CN1071027A - High-magnetic heat stability cobalt improved r-di-iron trioxide magnetic and manufacture method thereof - Google Patents
High-magnetic heat stability cobalt improved r-di-iron trioxide magnetic and manufacture method thereof Download PDFInfo
- Publication number
- CN1071027A CN1071027A CN 92105419 CN92105419A CN1071027A CN 1071027 A CN1071027 A CN 1071027A CN 92105419 CN92105419 CN 92105419 CN 92105419 A CN92105419 A CN 92105419A CN 1071027 A CN1071027 A CN 1071027A
- Authority
- CN
- China
- Prior art keywords
- magnetic
- heat stability
- cobalt improved
- preparation
- improved
- 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.)
- Granted
Links
Abstract
The present invention relates to a kind of preparation cobalt improved r-Fe that mixes
2O
3The method of magnetic, particularly preparation have the cobalt improved r-Fe that mixes Mn or P of high-magnetic heat stability
2O
3Magnetic and preparation method thereof.The present invention is at cobalt improved r-Fe
2O
3Surface attached Mn of bag or P after heat treatment, make these ions diffusion in the lattice of magnetic, do the time spent simultaneously when being subjected to magnetic field and temperature, and the activation energy of Co ion migration improves greatly, and then improves the coercitive magnetic heat stability of magnetic.The CO of this method preparation
xR
yFe
3-x-yO
4, R=Mn or P, magnetic are applicable to the manufacturing record-reproduce head, digital record tape and disk etc.
Description
The present invention relates to a kind of preparation cobalt improved γ-Fe that mixes
2O
3The method of magnetic, particularly preparation have the cobalt improved γ-Fe that mixes Mn or P of high-magnetic heat stability
2O
3Magnetic and preparation method thereof.
γ-Fe that the Conjugate ferrite bag is attached
2O
3Magnetic is the magnetic that is widely used in video recording and aspects such as digital record tape and disk at present.But there is the imperfect shortcoming of coercitive magnetic heat stability in it: the tape made from it under magnetic field and temperature act on simultaneously, has the signal of former record to be difficult for wiping, shortcoming such as print-through is big.People such as Eiling mention in article
(1), invented a kind of cobalt improved γ-Fe of high-magnetic heat stability
2O
3Magnetic, it is at 40 ℃ and 3000 Oe the action of a magnetic fields after 100 hours, its coercive force about 1% of original value that only descended, but do not provide the preparation technology of this magnetic.People such as Marcot narrate in its patent
(2), when preparation FeOOH, add CoSO simultaneously
4Solution and phosphatase reaction after reduction and oxidation, are made the γ-Fe that contains Co or contain P
2O
3Magnetic.The coercive force of magnetic is improved.But they do not refer to the concrete preparation method and the magnetic coercive force of this magnetic and improve.But whether they do not refer to the concrete preparation method and the coercitive magnetic heat stability of magnetic of this magnetic good.
List of references:
（1）A.Eiling and R.A.Rott，IEEE T..Magn.MAG-21（5）（1985）1497
（2）Guy C.Marcott，pulaski，va，U.S.P.4209412
The objective of the invention is to overcome the shortcoming and defect of above-mentioned prior art, in order to improve cobalt improved γ-Fe
2O
3The magnetic heat stability of magnetic, thus provide a kind of at cobalt improved γ-Fe
2O
3The magnetic surface is with the attached one deck M of chemical coprecipitation method bag
nOr the p ion, when the attached P of bag, also to make it to form Co through Overheating Treatment
xP
yFe
3-x-yO
4The method of magnetic (wherein R is Mn.P).
The object of the present invention is achieved like this:
With γ-Fe
2O
3Magnetic places in the reactor, and the distilled water that adds 10 times of magnetic weight is warming up to 90-100 ℃, stirs with the blender limit that rotating speed is about 100 rev/mins, and the limit is sequentially added into FexSO
47H
2O, CoSO
47H
2O and MnSO
47H
2O solution (or NaPO
3)
6Solution, after stirring in 10-60 minute, still adding concentration while stirring is the NaOH solution of 200g/l.Afterwards, continue after stirring 50-150 minute between 90-100 ℃, to filter, be washed till (neutrality) between the PH=6-8 with distilled water, 60-80 ℃ of oven dry down, get final product the Co of high-magnetic heat stability
xR
yFe
3-x-yO
4Magnetic, wherein R is Mn.P; Also comprise Co
xP
yFe
3-x-yO
4Magnetic is put into tube furnace, under inert atmosphere, adds nitrogen and is heated to 390 ℃ of heat treatments 2 hours, reduces between 200-250 ℃ again, oxidation 5-15 minute, forms Co
xP
yFe
3-x-yO
4Magnetic.Used CoSO in reaction
47H
2O Fe
xSO
47H
2O, MnSO
4H
2O and (Napo
3)
6Amount equal γ-Fe respectively
2O
3The 5-40Wt%.50-100Wt%.2.5-25Wt%.10-40Wt% of magnetic weight, its surplus is γ-Fe
2O
3And unavoidable impurities.Because at cobalt improved γ-Fe
2O
3In the Conjugate ferrite superficial layer of magnetic, add the Mn ion, thereby make the Conjugate ferrite epitaxial loayer become cobalt Mn ferrite Co
xMn
yFe
3-x-yO
4; Wherein x=y=0.01-0.2 generates Co
xMn
yFe
3-x-yO
4Main chemical reactions as follows:
Because introduce the Mn ion, the activation energy that the Co ion is moved under the action of a magnetic field improves greatly, be difficult for migration, and then improve the coercitive magnetic heat stability of this magnetic.
Phosphorus is introduced cobalt improved γ-Fe
2O
3After in the magnetic body, must mix the cobalt improved CoxP ferrite of phosphorus Fe
3-x-yO
4; X=y=0.01-0.2 wherein, owing to P is diffused into crystals through heat treatment under inert atmosphere, the activation energy that cobalt ions is moved under the action of a magnetic field improves, thereby the coercitive magnetic heat stability of this magnetic is improved, and main chemical reactions is as follows:
High-magnetic heat stability cobalt improved γ-Fe of the present invention
2O
3The composition formula of magnetic is as follows:
Co
xR
yFe
3-x-yO
4;
Wherein: x=y=0.01-0.2
R＝Mn.P
Be elaborated below in conjunction with embodiment:
Embodiment 1
At room temperature with 10 gram needle-like γ-Fe
2O
3(long 0.5 μ m, mean axis be than 10: 1, Hc-4000o) puts into the reaction vessel of one 0.5 liter, and 200 milliliters of adding distil waters disperse stirring 1 hour for magnetic.
After disperseing to finish, every interval added 95 grams per liter CoSO in 10 minutes successively
47H
220 milliliters of O solution, 5 milliliters of 200 grams per liter NaOH solution, 125 grams per liter FeSO
47H
235 milliliters of 40 milliliters of O solution and 200 grams per liter NaOH solution should constantly stir in the course of reaction.Temperature with suspension system after 20 minutes rises to 85 ℃, and constant temperature 1 hour filters then, is washed to neutral PH=7.
In 200 ml distilled waters, the PH=8.0 with NaOH adjusts suspension adds 20 grams per liter (NaPO with filter cake dispersed with stirring again
3)
620 milliliters of solution are warming up to 70 ℃, stir 1 hour, filter then in oven dry below 60 ℃.
The magnetic that above-mentioned cladding is good is put into tube furnace, at N
2Under the atmosphere, 390 ℃ of heat treatment 2 hours, then in 210 ℃ of oxidations 10 minutes to powder in ferrous content at 1-3%.
Products therefrom chemical composition analysis result is: Co
2+3.49wt%, Fe
2+2.1wt%, P 0.88wt%
VSM measures powder Hc=721 Oe σ
8=71.6emu/g
Smear sample Hc
"=803 Oe
Smear sample is placed in the magnetic field of 3000 Oe, magnetic direction is perpendicular to the diaphragm direction, 90 ℃ of annealing 12 hours.
After VSM measures magnetic anneal, smear sample H
' 0 "=788 Oe
The ratio H of coercive force before coercive force and the magnetic anneal behind the smear sample magnetic anneal
' 0 "/ Hc=98%.
Embodiment 2
With 10 gram γ-Fe
2O
3Magnetic places in the reactor, adds 200 ml distilled waters again, and ultrasonic dispersion 30 minutes is sequentially added into 3.93 gram FeSO
47H
2O, 1.19 gram CoSO
47H
2O and 0.48 gram MnSOH
2O is heated to 95 ℃ and stirred 10 minutes, adds the NaOH solution that 50 ml concns are 200 grams per liters while stir then, adds alkali and finishes the back continuation 95 ℃ of stirrings 1 hour.Through being washed to neutrality, 80 ℃ of oven dry (drying by the fire approximately 15 hours) down obtain mixing the cobalt improved γ-Fe of Mn
2O
3Magnetic.
Products therefrom chemical composition analysis result is: Mn/ γ-Fe
2O
3=1.5wt%, Co/ γ-Fe
2O
3=2.3wt%, Fe
2+/ γ-Fe
2O
3=2.0wt%.
The magnetic that records magnetic with vibrating specimen magnetometer is:
γ-Fe
2O
3Hc＝360 Oe，σ
3＝72emu/g，
Mix Mn cobalt improved-γ-Fe
2O
3Magnetic: Hc=600 Oe, σ
3=72emu/g.
The magnetic anneal condition of smear sample is with embodiment 1
Before the smear sample magnetic thermal annealing: Hc=610 Oe
Behind the smear sample magnetic thermal annealing: H
' c=577 Oe
Behind the magnetic thermal annealing with the magnetic thermal annealing before the ratio of coercive force: H
' c/ Hc=94.6%.
Embodiment 3
This example is used to mix when prepared magnetic particle capability is compared behind Mn or the P, and example for referencial use is pressed the cobalt improved γ-Fe of embodiment 1 prepared
2O
3Magnetic is except that not adding (NaPO
3)
6Outside the aqueous solution, all the other steps are all constant, and VSM measures powder, Hc=729 Oe, σ
s=73.2emu/g smear sample Hc
"=815 Oe
Smear sample is carried out magnetic anneal, smear sample H behind the magnetic anneal by the condition identical with embodiment 1
' C "/ Hc
"=88%.
Claims (4)
1, the high-magnetic heat stability cobalt improved γ-Fe of a kind of preparation
2O
3The method of magnetic comprises the following steps:
With γ-Fe
2O
3Magnetic is that raw material places in the reaction vessel, is sequentially added into CoSO while stirring
47H
2O, FeSO
47H
2O, MnSO
4H
2O or (NaPO
3)
6Between the solution heating-up temperature arrives 90-100 ℃, stirred 10-60 minute, adding concentration more while stirring is the NaoH solution of 200g/l, is total to 50ml, till adding, continue constant temperature between 90-100 ℃, stir after 50-150 minute, filter, be washed till between neutral PH=6-8 with distilled water, 60-80 ℃ of oven dry down, the cobalt improved γ-Fe of preparation doping
2O
3Must measure percentage is: the CoSO of 5-40wt%
47H
2O, the FeSo of 50-100wt%
47H
2O, 2.5-25wt%MnSO
4H
2(the NaPO of O or 10-40wt%
3)
6, surplus is γ-Fe
2O
3And unavoidable impurities.
2, by the high-magnetic heat stability cobalt improved γ-Fe of the described preparation of claim 1
2O
3The method of magnetic is characterized in that: also comprise the cobalt improved γ-Fe of doping that above-mentioned 60-80 ℃ is dried down
2O
3Magnetic is put into tube furnace, is heated to 390 ℃ of heat treatments 2 hours under inert atmosphere protection, is cooled between 200 ℃ oxidation 5-15 minute again.
3, by the high-magnetic heat stability cobalt improved γ-Fe of the described preparation of claim 2
2O
3The method of magnetic is characterized in that: described inert gas is N
2
4, a kind of by the direct high-magnetic heat stability magnetic of manufacturing of the described preparation method of claim 1 institute, it is characterized in that: it consists of CoxR
yFe
3-x-yO
4;
Wherein: x=y=0.01-0.2
R＝Mn，P
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92105419A CN1035088C (en) | 1992-07-10 | 1992-07-10 | High-magnetic heat stability cobalt improved r-ferric oxide magnet powder and its made method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92105419A CN1035088C (en) | 1992-07-10 | 1992-07-10 | High-magnetic heat stability cobalt improved r-ferric oxide magnet powder and its made method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1071027A true CN1071027A (en) | 1993-04-14 |
| CN1035088C CN1035088C (en) | 1997-06-04 |
Family
ID=4941374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92105419A Expired - Fee Related CN1035088C (en) | 1992-07-10 | 1992-07-10 | High-magnetic heat stability cobalt improved r-ferric oxide magnet powder and its made method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1035088C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824237A (en) * | 2010-05-05 | 2010-09-08 | 太原理工大学 | Method for modifying and whitening kaolin |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5719052B2 (en) * | 1974-09-20 | 1982-04-20 | ||
| JPS5719053B2 (en) * | 1974-09-20 | 1982-04-20 | ||
| JPS53132799A (en) * | 1977-04-22 | 1978-11-18 | Fuji Photo Film Co Ltd | Manufacture of strong magnetic powder |
| US4305753A (en) * | 1980-07-31 | 1981-12-15 | Hercules Incorporated | Process for producing ferromagnetic metallic particles |
| AU558199B2 (en) * | 1982-09-16 | 1987-01-22 | Ishihara Sangyo Kaisha Ltd. | Production of magnetic powder |
| JPH0676218B2 (en) * | 1988-02-10 | 1994-09-28 | 石原産業株式会社 | Method for producing cobalt-containing ferromagnetic iron oxide |
-
1992
- 1992-07-10 CN CN92105419A patent/CN1035088C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824237A (en) * | 2010-05-05 | 2010-09-08 | 太原理工大学 | Method for modifying and whitening kaolin |
| CN101824237B (en) * | 2010-05-05 | 2012-07-04 | 太原理工大学 | Method for modifying and whitening kaolin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1035088C (en) | 1997-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR890005158B1 (en) | The magnetic recording medium | |
| US4296149A (en) | Manufacture of acicular cobalt-containing magnetic iron oxide | |
| DE2705967A1 (en) | Process for the production of acicular cobalt-containing magnetic iron oxide | |
| KR890001971B1 (en) | Process for producing cobalt-containing magnetic iron oxide powder | |
| CN1071027A (en) | High-magnetic heat stability cobalt improved r-di-iron trioxide magnetic and manufacture method thereof | |
| DE2649714A1 (en) | MAGNETIC MIXED OXIDES AND PROCESS FOR THEIR PRODUCTION | |
| JPS5856232A (en) | Magnetic recording medium | |
| US4457982A (en) | Acicular ferrimagnetic iron oxide and its preparation | |
| JPS60255628A (en) | Fine powder of ba ferrite plate particle for magnetic recording use and its preparation | |
| JP3119362B2 (en) | Method for producing cobalt-modified acicular iron oxide | |
| JPS6051243B2 (en) | Method for producing magnetic iron oxide particles for magnetic recording materials | |
| WO1988003308A1 (en) | A process for the preparation of magnetic hexaferrite particles, particles obtained and products containing them | |
| JPH0270003A (en) | Method for treating ferromagnetic iron powder | |
| JPH0717385B2 (en) | Method for producing composite ferrite magnetic powder | |
| JP3429881B2 (en) | Composite type hexagonal ferrite magnetic powder and method for producing the same | |
| JP3169105B2 (en) | Needle-like alloy magnetic fine particle powder containing iron as a main component and method for producing the same | |
| JPH07335417A (en) | Magnetic powder | |
| Sadamura et al. | Crystallographic study of cobalt treatment on γ‐Fe2O3 | |
| EP0583621B1 (en) | Process for producing acicular gamma iron (III) oxyhydroxide particles | |
| JPH0755832B2 (en) | Method for producing cobalt-containing ferromagnetic iron oxide powder | |
| JPS5919964B2 (en) | Method for producing ferromagnetic metal powder | |
| EP0299332B1 (en) | Process for preparing ferromagnetic fine particles for magnetic recording | |
| JP3246943B2 (en) | Stabilization method of acicular ferromagnetic metal powder consisting essentially of iron | |
| JPH0832564B2 (en) | Method for producing needle-shaped alpha-iron oxide (III) | |
| JP3242102B2 (en) | Magnetic powder and method for producing the same |
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 | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |