CN103288437B - Six-layer ferrotitanium yttrium bismuth cobaltate ceramic material with multiferroic performance and preparation method thereof - Google Patents
Six-layer ferrotitanium yttrium bismuth cobaltate ceramic material with multiferroic performance and preparation method thereof Download PDFInfo
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- CN103288437B CN103288437B CN201210209229.7A CN201210209229A CN103288437B CN 103288437 B CN103288437 B CN 103288437B CN 201210209229 A CN201210209229 A CN 201210209229A CN 103288437 B CN103288437 B CN 103288437B
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Abstract
The invention relates to a six-layer ferrotitanium yttrium bismuth cobaltate ceramic material with multiferroic performance and a preparation method thereof. The Aurivillius-type oxide ceramic with a chemical formula Bi6YFe2CoTi3O21 has good ferroelectricity and ferromagnetism over room temperature. A Bi6YFe2CoTi3O21 sample is prepared by an improved Pechini method, and the Fe-O and Co-O octahedrons are orderly arranged relatively so as to locally obtain coupling between Fe-O-Co and Y-O-Co/Fe to improve the ferroelectric and magnetic performance of the sample. The technology is simple, reasonable and efficient, the sample preparation temperature is far lower than the preparation temperature of the prior art, and the technology is environment-friendly and very convenient for industrial production.
Description
Technical field
The present invention relates to many ferriferous oxides stupalith field, more specifically, relate to a kind of six laminate structure ferrotianium cobalt acid yttrium bismuth stupaliths with multi-ferrum property and preparation method thereof.
Background technology
Magnetoelectricity multi-iron material refers in certain warm area, shows ferroelectric sequence and Ferromagnetic/Antiferromagnetic sequence simultaneously, and there is the material of certain coupling each other.Recently, this material is attracted attention day by day, on the one hand because it not only can be used in ferroelectric with in the research and development of magnetic apparatus, what is more important it can utilize coupling between magnetoelectricity, design and devdlop for equipment provides additional one degree of freedom, thus shows very tempting application prospect on emerging spintronics, polymorphism information storage, electric drive ferro-resonance device and magnetic tuning piezoelectric transducer.Up to the present, in the multi-iron material found, ABO is only had
3the BiFeO of type structure
3there is ferroelectricity and ferromegnetism more than room temperature, but the leakage current of sample is comparatively large and more than room temperature be the demand that the characteristic such as antiferromagnetic can not meet practical application.In recent years, to BiFeO
3sample conducts extensive research, and result of study shows, may improve the electric property of sample by the method for A position doping, reduce the leakage current of sample, the ferroelectric properties of sample have also been obtained and significantly improves.Due to BiFeO
3be antiferromagnetism at normal temperatures, and antiferromagnetism is responsive not to the response of externally-applied magnetic field, does not also have the BiFeO of single-phase structure at present
3the report of material in practical application.
In order to meet multi-iron material needs in actual applications, in recent years, many ferroelectric materials become one of focus of material subject research.A Main way of the many ferroelectric materials of current research is the material of research single structure, and in this kind of material, double perovskite materials obtains people and payes attention to widely.Find with two kinds, to there is d in the B position of sample under study for action
0the magnetic ion of electronic structure carries out being coupled and greatly can improve the ferromagnetic property of sample, but in double perovskite materials research, also there are two subject matters at present: the synthesis of (1) sample must under high pressure be prepared, and is difficult to accomplish that sample B position ion has good order; (2) when ferroelectric with the ferromagnetic transformation temperature of sample is different more than room temperature.There is Aurivillius type stratified material in perovskite-like, with the crystalline structure of its uniqueness and performance, obtain in recent years and pay attention to comparatively widely.Its structural formula of Aurivillius type stratiform multi-iron material can be write as: Bi
2a
m-1b
mo
3m+3, be Bi specific to system of the present invention
2bi
m+2fe
mti
3o
3m+12, or be written as Bi
2o
2+ Bi
4ti
3o
12(BTO)+nBiMO
3(n=1,2..., M are magnetic ion), namely material can be regarded as and has the ferroelectric material BTO of perovskite structure by three layers and have the ionic group BiFeO of one or more magnet unit
3combine, its structure is at 2 bismuth oxygen layer ((Bi
2o
2)
2+) between clip 3 titanyls (Ti-O) octahedra and one or more magnet units (Fe-O) octahedra.Because bismuth oxygen layer has the effect of insulation layer and charge reservoir, effectively can reducing the leakage current of sample, having positive effect to improving sample electric property.
Summary of the invention
In order to optimize the ceramic layered ferroelectric properties of Aurivillius type and ferromagnetic property, the invention provides a kind of six laminate structure ferrotianium cobalt acid yttrium bismuth potteries with multi-ferrum property, its chemical formula is Bi
6yFe
2coTi
3o
21.
Ferrotianium cobalt acid yttrium bismuth pottery of the present invention has ferroelectricity and ferromegnetism more than room temperature simultaneously, and leakage current is less, and ferromegnetism is considerable, for the application in information storage, resonance, sensing etc. provides possibility.
Another object of the present invention is to provide the preparation method of this Aurivillius type many ferriferous oxides pottery (having six laminate structure ferrotianium cobalt acid yttrium bismuth potteries of multi-ferrum property), and described method comprises:
By titanic acid ester (preferred tetrabutyl titanate (C
16h
36o
4ti)), Bismuth trinitrate (preferably five nitric hydrate bismuth (Bi (NO
3)
35H
2o)), Yttrium trinitrate (preferably six nitric hydrate yttrium (Y (NO
3)
36H
2o)), iron nitrate (preferred Fe(NO3)39H2O (Fe (NO
3)
39H
2o)), cobaltous acetate (preferably four acetate hydrate cobalt (C
4h
6o
4co4H
2o)) be stoichiometrically dissolved in salpeter solution at 3: 6: 1: 2: 1, add complexing agent (preferred ethylenediamine tetraacetic acid (EDTA) (EDTA) and citric acid), EDTA, citric acid and metal ion mol ratio are preferably 0.7: 1: 1; By solution evaporate to dryness, gained powder, at 700-800 DEG C of pre-burning 2-4 hour, removes organism; At 800-1100 DEG C of sintering 5-10 hour, finally obtained target product after the powder compression molding of pre-burning.In the inventive method except retort furnace sintering, hot pressed sintering can also be adopted.
Present invention process is simple, adopts the Pechini method improved, has prepared Bi
6yFe
2coTi
3o
21the many ferriferous oxide potteries of six stratiform Aurivillius types, structure is 2 bismuth oxygen layer ((Bi
2o
2)
2+) between clip that 3 titanyls (Ti-O) are octahedra, 2 iron oxygen (Fe-O) are octahedra and 1 cobalt oxygen (Co-O) octahedron.Wherein replace the Bi ion of A position with Y ionic portions, can leakage current be effectively reduced, improve the ferroelectric properties of sample; With two kinds, there is d
0magnetic ion (M) Fe and Co of electronic structure, as B position ion, by coupling, improves the ferromagnetic property of sample.
Ferriferous oxide more than six layers provided by the invention pottery at room temperature has good ferroelectricity and ferromegnetism, sample when to measure electric field be 50kV/cm, remnant polarization (2P
r) be 0.88 μ C/cm
2, coercive field (2E
c) be 20kV/cm; Sample remanence rate (2M
r) be 1.48emu/g, coercive field (2H
c) be 244Oe.
Accompanying drawing explanation
Fig. 1 is the X ray picture of sample in the embodiment of the present invention 1;
Fig. 2 is the stereoscan photograph of sample in the embodiment of the present invention 1;
Fig. 3 is the transmission electron microscope photo of sample in the embodiment of the present invention 1;
Fig. 4 is the ferroelectric properties survey sheet of sample in the embodiment of the present invention 1;
Fig. 5 is the ferromagnetic property survey sheet of sample in the embodiment of the present invention 1.
Specific implementation method
Embodiment 1
Choose chemical pure tetrabutyl titanate (C
16h
36o
4ti), analytical pure five nitric hydrate bismuth (Bi (NO
3)
35H
2o), high-purity (4N) six nitric hydrate yttrium (Y (NO
3)
36H
2o), analytical pure Fe(NO3)39H2O (Fe (NO
3)
39H
2o), analytical pure four acetate hydrate cobalt (C
4h
6o
4co4H
2o) be raw material, stoichiometrically be dissolved in salpeter solution after 3: 6: 1: 2: 1 precise, add ethylenediamine tetraacetic acid (EDTA) (EDTA) and citric acid as complexing agent, EDTA, citric acid and metal ion mol ratio are 0.7: 1: 1, average rate stirs, and forms settled solution.
Bi prepared by table 1
6yFe
2coTi
3o
21
| Nomenclature of drug | Molecular weight | Medicine purity | Take quality/g |
| C 16H 36O 4Ti | 340.36 | 98％ | 7.893 |
| Bi(NO 3) 3·5H 2O | 485.07 | 99％ | 22.4977 |
| Y(NO 3) 3·6H 2O | 383.01 | 98％ | 2.9607 |
| Fe(NO 3) 3·9H 2O | 404 | 98.5％ | 6.2459 |
| C 4H 6CoO 4·4H 2O | 249.08 | 99.5％ | 1.9254 |
| EDTA | 292.24 | 98％ | 20.5572 |
| Citric acid | 210.14 | 98％ | 21.1171 |
The solution of above-mentioned preparation is placed in crucible evaporate to dryness and burns into powder; The 750 DEG C of pre-burnings 3 hours in retort furnace of gained powder, removing organism; The powder of pre-burning is make cylindrical samples under the condition of below 5Mpa at pressure, and sample size is φ 12mm × 2mm; After compression molding in retort furnace 1000 DEG C of sintering 10 hours, finally obtained target product.
With X-ray diffractometer (Japanese Bruker company D8 type), structural analysis is carried out to the sample after sintering, obtain Fig. 1.As seen from the figure, sample is the ceramics sample of single perovskite structure, does not find second-phase.
Observe the pattern of sample by scanning electronic microscope (Japanese JEOL company JSM-6510 type), obtain Fig. 2.As seen from the figure, the grain shape of sample is basically identical, and the density of sample is better, and obviously cavity does not occur.
Observe the electron diffraction pattern of sample with transmission electron microscope (Japanese JEOL company 2010 type), obtain Fig. 3.As seen from the figure, sample is six Rotating fields.
With ferroelectric properties survey meter (Radiant Technologies company of U.S. Precision LC type) measure sample ferroelectric properties at normal temperatures, obtain Fig. 4.As seen from the figure, under normal temperature, sample demonstrates ferroelectricity, when measurement electric field is 50kV/cm, and remnant polarization (2P
r) be 0.88 μ C/cm
2, coercive field (2E
c) be 20kV/cm.
With vibrating sample magnetometer (ADE Co. of U.S. EV7 type) measure sample magnetic performance at normal temperatures, obtain Fig. 5.As seen from the figure, under normal temperature, sample demonstrates ferromegnetism, and remanence rate (2Mr) is 1.48emu/g, and coercive field (2Hc) is 244Oe.
Embodiment 2
Choose chemical pure tetrabutyl titanate (C
16h
36o
4ti), analytical pure five nitric hydrate bismuth (Bi (NO
3)
35H
2o), high-purity (4N) six nitric hydrate yttrium (Y (NO
3)
36H
2o), analytical pure Fe(NO3)39H2O (Fe (NO
3)
39H
2o), analytical pure four acetate hydrate cobalt (C
4h
6o
4co4H
2o) be raw material, stoichiometrically be dissolved in salpeter solution after 3: 6: 1: 2: 1 precise, add ethylenediamine tetraacetic acid (EDTA) (EDTA) and citric acid as complexing agent, EDTA, citric acid and metal ion mol ratio are 0.7: 1: 1, average rate stirs, and forms settled solution.
Bi prepared by table 2
6yFe
2coTi
3o
21
| Nomenclature of drug | Molecular weight | Medicine purity | Take quality/g |
| C 16H 36O 4Ti | 340.36 | 98％ | 8.016 |
| Bi(NO 3) 3·5H 2O | 485.07 | 99％ | 22.8483 |
| Y(NO 3) 3·6H 2O | 383.01 | 98％ | 3.0068 |
| Fe(NO 3) 3·9H 2O | 404 | 98.5％ | 6.3432 |
| C 4H 6CoO 4·4H 2O | 249.08 | 99.5％ | 1.9554 |
| EDTA | 292.24 | 98％ | 20.8776 |
| Citric acid | 210.14 | 98％ | 21.5009 |
The solution of above-mentioned preparation is placed in crucible evaporate to dryness and burns into powder; The 700 DEG C of pre-burnings 2 hours in retort furnace of gained powder, removing organism; The powder of pre-burning is make cylindrical samples under the condition of below 5Mpa at pressure, and sample size is φ 12mm × 2mm; After compression molding in hot pressing furnace 900 DEG C of sintering 5 hours, finally obtained target product.
Carry out structural analysis with X-ray diffractometer (Japanese Bruker company D8 type) to the sample after sintering, sample is the ceramics sample of single perovskite structure, does not find second-phase.
Observe the pattern of sample by scanning electronic microscope (Japanese JEOL company JSM-6510 type), the grain shape of sample is basically identical, and the density of sample is better, and obviously cavity does not occur.
Observe the electron diffraction pattern of sample with transmission electron microscope (Japanese JEOL company 2010 type), determine that sample is six Rotating fields.
With ferroelectric properties survey meter (Radiant Technologies company of U.S. Precision LC type) measure sample ferroelectric properties at normal temperatures, under normal temperature, sample demonstrates ferroelectricity, when measurement electric field is 50kV/cm, and remnant polarization (2P
r) be 0.92 μ C/cm
2, coercive field (2E
c) be 28kV/cm.
With vibrating sample magnetometer (ADE Co. of U.S. EV7 type) measure sample magnetic performance at normal temperatures, under normal temperature, sample demonstrates ferromegnetism, and remanence rate (2Mr) is 1.84emu/g, and coercive field (2Hc) is 216Oe.
Claims (5)
1. preparative chemistry formula is Bi
6yFe
2coTi
3o
21the method with six laminate structure ferrotianium cobalts acid yttrium bismuth potteries of multi-ferrum property, it is characterized in that comprising the following steps:
1) tetrabutyl titanate, five nitric hydrate bismuths, six nitric hydrate yttriums, Fe(NO3)39H2O, four acetate hydrate cobalts are stoichiometrically dissolved in salpeter solution at 3: 6: 1: 2: 1, and add complexing agent;
2) by solution evaporate to dryness, gained powder, at 700-800 DEG C of pre-burning 2-4 hour, removes organism;
3) at 800-1100 DEG C of sintering 5-10 hour, finally obtained target product after the powder compression molding of pre-burning,
Wherein said complexing agent is ethylenediamine tetraacetic acid (EDTA) and citric acid, and ethylenediamine tetraacetic acid (EDTA), citric acid and metal ion mol ratio are 0.7: 1: 1.
2., by method according to claim 1, it is characterized in that step 3) described in sintering be retort furnace sintering or hot pressed sintering.
3. a chemical formula is Bi
6yFe
2coTi
3o
21the six laminate structure ferrotianium cobalts acid yttrium bismuths potteries with multi-ferrum property, it is prepared in accordance with the method for claim 1.
4., by ferrotianium cobalt acid yttrium bismuth pottery according to claim 3, it is characterized in that structure is six layers of perovskite-like structure, namely at (Bi
2o
2)
2+3 Ti-O octahedrons, 2 Fe-O octahedrons and 1 Co-O octahedron is clipped between layer.
5., by ferrotianium cobalt acid yttrium bismuth pottery according to claim 3, it is characterized in that, in room temperature, there is ferroelectricity and ferromegnetism simultaneously.
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|---|---|---|---|
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|---|---|---|---|
| CN201210209229.7A CN103288437B (en) | 2012-06-21 | 2012-06-21 | Six-layer ferrotitanium yttrium bismuth cobaltate ceramic material with multiferroic performance and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
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| CN103288437B true CN103288437B (en) | 2015-01-07 |
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| CN107159226B (en) * | 2017-06-20 | 2019-11-22 | 信阳师范学院 | More catalysis single phase nano materials and preparation method thereof |
| CN108558387B (en) * | 2018-01-15 | 2020-10-30 | 信阳师范学院 | Single-phase multi-iron microwave absorbing material and preparation method thereof |
| CN111187066A (en) * | 2020-02-26 | 2020-05-22 | 扬州大学 | Single-layer orthogonal structure magnetoelectric multiferroic ceramic and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5198923A (en) * | 1991-01-17 | 1993-03-30 | Shin-Etsu Chemical Co., Ltd. | Optical isolator |
-
2012
- 2012-06-21 CN CN201210209229.7A patent/CN103288437B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5198923A (en) * | 1991-01-17 | 1993-03-30 | Shin-Etsu Chemical Co., Ltd. | Optical isolator |
Non-Patent Citations (2)
| Title |
|---|
| INVESTIGATION OF DIELECTRIC AND MAGNETIC NATURE OF Bi7Fe3Ti3O21;A.Srinivas et al.;《Materials Research Bulletin》;19991231;第34卷(第6期);第989~996页 * |
| Structural, magnetic and dielectric properties of Bi5-xLaxTi3Co0.5Fe0.5O15 ceramics;C.H. Wang et al.;《Materials Science and Engineering B》;20110629;第176卷;第1243~1246页 * |
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