CN103449808A - Preparation method of biphase composite hard magnetic ferrite nano-powder with exchange coupling - Google Patents
Preparation method of biphase composite hard magnetic ferrite nano-powder with exchange coupling Download PDFInfo
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- CN103449808A CN103449808A CN2013104156230A CN201310415623A CN103449808A CN 103449808 A CN103449808 A CN 103449808A CN 2013104156230 A CN2013104156230 A CN 2013104156230A CN 201310415623 A CN201310415623 A CN 201310415623A CN 103449808 A CN103449808 A CN 103449808A
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Abstract
The invention discloses a preparation method of biphase composite hard magnetic ferrite nano-powder with hard magnetic/soft magnetic exchange coupling, belonging to the technical field of preparation of magnetic ferrites. The method comprises the following steps: directly adding hydrochloric acid-cleaned SrFe12O19 ferrite nano-powder which is prepared by a hydrothermal method into a reaction kettle for preparing NixZn(1-x)Fe2O4 ferrite nano-powder by the hydrothermal method; directly preparing the nano composite ferrite powder at a low temperature, wherein the prepared biphase powder which is not sintered at a high temperature shows a single phase magnetic behavior, namely the powder has the exchange coupling effect. The preparation method disclosed by the invention is simple and applicable tofor preparing pure oxide biphase composite hard magnetic ferrite nano-powder with hard magnetic/soft magnetic exchange coupling.
Description
Technical field
The present invention relates to the preparing technical field of magnetic ferrite, be specifically related to a kind of preparation method who possesses the compound hard ferrite nano-powder of pure-oxide two-phase of Hard Magnetic/soft magnetism spin-exchange-coupled.
Background technology
Hard ferrite is one of modal ferrimagnetic material, although with a long history, because its high performance-price ratio, starting material are cheap and good chemical stability, in a lot of industries, still be widely used at present, output is very huge.Yet, the big country that China produces as hard ferrite, production technology is compared American-European Japan, and to wait state to fall behind a lot, are not still the poweies of hard ferrite production.For this reason, be badly in need of seeking new hard ferrite preparation method, the level of producing to improve China's hard ferrite.
Utilize the exchange-coupling interaction between Hard Magnetic phase and soft magnetism phase, can effectively improve the magnetic property of hard magnetic material.Because hard magnetic phase and soft magnetism well are coupled mutually, although make material by two phase composites, but present single-phase magnetic behavior.This technology has obtained realization in widely used rare earth permanent magnet, has improved to a certain extent the magnetic property of rare earth permanent magnet.The patent of invention that is ZL201010289049.5 such as the patent No. discloses a kind of nanocrystalline two-phase coupling rare-earth permanent magnet and preparation method thereof; The patent of invention that the patent No. is ZL201010524561.3 discloses a kind of spin-exchange-coupled biphase composite NdFeB permanent magnetism particle and preparation method and application.
But, due to the impact of the factors such as control of the selection of soft magnetism phase, grain size, up to the present utilize exchange-coupling interaction to go to improve the progress of pure-oxide hard ferrite performance slow.Patent of invention number is the patent of ZL200610048970.4, added a kind of special L material and replaced non magnetic addition material in Hard Magnetic Sr ferrite, and suitably control the granularity of L material, density and the orientation degree of product have not only significantly been improved, and find wherein to have exchange-coupling interaction, thereby improved magnetic property.The preparation method that invention is used is traditional conventional ceramic technique, and conventional ceramic technique often need at high temperature sinter phase into, often makes ferritic crystal grain look very large.And micromagnetics research shows, when the size of soft magnetism phase approaches the twice (about 10nm) of hard magnetic phase domain wall thickness, the exchange sclerosis between soft or hard magnetic phase is not only very effective, but also has avoided the coercitive decline caused by spin-exchange-coupled.Therefore, adopt conventional ceramic technique to be unfavorable for the formation of spin-exchange-coupled effect.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of the pure-oxide two-phase complex ferrite nano-powder that possesses Hard Magnetic/soft magnetism spin-exchange-coupled newly.Although prepared ferrite nano powder, by two phase composites, but externally presents single-phase magnetic behavior in this way, thereby has good exchange-coupling interaction.
A kind of preparation method who possesses the compound hard ferrite nano-powder of two-phase of spin-exchange-coupled provided by the invention, its preparation process is as follows:
(1) first prepare SrFe
12o
19phase: with analytical pure Sr (NO
3)
2, Fe (NO
3)
3and NaOH is raw material, consider a large amount of losses of Sr element in preparation process, in raw material, Fe and Sr mol ratio are according to 4:1 proportioning, OH
-with
mol ratio is according to the 3:1 proportioning, after above-mentioned nitrate and NaOH are dissolved in to deionized water respectively, make precipitation by metallic ion while stirring to dripping NaOH in mixed nitrate solution, precipitated liquid and throw out immigration hydrothermal reaction kettle are carried out to hydro-thermal reaction, control the hydrothermal reaction kettle compactedness is 80% simultaneously, reaction conditions is 220 ℃ * 5h, for guaranteeing the purity of phase, after reaction, the gained powdered product is carried out to pickling;
(2) preparation of complex ferrite nano-powder: with analytical pure Ni (NO
3)
2, Zn (NO
3)
2and Fe (NO
3)
3for raw material, in raw material according to Ni
xzn
1-xfe
2o
4ni in (0 ﹤ x ﹤ 1) molecular formula, Zn and Fe molar ratio ingredient, be dissolved in respectively deionized water by above-mentioned nitrate and NaOH, while then stir to dripping NaOH in mixed nitrate solution, makes precipitation by metallic ion, considers Zn (OH)
2be a kind of amphoteric hydroxide, dissolve in pH 11 highly basic, therefore drip NaOH until pH=11 stops, then by the SrFe of preparation in step (1)
12o
19according to the Ni with required preparation
xzn
1-xfe
2o
4add in above-mentioned precipitated liquid phase mass ratio 1:0.5～4, the rear immigration hydrothermal reaction kettle that again mixture stirred carries out hydro-thermal reaction, control the hydrothermal reaction kettle compactedness is 80% simultaneously, reaction conditions is 200 ℃ * 8h, after reacting, products therefrom cleans with deionized water and dehydrated alcohol respectively, and final gained powder is possesses Hard Magnetic/the compound hard ferrite nano-powder of two-phase of soft magnetism spin-exchange-coupled.
Further, the Ni in described step (2)
xzn
1-xfe
2o
4for Ni
0.4zn
0.6fe
2o
4.
Further, SrFe in described step (2)
12o
19phase and Ni
0.4zn
0.6fe
2o
4the mass ratio of phase is 2:1.
Pure-oxide two-phase complex ferrite nano-powder provided by the present invention is mainly by hard magnetic SrFe
12o
19ferrite and soft magnetism Ni
xzn
1-xfe
2o
4the ferrite two-phase forms according to the different mass ratio.SrFe
12o
19phase and Ni
xzn
1-xfe
2o
4by hydrothermal method, prepare.The characteristics of hydrothermal method are in the lower ferrite phase that directly forms of lesser temps (200 ℃ of left and right), without high temperature sintering, to become phase.And, even the prepared pure-oxide two-phase complex ferrite powder of the present invention at high temperature calcining externally also present the behavior of single-phase magnetic, thereby have exchange-coupling interaction preferably.
Compared with prior art, the present invention has following technique effect:
1) directly prepare complex ferrite by hydrothermal method, gained crystal grain tiny (about 10nm), more be conducive to the formation of exchange-coupling interaction;
2) prepared complex ferrite nanometer powder presents the single-phase behavior of magnetic without high temperature sintering, has the spin-exchange-coupled characteristic;
3) preparation method of the present invention is simple and easy, is applicable to the compound hard ferrite nano-powder of pure-oxide two-phase that there is Hard Magnetic/soft magnetism spin-exchange-coupled in preparation.
The accompanying drawing explanation
X-ray diffraction (XRD) collection of illustrative plates of the complex ferrite that Fig. 1 is embodiment 1 preparation.
High-resolution-ration transmission electric-lens (HRTEM) photo of the complex ferrite that Fig. 2 is embodiment 1 preparation.
The magnetic hysteresis loop figure of the complex ferrite that Fig. 3 is embodiment 1 preparation.
The magnetic hysteresis loop figure of the complex ferrite that Fig. 4 is embodiment 2～5 preparations.
Embodiment
First prepare separately SrFe
12o
19powder: with analytical pure nitrate (Sr (NO
3)
2, Fe (NO
3)
3) prepare the SrFe of 2mmol for raw material
12o
19powder, in starting material, Fe and Sr mol ratio, according to the 4:1 proportioning, need Sr (NO
3)
22mmol, Fe (NO
3)
38mmol; According to mol ratio
the required NaOH of proportioning, need 84mmol NaOH.The nitrate starting material are dissolved in to the 45ml deionized water, NaOH is dissolved in to the 30ml deionized water.Then, while stir to mixed nitrate solution dropping NaOH solution, make precipitation by metallic ion, precipitated liquid and throw out immigration 100ml hydrothermal reaction kettle are carried out to hydro-thermal reaction, control the reactor compactedness is 80% simultaneously, and reaction conditions is 220 ℃ * 5h.After reacting, products therefrom cleans respectively 3 times and 2 times with deionized water and dehydrated alcohol.For guaranteeing the purity of phase, gained Sr ferrite powder cleans one time with 2% dilute hydrochloric acid, and then cleans respectively 3 times and 1 time with deionized water and dehydrated alcohol.
The preparation of the compound hard ferrite of pure-oxide: with preparation 1mmol Ni
0.4zn
0.6fe
2o
4the proportioning starting material, starting material are all analytical pure.By 0.4mmol Ni (NO
3)
2, 0.6mmol Zn (NO
3)
2with 2mmol Fe (NO
3)
3be dissolved in the 60ml deionized water, and get 3g NaOH and be dissolved in 100ml water.Then, while stir, drip NaOH solution to mixed nitrate solution and make precipitation by metallic ion, until after pH=11 by the 2mmol SrFe prepared
12o
19powder adds precipitated liquid to, i.e. mass ratio SrFe
12o
19: Ni
0.4zn
0.6fe
2o
4=2:1.The mixture rear immigration 100ml hydrothermal reaction kettle that stirs is carried out to hydro-thermal reaction, and control the hydrothermal reaction kettle compactedness is 80% simultaneously, and reaction conditions is 200 ℃ * 8h.After reacting, products therefrom cleans respectively 3 times and 2 times with deionized water and dehydrated alcohol, and finally gained is and possesses Hard Magnetic/the compound hard ferrite nano-powder of pure-oxide two-phase of soft magnetism spin-exchange-coupled.
The preparation method is with embodiment 1, and the parameter of change is: control mass ratio SrFe
12o
19: Ni
0.4zn
0.6fe
2o
4for 1:1.The magnetic hysteresis loop of the final pure-oxide complex ferrite of gained is listed in Fig. 4.As seen from the figure, the two-phase characteristic curve of step type or necking down type does not appear in the complex ferrite powdered sample, but presents good single-phase Hard Magnetic characteristic curve, exists good exchange-coupling interaction in this interpret sample.
The preparation method is with embodiment 1, and the parameter of change is: control mass ratio SrFe
12o
19: Ni
0.4zn
0.6fe
2o
4for 1:2.From the magnetic hysteresis loop of Fig. 4, exist good exchange-coupling interaction in the complex ferrite powdered sample.
The preparation method is with embodiment 1, and the parameter of change is: control mass ratio SrFe
12o
19: Ni
0.4zn
0.6fe
2o
4for 1:3.From the magnetic hysteresis loop of Fig. 4, exist good exchange-coupling interaction in the complex ferrite powdered sample.
Embodiment 5
The preparation method is with embodiment 1, and the parameter of change is: control mass ratio SrFe
12o
19: Ni
0.4zn
0.6fe
2o
4for 1:4.From the magnetic hysteresis loop of Fig. 4, exist good exchange-coupling interaction in the complex ferrite powdered sample.
Claims (3)
1. a preparation method who possesses the compound hard ferrite nano-powder of two-phase of spin-exchange-coupled, is characterized in that, its preparation process is as follows:
(1) first prepare SrFe
12o
19phase: with analytical pure Sr (NO
3)
2, Fe (NO
3)
3and NaOH is raw material, in raw material, Fe and Sr mol ratio are according to 4:1 proportioning, OH
-with
mol ratio is according to the 3:1 proportioning, after above-mentioned nitrate and NaOH are dissolved in to deionized water respectively, make precipitation by metallic ion while stirring to dripping NaOH in mixed nitrate solution, precipitated liquid and throw out immigration hydrothermal reaction kettle are carried out to hydro-thermal reaction, control the hydrothermal reaction kettle compactedness is 80% simultaneously, reaction conditions is 220 ℃ * 5h, for guaranteeing the purity of phase, after reaction, the gained powdered product is carried out to pickling;
(2) preparation of complex ferrite nano-powder: with analytical pure Ni (NO
3)
2, Zn (NO
3)
2and Fe (NO
3)
3for raw material, in raw material according to Ni
xzn
1-xfe
2o
4ni in (0 ﹤ x ﹤ 1) molecular formula, Zn and Fe molar ratio ingredient, be dissolved in respectively deionized water by above-mentioned nitrate and NaOH, while then stir to dripping NaOH in mixed nitrate solution, makes precipitation by metallic ion, until pH=11 stops, then by the SrFe of preparation in step (1)
12o
19according to the Ni with required preparation
xzn
1-xfe
2o
4add in above-mentioned precipitated liquid phase mass ratio 1:0.5～4, the rear immigration hydrothermal reaction kettle that again mixture stirred carries out hydro-thermal reaction, control the hydrothermal reaction kettle compactedness is 80% simultaneously, reaction conditions is 200 ℃ * 8h, after reacting, products therefrom cleans with deionized water and dehydrated alcohol respectively, and final gained powder is possesses Hard Magnetic/the compound hard ferrite nano-powder of two-phase of soft magnetism spin-exchange-coupled.
2. a kind of preparation method who possesses the compound hard ferrite nano-powder of two-phase of spin-exchange-coupled as claimed in claim 1, is characterized in that the Ni in described step (2)
xzn
1-xfe
2o
4for Ni
0.4zn
0.6fe
2o
4.
3. a kind of preparation method who possesses the compound hard ferrite nano-powder of two-phase of spin-exchange-coupled as claimed in claim 2, is characterized in that, SrFe in described step (2)
12o
19phase and Ni
0.4zn
0.6fe
2o
4the mass ratio of phase is 2:1.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104211387A (en) * | 2014-09-03 | 2014-12-17 | 安徽工业大学 | Method for improving coercive force of spinelle iron-cobalt ferrite CoFe2O4 |
| CN104529424A (en) * | 2015-01-16 | 2015-04-22 | 安徽工业大学 | Composite permagnetferrite with functions of two-phase exchange coupling and keeping high coercive force |
| CN104973859A (en) * | 2015-06-29 | 2015-10-14 | 安徽工业大学 | Preparation method for composite ferrite powder with exchange coupling effect |
| CN106567123A (en) * | 2016-11-15 | 2017-04-19 | 彭晓领 | Preparation method of high-coercivity strontium ferrite |
| CN112851324A (en) * | 2021-01-21 | 2021-05-28 | 安徽大学 | Composite material applied to high-frequency field |
| CN113192717A (en) * | 2021-04-22 | 2021-07-30 | 兰州大学 | Metal soft magnetic composite material and preparation method thereof |
| CN114524668A (en) * | 2022-03-15 | 2022-05-24 | 宜宾金川电子有限责任公司 | Method for adding and recycling manganese zinc ferrite waste in strontium ferrite |
| CN115295266A (en) * | 2022-08-12 | 2022-11-04 | 安徽鑫磁源磁业有限公司 | M-type strontium ferrite-based dual-phase composite permanent magnetic ferrite block and preparation method thereof |
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|---|---|---|---|---|
| CN101950650A (en) * | 2010-09-21 | 2011-01-19 | 中北大学 | Nanocrystalline two-phase coupling rare-earth permanent magnet and preparation method thereof |
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2013
- 2013-09-12 CN CN201310415623.0A patent/CN103449808B/en active Active
Patent Citations (1)
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|---|---|---|---|---|
| CN101950650A (en) * | 2010-09-21 | 2011-01-19 | 中北大学 | Nanocrystalline two-phase coupling rare-earth permanent magnet and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| M.A. RADMANESH ET AL.: "Synthesis and magnetic properties of hard/soft SrFe12O19/Ni0.7Zn0.3Fe2O4 nanocomposite magnets", 《JOURNAL OF MAGNETISM AND MAGNETIC MATERIALS》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104211387A (en) * | 2014-09-03 | 2014-12-17 | 安徽工业大学 | Method for improving coercive force of spinelle iron-cobalt ferrite CoFe2O4 |
| CN104211387B (en) * | 2014-09-03 | 2015-12-02 | 安徽工业大学 | A kind of raising spinelle cobalt ferrite CoFe 2o 4coercitive method |
| CN104529424A (en) * | 2015-01-16 | 2015-04-22 | 安徽工业大学 | Composite permagnetferrite with functions of two-phase exchange coupling and keeping high coercive force |
| CN104973859A (en) * | 2015-06-29 | 2015-10-14 | 安徽工业大学 | Preparation method for composite ferrite powder with exchange coupling effect |
| CN106567123A (en) * | 2016-11-15 | 2017-04-19 | 彭晓领 | Preparation method of high-coercivity strontium ferrite |
| CN112851324A (en) * | 2021-01-21 | 2021-05-28 | 安徽大学 | Composite material applied to high-frequency field |
| CN113192717A (en) * | 2021-04-22 | 2021-07-30 | 兰州大学 | Metal soft magnetic composite material and preparation method thereof |
| CN114524668A (en) * | 2022-03-15 | 2022-05-24 | 宜宾金川电子有限责任公司 | Method for adding and recycling manganese zinc ferrite waste in strontium ferrite |
| CN115295266A (en) * | 2022-08-12 | 2022-11-04 | 安徽鑫磁源磁业有限公司 | M-type strontium ferrite-based dual-phase composite permanent magnetic ferrite block and preparation method thereof |
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