CN113666742A - Material and method for realizing relaxation-normal ferroelectric phase transition by doping - Google Patents
Material and method for realizing relaxation-normal ferroelectric phase transition by doping Download PDFInfo
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- 230000007704 transition Effects 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000012071 phase Substances 0.000 claims abstract description 52
- 239000000843 powder Substances 0.000 claims abstract description 50
- 239000010937 tungsten Substances 0.000 claims abstract description 27
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 27
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 13
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 229910000906 Bronze Inorganic materials 0.000 claims abstract description 5
- 239000010974 bronze Substances 0.000 claims abstract description 5
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 4
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 3
- 238000000498 ball milling Methods 0.000 claims description 9
- 229910003378 NaNbO3 Inorganic materials 0.000 claims description 7
- 229910019695 Nb2O6 Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- MUPJWXCPTRQOKY-UHFFFAOYSA-N sodium;niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Na+].[Nb+5] MUPJWXCPTRQOKY-UHFFFAOYSA-N 0.000 claims description 5
- 239000011812 mixed powder Substances 0.000 claims description 3
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- 229910052593 corundum Inorganic materials 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 description 11
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 230000010287 polarization Effects 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000005621 ferroelectricity Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 1
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Inorganic materials [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 1
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Abstract
The invention discloses a material for realizing relaxation-normal ferroelectric phase transition by doping and a method thereof. The chemical formula of the material is (1-x) SBN-xNN (x is 0-0.8); na in the material+Occupying the tungsten bronze structure without being Sr2+And Ba2+The occupied lattice position at A position is in a non-filled tungsten bronze structure when x is 0, in a filled tungsten bronze structure when x is 0.4>0.4, the material has a composite structure of tungsten bronze and perovskite two phases. The invention adopts a two-step solid phase reaction method, firstly single-phase SBN powder is synthesized, and then the single-phase SBN powder and Na are mixed2CO3、Nb2O5Mixing the powder uniformlyAnd sintering at high temperature to obtain the corresponding ceramic material. According to the invention, the crystal structure of the SBN is converted from a non-filled type to a filled type by doping NN, and relaxation-normal ferroelectric phase transition is generated near x being 0.4, so that relaxation-normal ferroelectric phase transition which is difficult to realize under general conditions is realized.
Description
Technical Field
The invention relates to a method for preparing a compound through NaNbO3(NN) doped tungsten bronze Structure Sr0.75Ba0.25Nb2O6(SBN), a material for realizing relaxation-normal ferroelectric phase transition and a preparation method thereof.
Background
The relaxor ferroelectric generally has small and even nanoscale irregular-shaped ferroelectric domains, and macroscopically shows that the relaxor ferroelectric has the characteristics of a slender electric hysteresis loop, small residual polarization, small coercive field and the like. The normal ferroelectric has larger ferroelectric domain with regular shape, and macroscopically shows that the normal ferroelectric has the characteristics of saturated hysteresis loop, larger remanent polarization, larger coercive field and the like. Theoretically, the realization of the mutual transformation between relaxation and normal ferroelectrics can effectively regulate and control the size and the form of a ferroelectric domain, which has very important practical significance for optimizing macroscopic electrical properties.
At present, phase transition research in this respect is mainly focused on perovskite ferroelectric materials, and in particular, normal-relaxation ferroelectric phase change is generally easy to realize, because substitution or doping generally makes the chemical composition of the materials more complex, and will disturb the long-range ferroelectric sequence, inhibit the size of ferroelectric domains, thereby enhancing the relaxation degree of the ferroelectric materials, and result in normal-relaxation ferroelectric phase transition. This means that it is difficult to realize the relaxor-normal ferroelectric phase transition by means of doping, and therefore, studies on the relaxor-normal ferroelectric phase transition have been rarely reported.
Similar to the perovskite structure, the tungsten bronze structure has oxygen octahedrons as basic structural units, and the oxygen octahedrons connected by the common vertices form three voids: two 12-coordinate quadrangular prisms A1 bit, four 15-coordinate pentagonal prisms A2 bit and four 9-coordinate triangular prisms C bit, and the chemical formula is [ (A1)2(A2)4C4(B1)2(B2)8]O30. The A bit can be classified into a full fill type, a full fill type and a non-full fill type according to the occupation situation of the A bit. Sr0.75Ba0.25Nb2O6(SBN) has a non-filled tungsten bronze structure because of its A site occupancy of 5/6. SBN is a typical representative of tungsten bronze structure relaxor ferroelectric material, whichThe a site of 1/6 in the crystal lattice is not occupied, which makes it possible to realize the unfilled-filled type structural transformation, and further the relaxation-normal ferroelectric phase, by doping in the SBN unfilled tungsten bronze structure ferroelectric material. On the other hand, consider Sr2+、Ba2+Respectively has an ionic radius of
And
and Na+Respectively has an ionic radius of
The close ionic radii are such that NaNbO3(NN) can be used as a doping modification substance to pass Na+Occupying the unoccupied A bit, Nb in the SBN5+Direct homosubstitution of Nb at the B-position in SBN5+Thereby modifying the crystal structure of the SBN, reducing the average A-site ion radius in the structure, and the like to be closer to the value of normal ferroelectric, and further realizing relaxation-normal ferroelectric phase transition which is difficult to realize under general conditions.
Disclosure of Invention
Aiming at the current situation that relaxation-normal ferroelectric phase transition is difficult to realize in common ferroelectric materials by doping, the invention provides a material and a method for realizing relaxation-normal ferroelectric phase transition by doping NN in SBN.
The technical scheme for realizing the relaxation-normal ferroelectric phase transition is as follows:
a material for realizing relaxation-normal ferroelectric phase transition by doping, the chemical formula of the material is (1-x) SBN-xNN, wherein SBN represents tungsten bronze structure Sr0.75Ba0.25Nb2O6NN represents NaNbO3X is 0-0.8; na in the material+Occupying the tungsten bronze structure without being Sr2+And Ba2+The occupied lattice position at A position is in a non-filled tungsten bronze structure when x is 0, in a filled tungsten bronze structure when x is 0.4>0.4, the material has tungsten bronze and perovskiteTwo phases coexist.
The invention relates to a method for realizing relaxation-normal ferroelectric phase transition by doping, which comprises the following steps:
(1) firstly, obtaining single-phase SBN powder by a solid-phase reaction sintering method; secondly, weighing the single-phase SBN powder after drying treatment and Na satisfying the stoichiometric ratio according to the chemical formula (1-x) SBN-xNN2CO3、Nb2O5Powder; wherein SBN represents a tungsten bronze structure Sr0.75Ba0.25Nb2O6NN represents NaNbO3，x＝0-0.8；
(2) And (2) ball-milling the powder weighed in the step (1) to uniformly mix the powder, drying the mixed powder, pressing the dried powder into a sheet, placing the sheet in a crucible, and sintering the sheet at 1150-x 1350 ℃ for 3 hours to obtain the (1-x) SBN-xNN ceramic material with good compactness.
The invention has the beneficial effects that:
1. adopting a two-step solid-phase reaction sintering method, and mixing tungsten bronze structure oxide SBN with different molar ratios and Na with stoichiometric ratio2CO3、Nb2O5The powders were mixed uniformly and sintered at high temperature to form (1-x) SBN-xNN ceramic samples. The method for preparing the ceramic sample is convenient and efficient, does not have a complex process, does not relate to expensive equipment, is low in cost, and can be applied to actual industrial production.
2. Relaxation-normal ferroelectric phase transition which is difficult to realize under general conditions is realized through NN doping SBN, and a corresponding crystal structure is converted into a filled tungsten bronze structure from a non-filled tungsten bronze structure. The transformation of the structure and the relaxation property can remarkably regulate and control the electrical properties of the material, including ferroelectric, dielectric and piezoelectric properties. The invention provides a very convenient and efficient design idea for regulating and controlling the structure and the electrical property of the ferroelectric material.
Drawings
FIG. 1 is an x-ray diffraction spectrum of a series of (1-x) SBN-xNN ceramic samples prepared according to examples 1, 2, 3, 4, 5.
FIG. 2 shows a series of (1-x) SBN-xNN ceramics prepared according to examples 1, 2, 3, 4 and 5Dielectric constant ε of porcelain sampler(left axis) and dielectric loss tan δ (right axis). Wherein, the graphs (a), (b), (c), (d) and (e) are dielectric spectrums of components x which are 0,0.2,0.4,0.6 and 0.8 respectively, and the graph (f) is a relation graph of phase transition temperature and components.
FIG. 3 is a plot of the room temperature hysteresis of a series of (1-x) SBN-xNN ceramic samples prepared in examples 1, 2, 3, 4, 5.
FIG. 4 is a graph of piezoelectric coefficients versus composition for series (1-x) SBN-xNN ceramic samples prepared in examples 1, 2, 3, 4, and 5.
Detailed Description
The invention provides a method for preparing a high-performance polymer by NaNbO3(NN) doping to control Sr0.75Ba0.25Nb2O6The ferroelectricity of (SBN) enables SBN materials to achieve relaxation-normal ferroelectric phase transitions. The chemical formula of the doped material is (1-x) SBN-xNN (x is 0-0.8). Due to Na+Ionic radius and Sr occupying A position in SBN2+And Ba2+Have similar ionic radii, so Na+Ions can enter the lattice of the SBN and occupy the otherwise unoccupied a-sites. And as the NN content increases (x is 0-0.4), the original unoccupied A site is gradually and completely occupied, so that the crystal structure is changed from an unfilled type corresponding to x being 0 to a filled type corresponding to x being 0.4; meanwhile, its electrical properties show a process of converting from a relaxor ferroelectric to a normal ferroelectric, and shows a complete normal ferroelectric characteristic in the vicinity of x ═ 0.4. With further increase in NN content, i.e. x>At 0.4, the material has a composite structure in which two phases of tungsten bronze and perovskite coexist.
Example 1
3.9144 grams of SrCO were weighed3Powder, 1.7441 g BaCO3Powder with 9.3501 g Nb2O5The powder (x ═ 0) was put into a ball mill pot with an appropriate amount of ball milling beads and distilled water was added thereto in an amount of about 2/3 volumes of the ball mill pot, and ball milling was carried out for 24 hours to mix them uniformly. After the resulting powder was dried, a suitable amount of the powder was pressed into a block having a diameter of about 20 mm and a thickness of about 5 to 6 mm under a pressure of 15 MPa. In Al2O3Spreading a thin layer of uniformly mixed powder at the bottom of the crucible cover, and placing the powder into a formed blockAl2O3The wafer is covered on the crucible, so that the block body is in a sealed state. And (3) placing the crucible in a muffle furnace, preserving heat for 30 minutes from room temperature to 400 ℃, then heating to the sintering temperature (1400 ℃) and preserving heat for 3 hours, then cooling to 400 ℃, then cooling to room temperature along with the furnace, and controlling the temperature rise and fall rate at 5 ℃/minute in the whole process. And after the ceramic block is obtained, manually grinding the ceramic block, adding distilled water into the ceramic block, ball-milling the ceramic block for 24 hours, and drying the obtained slurry to obtain single-phase SBN powder. Then pressing a proper amount of the powder into a thin slice with the diameter of about 10 mm and the thickness of about 2-3 mm by using the pressure of 15 MPa. In Al2O3Spreading a thin layer of SBN powder at the bottom of the crucible, placing the formed sheet, covering the sheet with the powder, and finally, adding Al2O3The wafer is covered on the crucible, so that the wafer is in a sealed state. And (3) putting the crucible sealed with the sheet into a muffle furnace, heating, preserving heat for 30 minutes from room temperature to 400 ℃, then heating to the sintering temperature (1350 ℃), preserving heat for 3 hours, cooling to 400 ℃, then cooling to room temperature along with the furnace, and controlling the temperature rising and falling rate at 5 ℃/minute in the whole process. Single-phase SBN ceramics were obtained and their structural properties were characterized.
Example 2
3.2076 g of single-phase SBN powder, 0.1115 g of Na were weighed out2CO3Powder with 0.2805 g Nb2O5The powder (x ═ 0.2) was placed in a ball mill pot with the appropriate amount of ball milling beads and about 2/3 volumes of absolute ethanol were added and ball milled for 24 hours to mix well. After the resulting slurry was dried, an appropriate amount of the powder was pressed into a sheet having a diameter of about 10 mm and a thickness of about 2 to 3 mm under a pressure of 15 MPa. In Al2O3Spreading a thin layer of the powder at the bottom of the crucible, placing the formed sheet, covering the sheet with the powder, and adding Al2O3The wafer is covered on the crucible, so that the wafer is in a sealed state. And (3) putting the crucible sealed with the thin sheet into a muffle furnace, heating, preserving heat for 30 minutes from room temperature to 400 ℃, then heating to the sintering temperature (1250 ℃), preserving heat for 3 hours, cooling to 400 ℃, then cooling to room temperature along with the furnace, and controlling the temperature rising and falling rate at 5 ℃/minute in the whole process. NN ceramics with the chemical formula of 0.8SBN-0.2 are obtained, and the structure and the performance of the NN ceramics are characterized。
Example 3
2.4057 grams of single phase SBN powder was weighed in with 0.2230 grams of Na2CO3Powder with 0.5610 g Nb2O5The powder (x ═ 0.4) was placed in a ball mill pot with the appropriate amount of ball milling beads and about 2/3 volumes of absolute ethanol were added and ball milled for 24 hours to mix well. After the resulting slurry was dried, an appropriate amount of the powder was pressed into a sheet having a diameter of about 10 mm and a thickness of about 2 to 3 mm under a pressure of 15 MPa. In Al2O3Spreading a thin layer of the powder on the bottom of the crucible, placing the formed sheet, covering the sheet with the powder, and adding Al2O3The wafer is covered on the crucible, so that the wafer is in a sealed state. And (3) putting the crucible sealed with the thin sheet into a muffle furnace, heating, preserving the heat for 30 minutes from room temperature to 400 ℃, then heating to the sintering temperature (1200 ℃), preserving the heat for 3 hours, then cooling to 400 ℃, then cooling to room temperature along with the furnace, and controlling the temperature rising and reducing rate at 5 ℃/minute in the whole process. The NN ceramic with the chemical formula of 0.6SBN-0.4 is obtained, and the structure and the performance of the NN ceramic are characterized.
Example 4
1.6038 grams of single phase SBN powder was weighed in with 0.3345 grams of Na2CO3Powder with 0.8415 g Nb2O5The powder (x ═ 0.6) was placed in a ball mill pot with the appropriate amount of ball milling beads and about 2/3 volumes of absolute ethanol were added and ball milled for 24 hours to mix well. After the resulting slurry was dried, an appropriate amount of the powder was pressed into a sheet having a diameter of about 10 mm and a thickness of about 2 to 3 mm under a pressure of 15 MPa. In Al2O3Spreading a thin layer of the powder at the bottom of the crucible, placing the formed sheet, covering the sheet with the powder, and adding Al2O3The wafer is covered on the crucible, so that the wafer is in a sealed state. And (3) putting the crucible sealed with the thin sheet into a muffle furnace, heating, preserving the heat for 30 minutes from room temperature to 400 ℃, then heating to the sintering temperature (1200 ℃), preserving the heat for 3 hours, then cooling to 400 ℃, then cooling to room temperature along with the furnace, and controlling the temperature rising and reducing rate at 5 ℃/minute in the whole process. NN ceramics with the chemical formula of 0.4SBN-0.6 are obtained, and the structure and the performance of the NN ceramics are characterized.
Example 5
0.8019 grams of single phase SBN powder was weighed in with 0.4460 grams of Na2CO3Powder with 1.1220 g Nb2O5The powder (x ═ 0.8) was placed in a ball mill pot with the appropriate amount of ball milling beads and about 2/3 volumes of absolute ethanol were added and ball milled for 24 hours to mix well. After the resulting slurry was dried, an appropriate amount of the powder was pressed into a sheet having a diameter of about 10 mm and a thickness of about 2 to 3 mm under a pressure of 15 MPa. In Al2O3Spreading a thin layer of the powder at the bottom of the crucible, placing the formed sheet, covering the sheet with the powder, and adding Al2O3The wafer is covered on the crucible, so that the wafer is in a sealed state. And (3) putting the crucible sealed with the thin sheet into a muffle furnace, heating, preserving the heat for 30 minutes from room temperature to 400 ℃, then heating to the sintering temperature (1150 ℃) and preserving the heat for 3 hours, then cooling to 400 ℃, then cooling to room temperature along with the furnace, and controlling the temperature rising and falling rate at 5 ℃/minute in the whole process. NN ceramics with the chemical formula of 0.2SBN-0.8 are obtained, and the structure and the performance of the NN ceramics are characterized.
And (3) testing results:
FIG. 1 is an X-ray diffraction pattern (XRD) of a series of (1-X) SBN-xNN ceramic samples prepared in the above 5 examples, from which it can be seen that all diffraction peaks match the standard peak of a single-phase SBN (see bottom curve JCPDS #72-0284) at X ═ 0 to 0.4, confirming that only Na is present in this composition interval2+And entering the SBN crystal lattice position to form a solid solution. In the X-0.6, 0.8 component, the X-ray diffraction peaks are derived not only from the tungsten bronze structure but also partially from the perovskite structure NaNb3The standard peak (see top curve JCPDS #75-2102) demonstrates that in both components, the tungsten bronze and perovskite phases coexist and form a composite structure.
Fig. 2 is a dielectric constant and dielectric loss spectrum of the prepared series (1-x) SBN-xNN ceramic samples, and it can be seen that as the value of x increases to 0.4 (fig. (a) - (c)), the ferroelectric-paraelectric transition peak pattern exhibits a characteristic of decreasing from a relatively broad and flat dispersion until the transition temperature at each frequency approaches, corresponding to the process of transition from a relaxor ferroelectric to a normal ferroelectric. In the X ═ 0.6 and X ═ 0.8 components (fig. (d), (e)), the two-phase composite structure obtained by the aforementioned X-ray diffraction characterization also exhibits two phase transition peaks here, respectively, the low-temperature phase transition peak originating from NN and the high-temperature phase transition peak originating from SBN. The graph (f) shows the ferroelectric-paraelectric phase transition temperatures corresponding to different components, and it can be seen that the phase transition temperature increases from room temperature to about 200 ℃ with the increase of the value of x, and the electrical properties can be well applied in various high-temperature scenes while maintaining a high dielectric constant and a small dielectric loss.
Fig. 3 is a hysteresis loop diagram of a prepared series of (1-x) SBN-xNN ceramic samples, and it can be seen that as the value of x increases, the hysteresis loop shifts from an elongated relaxor ferroelectric characteristic to a relatively saturated normal ferroelectric characteristic with a larger remanent polarization and a larger coercive field. After a doping amount higher than 0.4, the formation of a two-phase composite structure microscopically forms more defects so that its ferroelectricity is deteriorated.
Fig. 4 is a piezoelectric coefficient-composition relationship diagram of the prepared series (1-x) SBN-xNN ceramic samples, and it can be seen that the piezoelectric coefficient of a single-phase SBN at room temperature is 0pC/N due to near-ideal relaxation properties, and the piezoelectric coefficient of x ═ 0.2-0.4 composition gradually increases from 5pC/N to 15pC/N due to relaxation-normal ferroelectric phase transition caused by NN doping. x is 0.6, the 0.8 component deteriorates its piezoelectric performance due to microscopic defects caused by the composite structure, and the piezoelectric coefficient value is gradually decreased to 9pC/N and 8 pC/N.
Claims (5)
1. A material for realizing relaxation-normal ferroelectric phase transition by doping is characterized in that the chemical formula of the material is (1-x) SBN-xNN, wherein SBN represents tungsten bronze structure Sr0.75Ba0.25Nb2O6NN represents NaNbO3X is 0-0.8; na in the material+Occupying the tungsten bronze structure without being Sr2+And Ba2+The occupied lattice position at A position is in a non-filled tungsten bronze structure when x is 0, in a filled tungsten bronze structure when x is 0.4>0.4, the material has a composite structure of tungsten bronze and perovskite two phases.
2. A material for achieving a relaxor-normal ferroelectric phase transition by doping according to claim 1, wherein x has a value of 0 to 0.4.
3. A method for effecting a relaxor-normal ferroelectric phase transition by doping, comprising the steps of:
(1) firstly, obtaining single-phase SBN powder by a solid-phase reaction sintering method; secondly, weighing the single-phase SBN powder after drying treatment and Na satisfying the stoichiometric ratio according to the chemical formula (1-x) SBN-xNN2CO3、Nb2O5Powder; wherein SBN represents a tungsten bronze structure Sr0.75Ba0.25Nb2O6NN represents NaNbO3，x＝0-0.8；
(2) And (2) ball-milling the powder weighed in the step (1) to uniformly mix the powder, drying the mixed powder, pressing the dried powder into a sheet, placing the sheet in a crucible, and sintering the sheet at a high temperature to obtain the (1-x) SBN-xNN ceramic material with good compactness.
4. The method for realizing relaxation-normal ferroelectric phase transition by doping as claimed in claim 3, wherein in the step (2), the temperature of high temperature sintering is 1150-1350 ℃ for 1-5 hours.
5. A method for performing a relaxor-normal ferroelectric phase transition by doping according to claim 3, wherein in step (1), x is 0-0.4.
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