CN103819189A - Relaxation ferroelectric material Sr4CaBiTi3Nb7O30 and preparation method thereof - Google Patents

Relaxation ferroelectric material Sr4CaBiTi3Nb7O30 and preparation method thereof Download PDF

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CN103819189A
CN103819189A CN201410082646.9A CN201410082646A CN103819189A CN 103819189 A CN103819189 A CN 103819189A CN 201410082646 A CN201410082646 A CN 201410082646A CN 103819189 A CN103819189 A CN 103819189A
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cabiti
room temperature
preparation
ferroelectric material
relaxation
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CN103819189B (en
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袁松柳
方玉娇
龚高尚
王好文
郭谦
朱长明
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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Abstract

The invention relates to the technical field of ferroelectric material preparation, and discloses a relaxation ferroelectric material Sr4CaBiTi3Nb7O30 synthesized through a conventional solid phase method. The relaxation ferroelectric material Sr4CaBiTi3Nb7O30 is prepared through the following steps: at room temperature, weighing powdery SrCO3, CaCO3, Bi2O3, TiO2 and Nb2O5 according to the stoichiometric ratio of 8:2:1:6:7, uniformly mixing, drying, then presintering, and performing high temperature sintering. The ceramic material has is single-phase in structure, has a relaxation characteristic above room temperature, is low in leakage current, high in breakdown voltage and strong in ferroelectricity at room temperature, and the prepared sample has the property of preferred growth along a single phase. In the preparation of the relaxation ferroelectric material Sr4CaBiTi3Nb7O30, reducing atmosphere is not required, the process is simple, the cost is low, and environmental protection, no toxicity and no pollution are achieved. The relaxation ferroelectric material has a high potential of substituting lead-based relaxation ferroelectric material used as ferroelectric photovoltaic material.

Description

Pb-Based Relaxor Ferroelectric Materials Sr 4caBiTi 3nb 7o 30and preparation method thereof
Technical field
The present invention relates to ferroelectricity technical field of ceramic material, be specifically related to a kind of Pb-Based Relaxor Ferroelectric Materials Sr 4caBiTi 3nb 7o 30preparation method.
Background technology
Ferroelectric material, refers to a class material with ferroelectric effect.Relaxation ferroelectric is as a branch of ferroelectric material, because its excellent dielectric properties has application space more widely.Pb-Based Relaxor Ferroelectric Materials refers to that para-electric-ferroelectric transformation belongs to a class ferroelectric material of disperse phase transformation, and it has ferroelectricity and relaxation phenomena simultaneously.Compared with typical ferroelectrics, a characteristic feature of Relaxation Ferroelectrics is complex permittivity, ε * (ω)=ε ' (ω)-" (ω); the real part that ω is radian frequency; ε ' (ω) varies with temperature and presents relatively wide and change mild peak, its maximum ε ' (ω) is worth corresponding temperature T to ε mwith the increase of ω to high-temperature mobile.This feature is very similar to the feature that structural glass transformation, spin glassization change.Relaxation ferroelectric can the microtexture to material regulate and control on molecular level, thereby realizes and have the functional materials of our needed performance from structure properties angle, can be used for ferroelectric photovoltaic, FERROELECTRICS MEMORIES TECHNOLOGY and realize solid coolant.
Molecular formula is M 4r 2ti 3nb 7o 30(M=Ba, Sr) tungsten bronze(s) material, its dielectric essence is subject to A 1position (R occupies) and A 2the poor Δ R impact of ionic radius of position (M occupies).It is reported that the poor Δ R of larger ionic radius tends to occur normal ferroelectric transformation peaks, tend to form relaxation ferroelectric and less ionic radius is poor.At present by high temperature sintering at A 1position ginseng Bi synthesize ceramic material Sr 4caBiTi 3nb 7o 30still without any report.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of Pb-Based Relaxor Ferroelectric Materials Sr 4caBiTi 3nb 7o 30and preparation method thereof, the stupalith that this preparation method obtains is along unidirectional preferential growth, and it is single-phase to possess structure, the above relaxation behavior of room temperature, the feature such as leakage current is low, the room temperature ferroelectricity that voltage breakdown is high and very strong.
For solving the problems of the technologies described above, first the present invention proposes a kind of Pb-Based Relaxor Ferroelectric Materials Sr 4caBiTi 3nb 7o 30preparation method, comprise the following steps:
Under A, room temperature, take Powdered SrCO by stoichiometric ratio 8:2:1:6:7 3, CaCO 3, Bi 2o 3, TiO 2, Nb 2o 5, after fully mixing, add dehydrated alcohol ball milling 20-30 hour, the liquid mixture obtaining is cured, obtain dry solid mixture;
B, the solid mixture of aforementioned gained is ground, obtain solid powdery mixture, by gained mixture pre-burning 3-6 hour at 1000--1150 ℃ of temperature, obtain powdery substance;
C, by powdery substance sintering 2--6 hour at 1300 ± 50 ℃ of temperature, naturally drop to room temperature, can obtain molecular formula is Sr 4caBiTi 3nb 7o 30powdered ceramic sample.
Preferably, in described step C, before sintering, described powdery substance is suppressed in flakes with the pressure of 20-40MPa at 1300 ± 50 ℃ of temperature at described powdery substance, then sheet sample is carried out to sintering, can obtain molecular formula is Sr 4caBiTi 3nb 7o 30flaky pottery sample.
Pb-Based Relaxor Ferroelectric Materials prepared by the inventive method, its molecular formula is Sr 4caBiTi 3nb 7o 30, this material structure is single-phase, and even particle distribution, along unidirectional preferential growth; The above relaxation behavior of room temperature, under the extra electric field of 70kV/cm, maximum leakage current density is lower than 10 -6a/cm 2; Breakdown electric field, higher than 80kV/cm, has strong room temperature ferroelectricity.
The Pb-Based Relaxor Ferroelectric Materials Sr that the present invention prepares 4caBiTi 3nb 7o 30, possess structure single-phase, the above relaxation behavior of room temperature, low-leakage current, high-breakdown-voltage and very strong room temperature ferroelectricity, and possess along characteristics such as unidirectional preferential growths.Be a kind of multifunctional ceramic material with broad prospect of application, be especially expected to replace the application of lead based relaxor ferroelectric material at aspects such as ferroelectric photovoltaics.In addition, preparation technology of the present invention is simple, and cost is low, and without reducing atmosphere, environment-protecting asepsis is pollution-free.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, technical scheme of the present invention is further described in detail.
Fig. 1 is Sr in the embodiment of the present invention 4caBiTi 3nb 7o 30the XRD figure spectrum of ferroelectric ceramic material sample;
Fig. 2 is Sr in embodiment 4caBiTi 3nb 7o 30the SEM collection of illustrative plates of ferroelectric ceramic material sample;
Fig. 3 is under the survey frequency of 100Hz, 1kHz, 10kHz, 100kHz, 1MHz, 2MHz, Sr in embodiment 4caBiTi 3nb 7o 30ferroelectric ceramic material sample dielectric properties collection of illustrative plates.Fig. 3 (a), 3(b) be respectively specific inductivity and loss variation with temperature is related to collection of illustrative plates;
Fig. 4 is Sr in embodiment 4caBiTi 3nb 7o 30the contrast figure of the ferroelectric hysteresis loop that ferroelectric ceramic material sample is measured in the time of 20Hz, 4 added electric fields of ferroelectric hysteresis loop are respectively 50kV/cm, 60kV/cm, 70kV/cm and 80kV/cm.
Fig. 5 is Sr in embodiment 4caBiTi 3nb 7o 30ferroelectric ceramic material sample under the extra electric field of 70kV/cm leakage current with the contrast figure of the variation relation of strength of electric field.
Embodiment
Specific embodiment of the invention conventional solid-state method, produces ferroelectric ceramic(s) sample Sr through pre-burning and sintering 4caBiTi 3nb 7o 30, comprise the following steps:
The first step, takes pressed powder SrCO 3, CaCO3, Bi 2o 3, TiO 2, Nb 2o 5, its stoichiometry is respectively 0.12,0.03,0.015,0.09,0.105mol, after fully mixing, adds dehydrated alcohol ball milling 20-30 hour.
Second step, by gained mixed solution add dehydrated alcohol from ball grinder completely sucking-off to beaker.The beaker that mixed solution is housed is put into baking oven, and 110 ℃ of bakings obtain solid mixture for 10 hours.The solid mixture of aforementioned gained is put into mortar and grind 2 hours, obtain solid powdery mixture.Gained mixture is transferred in alumina crucible, and put into program stove, 1000--1150 ℃ of pre-burning 3-6 hour.
The 3rd step is in blocks with the pressure compacting of 20-40MPa by gained powder, and sheet sample is transferred in crucible.The crucible that sheet sample is housed is placed in to program stove, and 1300 ± 50 ℃ of sintering 2--6 hour, drop to room temperature naturally.Can obtain molecular formula is Sr 4caBiTi 3nb 7o 30ceramics sample.
The pottery that adopts above method to prepare possesses that structure is single-phase, low-leakage current, the above relaxation behavior of room temperature, high-breakdown-voltage and room temperature multiferroic, and possesses single-phase preferential growth.It is the ceramic material that a class has broad prospect of application.To the sign of sample microtexture, adopt X-ray diffractometer (XRD) to its material phase analysis; Ferroelectricity and the leakage current of the ferroelectric test macro of Primer II of employing Radiant Technologies to sample measured.
Adopt the ferroelectricity ceramics sample Sr making in embodiment 4caBiTi 3nb 7o 30xRD as shown in Figure 1, all diffraction peaks and JCPDS (JCPDS) publish the ICDD-PDF card that is numbered NO.40-358 coincide, confirmed ceramics sample Sr 4caBiTi 3nb 7o 30structure is single-phase.
Fig. 2 has provided ferroelectricity ceramics sample Sr 4caBiTi 3nb 7o 30sEM collection of illustrative plates, from figure, can observe sample particle and be evenly distributed, grain growing is good, and elongated bar-shaped enlarged view shows that crystal grain has the characteristic along unidirectional preferential growth.
Fig. 3 has provided ferroelectricity ceramics sample Sr 4caBiTi 3nb 7o 30specific inductivity and dissipation factor with measuring the change curve of temperature, from Fig. 3 (a), can find out and near 100 ℃, occur ferroelectric transformation peaks, and we can obviously observe peak with the increase of frequency toward this relaxation behavior of high-temperature mobile.
Fig. 4 is Sr in embodiment 4caBiTi 3nb 7o 30the contrast figure of 4 ferroelectric hysteresis loops that ferroelectric ceramic material sample is measured in the time of 20Hz, added electric field is respectively 50kV/cm, 60kV/cm, 70kV/cm and 80kV/cm.As can be seen from the figure sample shows very strong ferroelectricity, and its breakdown electric field is higher than 80kV/cm.Under the strength of electric field of room temperature 80kV/cm, maximum polarization and remnant polarization are respectively 9.57 μ C/cm 2with 2.74 μ C/cm 2.
Fig. 5 is Sr in embodiment 4caBiTi 3nb 7o 30ferroelectric ceramic material sample leakage current under the strength of electric field of 70kV/cm is schemed with the variation relation contrast of extra electric field.As can be seen from the figure the leakage current of sample is very little, and under the extra electric field of 70kV/cm, maximum leakage current density is lower than 10 -6a/cm 2.
It should be noted last that, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement technical scheme of the present invention, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of claim scope of the present invention.

Claims (3)

1. a Pb-Based Relaxor Ferroelectric Materials Sr 4caBiTi 3nb 7o 30preparation method, it is characterized in that, comprise the following steps:
Under A, room temperature, take Powdered SrCO by stoichiometric ratio 8:2:1:6:7 3, CaCO 3, Bi 2o 3, TiO 2, Nb 2o 5, after fully mixing, add dehydrated alcohol ball milling 20-30 hour, the liquid mixture obtaining is cured, obtain dry solid mixture;
B, the solid mixture of aforementioned gained is ground, obtain solid powdery mixture, by gained mixture pre-burning 3-6 hour at 1000--1150 ℃ of temperature, obtain powdery substance;
C, by powdery substance sintering 2--6 hour at 1300 ± 50 ℃ of temperature, naturally drop to room temperature, can obtain molecular formula is Sr 4caBiTi 3nb 7o 30powdered ceramic sample.
2. Pb-Based Relaxor Ferroelectric Materials Sr according to claim 1 4caBiTi 3nb 7o 30preparation method, it is characterized in that, in described step C, at described powdery substance at 1300 ± 50 ℃ of temperature before sintering, described powdery substance is in blocks with the pressure compacting of 20-40MPa, then sheet sample is carried out to sintering, can obtain molecular formula is Sr 4caBiTi 3nb 7o 30flaky pottery sample.
3. one kind according to Pb-Based Relaxor Ferroelectric Materials Sr described in claim 1 or 2 4caBiTi 3nb 7o 30the prepared Pb-Based Relaxor Ferroelectric Materials of preparation method, it is characterized in that, its molecular formula is Sr 4caBiTi 3nb 7o 30, its structure is single-phase, and even particle distribution, along unidirectional preferential growth; The above relaxation behavior of room temperature, under the extra electric field of 70kV/cm, maximum leakage current density is lower than 10 -6a/cm 2; Breakdown electric field, higher than 80kV/cm, has strong room temperature ferroelectricity.
CN201410082646.9A 2014-03-07 2014-03-07 Relaxation ferroelectric material Sr4CaBiTi3Nb7O30 and preparation method thereof Expired - Fee Related CN103819189B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106478096A (en) * 2015-08-31 2017-03-08 中国民航大学 A kind of rare earth base novel non-full of type tungsten bronze ferroelectric material and preparation method thereof
CN114874009A (en) * 2022-06-09 2022-08-09 郑州轻工业大学 Near-room temperature relaxation ferroelectric material Ba 4 SrBiTi 3 Nb 7 O 30 And preparation method and application thereof

Citations (1)

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Publication number Priority date Publication date Assignee Title
CN102549790A (en) * 2009-09-30 2012-07-04 佳能株式会社 Piezolectric material comprising tungsten bronze structure metal oxide

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Publication number Priority date Publication date Assignee Title
CN102549790A (en) * 2009-09-30 2012-07-04 佳能株式会社 Piezolectric material comprising tungsten bronze structure metal oxide

Non-Patent Citations (1)

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Title
胡长征: "新型无铅铌、钽酸盐陶瓷的制备与介电、铁电特性研究", 《中国博士学位论文全文数据库 工程科技I辑》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106478096A (en) * 2015-08-31 2017-03-08 中国民航大学 A kind of rare earth base novel non-full of type tungsten bronze ferroelectric material and preparation method thereof
CN114874009A (en) * 2022-06-09 2022-08-09 郑州轻工业大学 Near-room temperature relaxation ferroelectric material Ba 4 SrBiTi 3 Nb 7 O 30 And preparation method and application thereof
CN114874009B (en) * 2022-06-09 2022-12-13 郑州轻工业大学 Near-room temperature relaxation ferroelectric material Ba 4 SrBiTi 3 Nb 7 O 30 And preparation method and application thereof

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