M + ＝Li + 、Na + Or K + X represents Li + 、Na + Or K + Doping amount of ions.
2. The method of claim 1, wherein x has a value of 0 to 0.2.
3. The method according to claim 2, comprising the steps of:
(1) Firstly, preparing single-phase SBN powder by a solid-phase chemical reaction sintering method; next, SBN-0.5xM according to the formula (1-x) 2 CO 3 WeighingSingle-phase SBN powder and M subjected to drying treatment 2 CO 3 Powder, said M 2 CO 3 Is Li 2 CO 3 、Na 2 CO 3 、K 2 CO 3 One of the following;
(2) Uniformly mixing the powder weighed in the step (1) by wet ball milling, drying, pressing into slices, placing in a crucible, sintering at high temperature, and carrying out M 2 CO 3 The C element in the powder is completely volatilized, and M + Ions then enter the lattice of the tungsten bronze structure and occupy unoccupied sites in the SBN, thereby obtaining M + Ion doped SBN ceramics.
4. A method according to claim 3, wherein the high temperature sintering in step (2) is carried out at a temperature of 1200-1350 ℃ for a period of 1-4 hours.
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| CN110668816A (en) * | 2019-10-16 | 2020-01-10 | 电子科技大学 | Lead-free energy storage dielectric ceramic material with tungsten bronze structure and preparation method thereof |
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| CN116425536A (en) * | 2023-04-11 | 2023-07-14 | 西安理工大学 | Ti-doped barium strontium gadolinium niobate ferroelectric ceramic material with non-axiom modulation structure and preparation method thereof |
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| CN110668816A (en) * | 2019-10-16 | 2020-01-10 | 电子科技大学 | Lead-free energy storage dielectric ceramic material with tungsten bronze structure and preparation method thereof |
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