CN110002506A - A kind of preparation method of pure phase nanometer crystalline substance bismuth ferrite - Google Patents
A kind of preparation method of pure phase nanometer crystalline substance bismuth ferrite Download PDFInfo
- Publication number
- CN110002506A CN110002506A CN201910383717.1A CN201910383717A CN110002506A CN 110002506 A CN110002506 A CN 110002506A CN 201910383717 A CN201910383717 A CN 201910383717A CN 110002506 A CN110002506 A CN 110002506A
- Authority
- CN
- China
- Prior art keywords
- bismuth ferrite
- bismuth
- preparation
- pure phase
- crystalline substance
- 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.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention belongs to the preparation technical fields of bismuth ferrite, disclose a kind of preparation method of pure phase nanometer crystalline substance bismuth ferrite.The present invention carries out high-energy ball milling to above-mentioned raw materials using iron oxide and bismuth oxide as raw material, by mechanical alloying method, obtains amorphous bismuth ferrite, then make amorphous bismuth ferrite that pure bismuth ferrate nano crystal structure be precipitated by the method for high-temperature heat treatment.Bismuth ferrite prepared by the method is pure bismuth ferrate nano crystal structure.
Description
Technical field
The invention belongs to the preparation technical fields of bismuth ferrite, and in particular to a kind of preparation side of pure phase nanometer crystalline substance bismuth ferrite
Method.
Background technique
BiFeO3It (BFO) is a kind of novel more ferroelectricity perovskite structural materials, its ferroelectric Curie point (TC=810
DEG C) and antiferromagnetic Néel point (TN=370 DEG C) be above room temperature, this makes BiFeO3Have simultaneously at room temperature as unique one kind
More ferroelectric substances of standby ferroelectricity and antiferromagnetic characteristic；At the same time, BiFeO3Forbidden bandwidth be only 2.16eV, compared to
The advantage that the photocatalysis material of titanium dioxide of extensive application has apparent forbidden bandwidth low can be completed directly using visible light
Photocatalytic process.Therefore, BiFeO3It has broad application prospects in fields such as electrical, storage, environment and the energy.
However, due to BiFeO3Often with Bi in synthesis process2Fe4O9Deng the appearance of other miscellaneous phases, and BiFeO3Pure phase
Firing range it is very narrow, so as to cause pure phase BiFeO3Prepare it is extremely difficult.Therefore, how purity is prepared
BiFeO that is higher, haveing excellent performance3Pure phase has become a great problem in the field.
In order to synthesize BiFeO3Pure phase, domestic and foreign scholars have put into a large amount of energy.Synthetic method common at present has: Gu
Phase reaction, sol-gal process, hydrothermal synthesis method, chemical solution deposition, phonochemistry method, pulse laser deposition method etc..Wherein, Gu
Although phase reaction can prepare bismuth ferrite material with rapid, high volume, product miscellaneous phase is more, is unable to get pure phase BiFeO3；It uses
It is more uniform that sol-gal process can be such that bismuth source and source of iron mixes, but prepare common nitrate and can generate during heating
Serious exhaust emission；And at present there is the problems such as the device is complicated, and technique is cumbersome in the common hydro-thermal method in laboratory, it is difficult to realize pure
Phase BiFeO3The volume production of bismuth ferrite, and some organic solvents or chelating agent etc. will be inevitably added during the preparation process,
This will cause certain pollution to environment.Therefore be badly in need of exploring at present it is a kind of simple, volume production, obtain pure phase, and it is right
One preparation process of environmental nonpollution.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of pure phase nanometer crystalline substance bismuth ferrite.
To achieve the above object, the technical solution adopted by the present invention is as follows:
A kind of preparation method of pure phase nanometer crystalline substance bismuth ferrite, steps are as follows:
S1, amorphous bismuth ferrite is prepared by mechanical alloying method:
S1.1, with molar ratio computing, by iron oxide: bismuth oxide=1: (0.9 ~ 1) weighs iron oxide and bismuth oxide, together grinding obtain
Mixture；
S1.2, according to ball material mass ratio be (10 ~ 30): 1, said mixture is put into planetary ball mill and carries out high-energy ball milling,
Main turntable revolving speed is arranged between 300 ~ 500 rpm, and planet disk rotating speed is arranged between 600 ~ 800 rpm, controls Ball-milling Time
>=25 h obtain amorphous bismuth ferrite powder；
S2, high-temperature heat treatment:
Under normal pressure, air atmosphere, with the heating rate of 3 ~ 10 DEG C/min, the amorphous bismuth ferrite that step S1 is obtained is warming up to
600 DEG C, heat treatment time >=20 min are to get pure phase nanometer crystalline substance bismuth ferrite.
Preferably, control Ball-milling Time is in 25 ~ 30 h, and heat treatment time is in 20 ~ 180 min.
The utility model has the advantages that the present invention carries out above-mentioned raw materials using iron oxide and bismuth oxide as raw material, by mechanical alloying method
High-energy ball milling, obtains amorphous bismuth ferrite, then makes amorphous bismuth ferrite that pure bismuth ferrite be precipitated by the method for high-temperature heat treatment and receive
Rice crystal structure；Meanwhile bismuth ferrite of the present invention it is single-phase firing temperature it is lower compared to conventional solid-state method, be conducive to preparation of industrialization；
This pure nanocrystalline bismuth ferrite material disclosed by the invention and its preparation process, production and storage, electrical, energy to bismuth ferrite
The application in the fields such as source is of great significance, and prepared bismuth ferrite has good multiferroic and superior photocatalysis effect.
Detailed description of the invention
Fig. 1: the XRD diagram of 1 gained final products of embodiment 1 and reference examples.
Fig. 2: the XRD diagram of intermediate product obtained by the different mechanical alloying times.
Fig. 3: iron oxide: bismuth oxide=1: the XRD diagram of final products obtained by different heat treatment temperature when 0.9.
Fig. 4: iron oxide: bismuth oxide=1: the XRD diagram of final products obtained by different heat treatment temperature when 1.
Fig. 5: it iron oxide: is kept the temperature obtained by 60min most at a temperature of different heat treatment when bismuth oxide is respectively 1: 0.9 and 1: 1
The particle size figure of finished product.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described.It should be understood that following embodiment is merely to illustrate this
The range of invention and is not intended to limit the present invention.
Embodiment 1
A kind of preparation method of bismuth ferrite, steps are as follows:
S1, amorphous bismuth ferrite is prepared by mechanical alloying method:
S1.1, with molar ratio computing, by iron oxide: bismuth oxide=1: 0.9 weighs iron oxide and bismuth oxide, together grinding mixed
Object；
S1.2, the ratio for being 20: 1 according to ball material mass ratio, said mixture is put into planetary ball mill and carries out high-energy ball milling,
The setting of main turntable revolving speed is 25 h in 800 rpm, control Ball-milling Time in 350 rpm, the setting of planet disk rotating speed, obtains intermediate production
Object；
S2, high-temperature heat treatment:
Under normal pressure, air atmosphere, with the heating rate of 5 DEG C/min, the obtained intermediate product of step S1 is warming up to 600
DEG C, 60 min are heat-treated to get final products.
Reference examples 1-omit mechanical alloying processing
A kind of preparation method of bismuth ferrite, steps are as follows:
S1, with molar ratio computing, by iron oxide: bismuth oxide=1: 0.9 weighs iron oxide and bismuth oxide, together grinding mixed
Object；
S2, high-temperature heat treatment:
Under normal pressure, air atmosphere, with the heating rate of 5 DEG C/min, the obtained mixture of step S1 is warming up to 600 DEG C,
60 min are heat-treated to get final products.
The XRD diagram of 1 gained final products of embodiment 1 and reference examples is shown in Fig. 1, as seen from the figure: same material rate with
And under heat treatment condition, use mechanical alloying method products obtained therefrom for pure phase bismuth ferric, and omit mechanical alloying processing after
Then it is unable to get pure phase bismuth ferric.
Reference examples 2-difference mechanical alloying the time
Difference from example 1 is that: controlling the Ball-milling Time in mechanical alloying time, that is, step S1.2 respectively is 1
H, 3 h, 5 h, 7 h, 10 h, 15 h, 20 h, it is other with embodiment 1.
The XRD diagram of intermediate product obtained by the different mechanical alloying times is shown in that Fig. 2,0 h intermediate product correspond to 1 institute of reference examples
Intermediate product is obtained, 25 h intermediate products correspond to 1 gained intermediate product of embodiment.As can be seen from Figure 2: not carrying out mechanical conjunction
Contain two kinds of object phases of iron oxide crystal and bismuth oxide crystal in the intermediate product (0 h) of aurification processing；To iron oxide and bismuth oxide
Mixed powder carry out mechanical alloying processing 1h after, intermediate product state starts to amorphous state transition, however in 2 θ=27.4
And 2 there is also the characteristic peaks for having bismuth oxide and iron oxide at θ=33.1, with the extension of mechanical alloying time, sample it is non-
Brilliant degree gradually increases, further, since the bond energy of Bi-O will be lower than the bond energy of Fe-O key, so as to cause Bi2O3It is more readily accomplished non-
Crystallization process；Gained intermediate product shows apparent noncrystalline state after 25 h of mechanical alloying, shows using mechanical alloying
After amorphous bismuth ferrite material can be made.
Reference examples 3-different heat treatment temperature
Difference from example 1 is that: controlling the temperature in heat treatment temperature, that is, step S2 respectively is 400 DEG C, 500
DEG C, 700 DEG C, 800 DEG C, it is other with embodiment 1.
Iron oxide: bismuth oxide=1: when 0.9, the XRD diagram of final products obtained by different heat treatment temperature is shown in Fig. 3,600 DEG C
Corresponding to 1 final products of embodiment.As can be seen from Figure 3: when heat treatment temperature is 400 ~ 500 DEG C, existing in bismuth ferrite
Two kinds of crystal forms, respectively BiFeO3Phase and Bi25FeO40Phase；When heat treatment temperature is at 600 DEG C, bismuth ferrite has typical empty
Between group be R3c BiFeO3Crystalline structure (JCPDS No.71-2494), is pure BiFeO in system at this time3Crystal form bismuth ferrite
Material；When heat treatment temperature is at 700 ~ 800 DEG C, occurs more miscellaneous peak near 2 θ=27, these are Bi2Fe4O9Feature
Peak.
Reference examples 4-different material ratio
Difference from example 1 is that: control iron oxide: bismuth oxide=1: 1, then control heat treatment temperature walks respectively
Temperature in rapid S2 is 400 DEG C, 500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C, other with embodiment 1.
Iron oxide: bismuth oxide=1: when 1, the XRD diagram of final products obtained by different heat treatment temperature is shown in Fig. 4.It can from Fig. 4
To find out: iron oxide: bismuth oxide=1: when 1 the object of products obtained therefrom accompany heat treatment temperature variation and iron oxide: bismuth oxide=1
: when 0.9 mutually there is same trend in the object of products obtained therefrom.
According to 4 products obtained therefrom of reference examples 3 and reference examples, by having a rest, happy formula calculates iron oxide: bismuth oxide is respectively 1: 0.9
Fig. 5 is seen with the particle size for keeping the temperature final products obtained by 60min when 1: 1 at a temperature of different heat treatment.As can be seen from Figure 5: working as oxygen
Change iron: the crystal grain for keeping the temperature final products obtained by 60 min when bismuth oxide is respectively 1: 0.9 and 1: 1 at a temperature of different heat treatment is big
It is small to substantially remain in nanoscale, and crystallite dimension increases with heat treatment temperature and is increased.
Claims (3)
1. a kind of preparation method of pure phase nanometer crystalline substance bismuth ferrite, which is characterized in that steps are as follows:
S1, amorphous bismuth ferrite is prepared by mechanical alloying method:
S1.1, with molar ratio computing, by iron oxide: bismuth oxide=1: (0.9 ~ 1) weighs iron oxide and bismuth oxide, together grinding obtain
Mixture；
S1.2, according to ball material mass ratio be (10 ~ 30): 1, said mixture is put into planetary ball mill and carries out high-energy ball milling,
Main turntable revolving speed is arranged between 300 ~ 500 rpm, and planet disk rotating speed is arranged between 600 ~ 800 rpm, controls Ball-milling Time
>=25 h obtain amorphous bismuth ferrite powder；
S2, high-temperature heat treatment:
Under normal pressure, air atmosphere, with the heating rate of 3 ~ 10 DEG C/min, the amorphous bismuth ferrite that step S1 is obtained is warming up to
600 DEG C, heat treatment time >=20 min are to get pure phase nanometer crystalline substance bismuth ferrite.
2. the preparation method of pure phase nanometer crystalline substance bismuth ferrite as described in claim 1, it is characterised in that: control Ball-milling Time is 25
~30 h。
3. the preparation method of pure phase nanometer crystalline substance bismuth ferrite as described in claim 1, it is characterised in that: heat treatment time 20 ~
180 min。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910383717.1A CN110002506A (en) | 2019-05-08 | 2019-05-08 | A kind of preparation method of pure phase nanometer crystalline substance bismuth ferrite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910383717.1A CN110002506A (en) | 2019-05-08 | 2019-05-08 | A kind of preparation method of pure phase nanometer crystalline substance bismuth ferrite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110002506A true CN110002506A (en) | 2019-07-12 |
Family
ID=67176364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910383717.1A Pending CN110002506A (en) | 2019-05-08 | 2019-05-08 | A kind of preparation method of pure phase nanometer crystalline substance bismuth ferrite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110002506A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111362690A (en) * | 2020-03-17 | 2020-07-03 | 东北大学秦皇岛分校 | Preparation method of bismuth ferrite-barium titanate composite piezoelectric ceramic |
| CN112871213A (en) * | 2020-06-30 | 2021-06-01 | 深圳大学 | Bismuth ferrite composite photocatalytic material and preparation method thereof |
| RU2816609C1 (en) * | 2023-06-07 | 2024-04-02 | Федеральное государственное бюджетное образовательное учреждение высшего образования "ДАГЕСТАНСКИЙ ГОСУДАРСТВЕННЫЙ УНИВЕРСИТЕТ" | Obtaining bismuth ferrite ceramics with high content of stoichiometric composition |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1686932A (en) * | 2005-04-08 | 2005-10-26 | 南京大学 | Method for preparing single-phase BiFeO3 ceramics through hardening process |
| CN101671173A (en) * | 2009-09-27 | 2010-03-17 | 哈尔滨工业大学 | Method for improving multi-ferrum property of BiFeO3 ceramic block material |
| US20120177902A1 (en) * | 2011-01-06 | 2012-07-12 | Driscoll Judith L | Multiferroics that are both ferroelectric and ferromagnetic at room temperature |
| CN104556238A (en) * | 2014-12-19 | 2015-04-29 | 上海师范大学 | Method for preparing pure-phase bismuth ferrite powder and block |
| CN106006752A (en) * | 2016-05-16 | 2016-10-12 | 中国科学院上海硅酸盐研究所 | Preparation method of pure-phase BiFeO3 powder |
| CN106927809A (en) * | 2015-12-30 | 2017-07-07 | 中国科学院上海硅酸盐研究所 | A kind of high polarization intensity bismuth ferrite ceramic material and preparation method thereof |
-
2019
- 2019-05-08 CN CN201910383717.1A patent/CN110002506A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1686932A (en) * | 2005-04-08 | 2005-10-26 | 南京大学 | Method for preparing single-phase BiFeO3 ceramics through hardening process |
| CN101671173A (en) * | 2009-09-27 | 2010-03-17 | 哈尔滨工业大学 | Method for improving multi-ferrum property of BiFeO3 ceramic block material |
| US20120177902A1 (en) * | 2011-01-06 | 2012-07-12 | Driscoll Judith L | Multiferroics that are both ferroelectric and ferromagnetic at room temperature |
| CN104556238A (en) * | 2014-12-19 | 2015-04-29 | 上海师范大学 | Method for preparing pure-phase bismuth ferrite powder and block |
| CN106927809A (en) * | 2015-12-30 | 2017-07-07 | 中国科学院上海硅酸盐研究所 | A kind of high polarization intensity bismuth ferrite ceramic material and preparation method thereof |
| CN106006752A (en) * | 2016-05-16 | 2016-10-12 | 中国科学院上海硅酸盐研究所 | Preparation method of pure-phase BiFeO3 powder |
Non-Patent Citations (4)
| Title |
|---|
| CH. SREE RAMA LINGA PRASAD等: "Electrical and Magnetic Properties of Nanocrystalline BiFeO3 Prepared by High Energy Ball Milling and Microwave Sintering", 《JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY》 * |
| M. AHMADZADEH等: "The effects of mechanical activation energy on the solid-state synthesis process of BiFeO3", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| V.F. FREITAS等: "Structural, microstructural and magnetic investigations in high-energy ball milled BiFeO3 and Bi0.95Eu0.05FeO3 powders", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| 王大伟等: "BiFeO3粉体的固相合成及其微观结构研究", 《压电与声光》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111362690A (en) * | 2020-03-17 | 2020-07-03 | 东北大学秦皇岛分校 | Preparation method of bismuth ferrite-barium titanate composite piezoelectric ceramic |
| CN112871213A (en) * | 2020-06-30 | 2021-06-01 | 深圳大学 | Bismuth ferrite composite photocatalytic material and preparation method thereof |
| RU2816609C1 (en) * | 2023-06-07 | 2024-04-02 | Федеральное государственное бюджетное образовательное учреждение высшего образования "ДАГЕСТАНСКИЙ ГОСУДАРСТВЕННЫЙ УНИВЕРСИТЕТ" | Obtaining bismuth ferrite ceramics with high content of stoichiometric composition |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101890354B (en) | Method for preparing bismuth ferrite photocatalyst | |
| CN108706637B (en) | A kind of preparation method of adjustable magnetic iron oxide mesomorphic material of uniform size | |
| CN113372108B (en) | Preparation method of high-entropy ceramic material with good light absorption performance | |
| CN103395837B (en) | Preparation method of Bi12TiO20 powder | |
| CN110002506A (en) | A kind of preparation method of pure phase nanometer crystalline substance bismuth ferrite | |
| CN105129861B (en) | Preparation method for bismuth ferrite BiFeO3 nanosheet | |
| CN113479918B (en) | Preparation method of nano spherical alpha-alumina powder | |
| CN105601264A (en) | Preparation method of high-densification multiferroic (1-y)BiFeO[3-y]Bi[1-x]RxFeO3 composite ceramic | |
| CN105060351A (en) | Flower-like cobaltosic oxide material composed of nanoparticles and preparation method thereof | |
| CN106084902B (en) | A kind of high infrared radiation powder and preparation method thereof | |
| CN101767997B (en) | Method for preparing NiTiO3 nano-powder by sol-gel | |
| CN101367539B (en) | Preparation of nano- luminescent powder body with colloidal sols gel rubber method | |
| CN107043121A (en) | A kind of preparation method of cerium dioxide nano hollow ball | |
| CN106745303A (en) | A kind of three-dimensional flower ball-shaped cadmium ferrite bismuth meal body and preparation method thereof | |
| CN103833080A (en) | Preparation method for cadmium molybdate porous spheres | |
| CN102491428A (en) | Method for preparing hexagonal BeFe12O19 (barium ferrite) magnetic nano powder by microwave-hydrothemal method | |
| CN103318954A (en) | Method for preparing sodium trititanate nanorods through solid-phase chemical reaction | |
| CN106316386A (en) | Preparation method of rare earth-doped bismuth system layered perovskite oxide ferroelectric up-conversion material | |
| CN104556217A (en) | Method for preparing divalent metal titanate microspheres | |
| CN100372759C (en) | Preparation method of mesopore metal oxide | |
| CN113336271B (en) | Micron-sized regular square strip Bi2Fe4O9Preparation method, product and application of multiferroic material | |
| CN104961162B (en) | A kind of method that single pure phase bismuth ferric material is prepared based on Lithium ions compensation | |
| CN110002505A (en) | A kind of preparation method of pure phase nanometer crystalline substance doped yttrium bismuth ferrite | |
| CN101746786B (en) | Method for preparing high-purity alpha-Al2O3 nano-crystalline material | |
| CN108640158A (en) | A kind of preparation method of high-purity hexagonal sheet-like barium ferrite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190712 |