CN103204546B - Method for preparing nano cobalt ferrite - Google Patents
Method for preparing nano cobalt ferrite Download PDFInfo
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- CN103204546B CN103204546B CN201310133530.9A CN201310133530A CN103204546B CN 103204546 B CN103204546 B CN 103204546B CN 201310133530 A CN201310133530 A CN 201310133530A CN 103204546 B CN103204546 B CN 103204546B
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Abstract
The invention discloses a method for preparing nano-powder of nano cobalt ferrite (CoFe2O4) with a spinel structure at a low temperature. The preparation method comprises the steps of weighing ferric trichloride and cobaltous chloride in proportion, and mixing to prepare water solution A; evenly mixing the prepared NaOH or HOK aqueous alkali, and then dropwise adding N2H4.H2O to obtain solution B; rapidly stirring the water solution A obtained in the step 1 at 20-40 DEG C, and slowly dropwise adding the mixed solution B prepared in the step 2 into the water solution A to react, so as to obtain cobalt ferrite (CoFe2O4) powder sediment with a black spinel structure.
Description
Technical field
The present invention relates to a kind of preparation method's of Nanometer Cobalt Ferrite Oxide powder, particularly a kind of spinel structure Nanometer Cobalt Ferrite Oxide CoFe
2o
4preparation method.
Background technology
The vectolite of spinel type is a kind of magneticsubstance of excellent property, has high saturation magnetization, the outstanding plurality of advantages such as corrosion resistance nature and abrasion resistance properties.Its aspect magnetic recording, magnetics and magnetic fluid aspect be widely used.In addition because its high resistivity and significant Kerr magnetooptical effect make it have great application potential aspect absorbing material and New Type Magneto recording materials.Referring to: [1] " vectolite preparation and research thereof ", Zhang Chao, He'nan University's master thesis; [2] chemical method preparation technology and the absorbing property thereof of vectolite micro mist, Che Renchao, Li Yongqing etc., " aerospace material technique ",, the 6th phase in 1999; [3] Synthesis and characterization of size-controlled cobalt-ferrite-based ionic ferrofluids, Journal of Magnetism and Magnetic Materials, 225 (2001) 37-40.
At present, the preparation method of cobalt ferrite powder mainly contains sol-gel method, microemulsion method, solid reaction process and coprecipitation method etc., the people such as Lee J G synthesize Nanometer Cobalt Ferrite Oxide with sol-gel method, after 500 DEG C of calcinings of the method, prepared vectolite nanoparticle mean sizes is about 30nm, referring to: Lee J G, Kim C S, Lee H M, et a1. Magnetic properties of CoFe2O4 powers and thin films by a sol-gel method [J]. J Magn Mater, 1998,177 (2): 900-902..T. the people such as Pannaparayil has prepared vectolite between 135 ~ 175 DEG C by hydrothermal method, particle size is at 100 ~ 300nm, referring to: T. Pannaparayil and S. Komarneni, SYNTHESIS AND CHARACTERIZATION OF ULTRAFINE COBALT FERRITES, IEEE TRANSACTIONS ON MAGNETICS, VOL. 25, NO. 5, SEPTEMBER 1989,4233-4235.N. the people such as Moumen has prepared the vectolite particle of size at 2 ~ 5nm with microemulsion method, referring to: N. Moumen and M. P. Pileni, New Syntheses of Cobalt Ferrite Particles in the Range 25 nm:Comparison of the Magnetic Properties of the Nanosized Particles in Dispersed Fluid or in Powder Form, Chem. Mater., 1996,8 (5), pp 1128 – 1134.In preceding method, solid reaction process and sol-gel method all need the calcination process of comparatively high temps, referring to Chinese patent application 200410018797.8(publication number: CN101168452A) and Chinese patent application 201010045635.5(publication number: CN 101786668 A); The temperature of reaction of hydrothermal method is higher; Granule-morphology and size prepared by microemulsion method are better, but complex process, productive rate are low, and have residual organic matter.Coprecipitation method is a kind of relatively simple method of technique, but general coprecipitation method also need to just can be converted at boiling water or more than 60 DEG C spinel structure vectolite [3 under temperature condition, 9] referring to Synthesis and characterization of size-controlled cobalt-ferrite-based ionic ferrofluids, Journal of Magnetism and Magnetic Materials, 225 (2001) 37-40 and Chinese patent application 200510018262.1(publication number: CN1657490A).Yeong Il Kim etc. directly prepare vectolite with NaOH precipitation molysite and cobalt salt solution, and by controlling reaction temperature particle size, but at 60 DEG C, what obtain below is amorphous particle instead of ferrospinel, referring to: Yeong Il Kim, Don Kim, Choong Su Lee, Synthesis and characterization of CoFe2O4 magnetic nanoparticles prepared by temperature-controlled coprecipitation method, PhysicaB337 (2003) 42 – 51.The people such as M.Rajendran have provided a kind of method of preparing vectolite with NaOH and H2O2 mixing solutions co-precipitation molysite and cobalt salt solution, but the crystallization in the time of 20 DEG C of this method is poor, referring to M.Rajendran, R.C.Pullar, A.K.Bhattacharya, D.Das S.N.Chintalapudi, C.K.Majumdar, Magnetic properties of nanocrystalline CoFe2O4 powders prepared at room temperature:variation with crystallitesize, Journal of Magnetism and Magnetic Materials, 232 (2001), 71 – 83.
Summary of the invention
The invention provides one and can overcome prior art deficiency, can at lower temperature, prepare the method for cobalt ferrite powder with coprecipitation method.
The spinel structure Nanometer Cobalt Ferrite Oxide CoFe for preparing of the present invention
2o
4method be:
1) be hybridly prepared into water solution A after taking in proportion iron trichloride and cobalt dichloride;
2) preparation NaOH or KOH alkaline solution, drip N wherein after stirring
2h
4.H
2o, to obtain solution B;
3) water solution A that rapid stirring step 1 obtains at 20 ~ 40 DEG C, and by step 2) the mixing solutions B for preparing is slowly added drop-wise in water solution A and reacts, and obtains black precipitate;
4) chocolate precipitation distilled water step 3) reaction being produced fully wash to pH value be 7, then use washing with alcohol, then drying treatment obtains the vectolite CoFe of spinel structure
2o
4powder.
In the embodiment that the present invention provides, prepare spinel structure Nanometer Cobalt Ferrite Oxide CoFe
2o
4the iron trichloride of Shi Suoyong is FeCl
3.6H
2o, cobalt dichloride used is CoCl
2.6H
2o, FeCl when preparation A solution
3.6H
2o and CoCl
2.6H
2the mol ratio of O is 2: 1, and the NaOH of preparation or KOH alkaline concentration are 1.5 ~ 2.5 mol/L, and in the solution B of preparation, the concentration of hydrazine hydrate is 4 ~ 7mol/L.
In solution A in the embodiment of the present invention, concentration of metal ions is 0.01M ~ 0.05M.
Method of the present invention can (between 20 DEG C to 40 DEG C) be prepared vectolite CoFe at lower temperature
2o
4nanometer powder, and the particle crystallization obtaining is better, and transmission electron microscope (TEM) photo shows that particle mean size is 3 ~ 9nm, and the grain-size of calculating with X-ray diffraction spectrum meets, and is single crystal particle.Vibrating sample magnetometer (VSM) test shows that particle is at room temperature superparamagnetism, and under 1.2 T foreign fields, the specific magnetising moment is 11 ~ 40 emu/g.
Brief description of the drawings
Fig. 1 is the X-ray diffraction spectrum of embodiment 1 product and embodiment 2 products.
Fig. 2 is TEM photo and the selected area electron diffraction figure (SAED) of embodiment 1 product.
Fig. 3 is TEM photo and the selected area electron diffraction figure (SAED) of embodiment 2 products.
Fig. 4 is embodiment 1 magnetic hysteresis loop that for product, vibrating sample magnetometer (VSM) is measured.
Fig. 5 is embodiment 2 magnetic hysteresis loop that for product, vibrating sample magnetometer (VSM) is measured.
Embodiment
The invention provides following specific embodiment.
1) take 0.1784g(0.00066mol with mol ratio 2:1) FeCl
3.6H
2o and 0.07815g(0.00033mol) CoCl
2.6H
2o, is dissolved in 50ml distilled water, fully stirring and dissolving, and concentration of metal ions is 0.02M.
2) taking 1.6g(0.04mol) NaOH is dissolved in 20ml distilled water, and NaOH concentration is 2M.After stirring, drip wherein N
2h
4.H
2o(85% hydrazine hydrate)
10ml, N
2h
4.H
2o concentration is 5.6mol/L.
3) exist
room temperatureunder (20
oc) rapid stirring under condition, by step 2) alkali configuring and the mixing solutions of hydrazine hydrate be slowly added drop-wise in the solution of Fe, Co salt, react 2 hours.
4) black precipitate step 3) reaction being produced is fully washed to pH value 7 left and right with distilled water, then uses washing with alcohol 2 ~ 3 times, and then seasoning or vacuum-drying, obtains CoFe2O4 particle.
In accompanying drawing 1, the X-ray diffraction of this routine gained sample spectrum shows the spinel nano crystal structure that crystal grain is, the grain-size of being calculated by diffraction peak is 3 nm left and right, shows that with the TEM photo of Fig. 2 particle size is consistent, is single crystal particle.In Fig. 1, in X-ray diffraction spectrum and Fig. 2, SAED figure all shows particle well-crystallized.Fig. 4 for this reason routine sample at room temperature uses the measured magnetic hysteresis loop of VSM, under result show sample ability room temperature, is superparamagnetism, and the specific magnetising moment under 1.2 T foreign fields is 17 emu/g.
Embodiment 2.
1) take 0.1784g(0.00066mol with mol ratio 2:1) FeCl
3.6H
2o and 0.07815g(0.00033mol) CoCl
2.6H
2o, is dissolved in 50ml distilled water, fully stirring and dissolving, and concentration of metal ions is 0.02M.
2) taking 1.6g(0.04mol) NaOH is dissolved in 20ml distilled water, and NaOH concentration is 2M.After stirring, drip wherein N
2h
4.H
2o(85% hydrazine hydrate)
10ml, N
2h
4.H
2o concentration is 5.6mol/L.
3) exist
40 o crapid stirring under water bath condition, by step 2) alkali configuring and the mixing solutions of hydrazine hydrate be slowly added drop-wise in the solution of Fe, Co salt, react 2 hours.
4) black precipitate step 3) reaction being produced is fully washed to pH value 7 left and right with distilled water, then uses washing with alcohol 2 ~ 3 times, and then seasoning or vacuum-drying, obtains CoFe2O4 particle.Average particle size particle size is 9nm, is superparamagnetism under room temperature, 1.2 T specific magnetising moment 40emu/g after the match outward.
In accompanying drawing 1, the X-ray diffraction of this routine gained sample spectrum shows the spinel nano crystal structure that crystal grain is, the particle size of being calculated by diffraction peak is 9 nm left and right, shows that with the TEM photo of Fig. 3 particle size is consistent, is single crystal particle.In Fig. 1, in X-ray diffraction spectrum and Fig. 3, SAED figure all shows particle well-crystallized, and TEM photo shows that particle dispersion is good.Fig. 5 for this reason routine sample at room temperature uses the measured magnetic hysteresis loop of VSM, under result show sample ability room temperature, is superparamagnetism, and the specific magnetising moment under 1.2 T foreign fields is 40 emu/g.
Embodiment 3.
1) take 0.1784g(0.00066mol with mol ratio 2:1) FeCl
3.6H
2o and 0.07815g(0.00033mol) CoCl
2.6H
2o, is dissolved in 50ml distilled water, fully stirring and dissolving, and concentration of metal ions is 0.02M.
2) take
1.2g(0.03mol) NaOH is dissolved in 20ml distilled water, and NaOH concentration is 1.5M.After stirring, drip wherein N
2h
4.H
2o(85% hydrazine hydrate) 14ml, N
2h
4.H
2o concentration is 7mol/L.
3) exist
20 o crapid stirring under water bath condition, by step 2) alkali configuring and the mixing solutions of hydrazine hydrate be slowly added drop-wise in the solution of Fe, Co salt, react 3 hours.
4) black precipitate step 3) reaction being produced is fully washed to pH value 7 left and right with distilled water, then uses washing with alcohol 2 ~ 3 times, and then seasoning or vacuum-drying, obtains CoFe2O4 particle.Average particle size particle size is 3nm, is superparamagnetism under room temperature, 1.2 T specific magnetising moment 11emu/g after the match outward.
Embodiment 4.
1) take 0.1784g(0.00066mol with mol ratio 2:1) FeCl
3.6H
2o and 0.07815g(0.00033mol) CoCl
2.6H
2o, is dissolved in 50ml distilled water, fully stirring and dissolving, and concentration of metal ions is 0.02M.
2) take
2g(0.05mol) NaOH is dissolved in 20ml distilled water, and NaOH concentration is 2.5M.After stirring, drip wherein N
2h
4.H
2o(85% hydrazine hydrate)
6ml, N
2h
4.H
2o concentration is 3.8mol/L.
3) exist
20 o crapid stirring under water bath condition, by step 2) alkali configuring and the mixing solutions of hydrazine hydrate be slowly added drop-wise in the solution of Fe, Co salt, react 3 hours.
4) black precipitate step 3) reaction being produced is fully washed to pH value 7 left and right with distilled water, then uses washing with alcohol 2 ~ 3 times, and then seasoning or vacuum-drying, obtains CoFe2O4 particle.Average particle size particle size is 5nm, is superparamagnetism under room temperature, the 1.2 T specific magnetising moment 13 emu/g after the match outward.
Above-described embodiment shows, method provided by the invention can at room temperature be prepared the good spinel structure Nanocrystalline Cobalt of crystallization ferrite, and particle size is below 10 nanometers, and particle dispersion is good.This method technique is simple, and cost is lower, for preparation and the application of Nanometer Cobalt Ferrite Oxide powder provide a kind of valuable selection.
Claims (1)
1. prepare spinel structure Nanometer Cobalt Ferrite Oxide CoFe for one kind
2o
4method, it is characterized in that:
1) be hybridly prepared into water solution A after taking in proportion iron trichloride and cobalt dichloride;
2) NaOH or the KOH alkaline solution of preparation, drip N wherein after stirring
2h
4h
2o, to obtain solution B;
3) water solution A that rapid stirring step 1 obtains at 20 ~ 40 DEG C, and by step 2) the mixing solutions B for preparing is slowly added drop-wise in water solution A and reacts, and obtains black precipitate.
4) black precipitate step 3) reaction being produced with distilled water fully wash to pH value be 7, then use washing with alcohol, then drying treatment obtains the vectolite CoFe of spinel structure
2o
4powder.
2. the spinel structure Nanometer Cobalt Ferrite Oxide CoFe for preparing according to claim 1
2o
4method, it is characterized in that: iron trichloride used is FeCl
36H
2o, cobalt dichloride used is CoCl
26H
2o, FeCl when preparation A solution
36H
2o and CoCl
26H
2the mol ratio of O is 2: 1, and the NaOH of preparation or KOH alkaline concentration are 1.5 ~ 2.5 mol/L, and in the solution B of preparation, the concentration of hydrazine hydrate is 4 ~ 7mol/L.
3. the spinel structure Nanometer Cobalt Ferrite Oxide CoFe for preparing according to claim 2
2o
4method, it is characterized in that in solution A, concentration of metal ions is 0.01M ~ 0.05M.
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| CN105129868B (en) * | 2015-07-16 | 2017-01-04 | 大连理工大学 | One prepares Cr3+the CoFe of doping2o4the method of high density magnetic recording material |
| CN107633946A (en) * | 2017-09-25 | 2018-01-26 | 常州市沃兰特电子有限公司 | A kind of preparation method of nanometer of magnet |
| CN109943285B (en) * | 2019-04-16 | 2021-09-17 | 贵州大学 | High-performance wave-absorbing material core-shell structure CoxFe3-xO4@MoS2Nano-composite and synthesis method thereof |
| CN110305364A (en) * | 2019-07-30 | 2019-10-08 | 济南大学 | A kind of preparation method of novel magnetic polyvinyl formal sponge |
| CN112588256A (en) * | 2021-01-28 | 2021-04-02 | 华东交通大学 | Magnetic nano bimetal oxide adsorbent and application thereof |
| CN112851326A (en) * | 2021-01-29 | 2021-05-28 | 兰州大学 | Co2Z-type ferrite material and preparation method thereof |
| CN113200572A (en) * | 2021-05-07 | 2021-08-03 | 景德镇陶瓷大学 | Process method for preparing cobalt ferrite powder at low temperature in dry state |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0555056A2 (en) * | 1992-02-05 | 1993-08-11 | Toda Kogyo Corp. | Magnetic iron oxide particles, a process for producing the same and a magnetic recording medium |
| CN102190483A (en) * | 2010-03-01 | 2011-09-21 | 中国科学院生态环境研究中心 | Three-dimensional micro-nano material composed of nano CoFe2O4 and preparation method thereof |
| CN102923785A (en) * | 2012-11-19 | 2013-02-13 | 兰州理工大学 | Preparation method of CoFe2O4 magnetic nano material |
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2013
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0555056A2 (en) * | 1992-02-05 | 1993-08-11 | Toda Kogyo Corp. | Magnetic iron oxide particles, a process for producing the same and a magnetic recording medium |
| CN102190483A (en) * | 2010-03-01 | 2011-09-21 | 中国科学院生态环境研究中心 | Three-dimensional micro-nano material composed of nano CoFe2O4 and preparation method thereof |
| CN102923785A (en) * | 2012-11-19 | 2013-02-13 | 兰州理工大学 | Preparation method of CoFe2O4 magnetic nano material |
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