CN103819189B - Relaxation ferroelectric material Sr4CaBiTi3Nb7O30 and preparation method thereof - Google Patents
Relaxation ferroelectric material Sr4CaBiTi3Nb7O30 and preparation method thereof Download PDFInfo
- Publication number
- CN103819189B CN103819189B CN201410082646.9A CN201410082646A CN103819189B CN 103819189 B CN103819189 B CN 103819189B CN 201410082646 A CN201410082646 A CN 201410082646A CN 103819189 B CN103819189 B CN 103819189B
- Authority
- CN
- China
- Prior art keywords
- cabiti
- room temperature
- preparation
- ferroelectric material
- relaxation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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
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, and the dielectric properties due to its excellence has application space more widely.Pb-Based Relaxor Ferroelectric Materials refers to that para-electric-ferroelectric transformation belongs to a class ferroelectric material of Diffuse phase transition, 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)-ε " (ω); ω is the real part of radian frequency; ε ' (ω) varies with temperature and presents relatively wide and change mild peak, the temperature T that its maximum ε ' (ω) value is corresponding
mwith the increase of ω to high-temperature mobile.This feature is very similar to the feature of structural glass transformation, spin-glass transition.Relaxation ferroelectric can regulate and control the microtexture of material on a molecular scale, thus realizes the functional materials with performance required for us 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 by A
1position (R occupies) and A
2the ionic radius difference Δ R impact of position (M occupies).It is reported that larger ionic radius difference Δ R tends to occur normal ferroelectric transformation peaks, and less ionic radius difference is tended to form relaxation ferroelectric.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 features such as 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, and 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, stoichiometrically 8:2:1:6:7 takes Powdered SrCO
3, CaCO
3, Bi
2o
3, TiO
2, Nb
2o
5, fully after mixing, add dehydrated alcohol ball milling 20-30 hour, the liquid mixture obtained cured, obtain dry solid mixture;
B, by the solid mixture of aforementioned gained grind, obtain solid powdery mixture, by gained mixture pre-burning 3-6 hour at 1000--1150 DEG C of temperature, obtain powdery substance;
C, powdery substance is sintered 2--6 hour at 1300 ± 50 DEG C 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 described powdery substance sinters at 1300 ± 50 DEG C of temperature, by described powdery substance with the pressure tabletted of 20-40MPa, then sintered by sheet sample, 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, 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 in ferroelectric photovoltaic etc. of lead based relaxor ferroelectric material.In addition, preparation technology of the present invention is simple, and cost is low, and without the need to 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 relation map;
Fig. 4 is Sr in embodiment
4caBiTi
3nb
7o
30the contrast figure of the ferroelectric hysteresis loop that ferroelectric ceramic material sample is measured when 20Hz, the electric field added by 4 ferroelectric hysteresis loops is 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, fully add dehydrated alcohol ball milling 20-30 hour after mixing.
Second step, gained mixed solution is added dehydrated alcohol from ball grinder complete sucking-off in beaker.The beaker that mixed solution is housed is put into baking oven, and 110 DEG C of bakings obtain solid mixture in 10 hours.The solid mixture of aforementioned gained is put into mortar grinding 2 hours, obtain solid powdery mixture.Gained mixture is transferred in alumina crucible, and puts into program stove, 1000--1150 DEG C of pre-burning 3-6 hour.
Sheet sample with the pressure tabletted of 20-40MPa, is transferred in crucible by the 3rd step by gained powder.The crucible that sheet sample is housed is placed in program stove, and 1300 ± 50 DEG C of sintering 2--6 hour, drop to room temperature naturally.Can obtain molecular formula is Sr
4caBiTi
3nb
7o
30ceramics sample.
The pottery adopting above method to prepare possesses that structure is single-phase, the above relaxation behavior of low-leakage current, 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; The ferroelectric test macro of Primer II of Radiant Technologies is adopted to measure the ferroelectricity of sample and leakage current.
Adopt ferroelectricity ceramics sample Sr obtained in embodiment
4caBiTi
3nb
7o
30xRD as shown in Figure 1, the ICDD-PDF card being numbered NO.40-358 that all diffraction peaks and JCPDS (JCPDS) publish coincide, confirm ceramics sample Sr
4caBiTi
3nb
7o
30structure is single-phase.
Fig. 2 gives ferroelectricity ceramics sample Sr
4caBiTi
3nb
7o
30sEM collection of illustrative plates, from figure, can observe sample particle 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 gives ferroelectricity ceramics sample Sr
4caBiTi
3nb
7o
30specific inductivity and dissipation factor with the change curve of measuring tempeature, can find out from Fig. 3 (a) and occur ferroelectric transformation peaks near 100 DEG C, and we obviously can observe the increase of peak with 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 when 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 in order to illustrate technical scheme of the present invention and unrestricted, although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of right 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, stoichiometrically 8:2:1:6:7 takes Powdered SrCO
3, CaCO
3, Bi
2o
3, TiO
2, Nb
2o
5, fully after mixing, add dehydrated alcohol ball milling 20-30 hour, the liquid mixture obtained cured, obtain dry solid mixture;
B, by the solid mixture of aforementioned gained grind, obtain solid powdery mixture, by gained mixture pre-burning 3-6 hour at 1000--1150 DEG C of temperature, obtain powdery substance;
C, powdery substance is sintered 2--6 hour at 1300 ± 50 DEG C 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, before described powdery substance sinters at 1300 ± 50 DEG C of temperature, by described powdery substance with the pressure tabletted of 20-40MPa, then sintered by sheet sample, can obtain molecular formula is Sr
4caBiTi
3nb
7o
30flaky pottery sample.
3. a Pb-Based Relaxor Ferroelectric Materials Sr according to claim 1 or 2
4caBiTi
3nb
7o
30the Pb-Based Relaxor Ferroelectric Materials prepared by preparation method, it is characterized in that, its molecular formula is Sr
4caBiTi
3nb
7o
30, its structure is single-phase, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410082646.9A CN103819189B (en) | 2014-03-07 | 2014-03-07 | Relaxation ferroelectric material Sr4CaBiTi3Nb7O30 and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410082646.9A CN103819189B (en) | 2014-03-07 | 2014-03-07 | Relaxation ferroelectric material Sr4CaBiTi3Nb7O30 and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103819189A CN103819189A (en) | 2014-05-28 |
| CN103819189B true CN103819189B (en) | 2015-07-08 |
Family
ID=50754529
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410082646.9A Expired - Fee Related CN103819189B (en) | 2014-03-07 | 2014-03-07 | Relaxation ferroelectric material Sr4CaBiTi3Nb7O30 and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103819189B (en) |
Families Citing this family (2)
| 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 |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011040630A1 (en) * | 2009-09-30 | 2011-04-07 | Canon Kabushiki Kaisha | Piezolectric material comprising tungsten bronze structure metal oxide |
-
2014
- 2014-03-07 CN CN201410082646.9A patent/CN103819189B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103819189A (en) | 2014-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101811866B (en) | Novel lead-free X8R type capacitor ceramic material and preparation method thereof | |
| Bhattacharyya et al. | Influence of excess sodium addition on the structural characteristics and electrical conductivity of Na0. 5Bi0. 5TiO3 | |
| CN109626988A (en) | High pressure electroresponse and the piezoceramic material of high-curie temperature and preparation method thereof | |
| CN104860672A (en) | High dielectric microwave ceramic dielectric material and preparation method thereof | |
| Puli et al. | Effect of lead borosilicate glass addition on the crystallization, ferroelectric and dielectric energy storage properties of Ba0. 9995La0. 0005TiO3 ceramics | |
| Xiao et al. | Crystal structure and microwave dielectric properties of MgZr1− xSnxNb2O8 ceramics | |
| Dong et al. | Microwave dielectric properties of Li (Mg1− xNix) PO4 ceramics for LTCC applications | |
| Brzozowski et al. | Grain growth control in Nb-doped BaTiO3 | |
| Sun et al. | Effects of sintering temperature on the microstructure and dielectric properties of BaZr0. 2Ti0. 8O3 ceramics | |
| Hu et al. | Microstructure and dielectric properties of highly tunable Ba0. 6Sr0. 4TiO3/MgO/Al2O3/ZnO composite | |
| CN103819189B (en) | Relaxation ferroelectric material Sr4CaBiTi3Nb7O30 and preparation method thereof | |
| Alkathy et al. | Effect of Bi and Li co-substituted SrTiO 3 ceramics on structural and dielectric properties | |
| Wei et al. | Ba9Y2Si6O24: A new silicate dielectric ceramic for microwave communication application | |
| Yun et al. | Dielectric properties of bismuth doped Ba1− xCaxTiO3 ceramics | |
| CN106007707B (en) | Mg-Nb doped bismuth titanate microwave-medium ceramics and preparation method thereof | |
| CN104649673A (en) | Neodymium niobate ceramic having improved microwave dielectric characteristic by substituting neodymium ions with lanthanum ions | |
| CN106518058A (en) | Lead-free compound ferroelectric ceramic composed of potassium-bismuth titanate and zinc oxide and preparation thereof | |
| Bhaskar Reddy et al. | Structural and dielectric characterization of Sr substituted Ba (Zr, Ti) O 3 based functional materials | |
| CN107311643A (en) | The leadless electronic ceramic material and preparation method of wide operation temperature area high dielectric property | |
| CN104876564A (en) | (1-x)Li0.45Re0.45Ca0.1TiO[3-x]Bi0.5Ae0.5MeO3 high-dielectric microwave ceramic and preparation method thereof | |
| Zhang et al. | Low dielectric loss of Bi-doped BaZr0. 15Ti0. 85O3 ceramics for high-voltage capacitor applications | |
| Shen et al. | Structural characteristics and dielectric properties of Nd-doped SrTiO3 ceramics by introducing Ti vacancies for valence compensation | |
| Wang et al. | Dielectric properties of new perovskite ceramics (Na1/4Bi3/4)(Mg1/4Ti3/4) O3 and (K1/4Bi3/4)(Mg1/4Ti3/4) O3 | |
| CN108689702A (en) | A kind of high-k low-loss barium zirconium phthalate dielectric material and preparation method thereof | |
| Yang et al. | Influence of the processing way for La3+-doping on crystal structure, microstructure, and microwave dielectric properties of Ca0. 7Ti0. 7La0. 3Al0. 3O3 ceramics |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150708 Termination date: 20160307 |