CN102173461A - Method for preparing MxR1-xFe2O4 nanometer powder quickly - Google Patents
Method for preparing MxR1-xFe2O4 nanometer powder quickly Download PDFInfo
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- CN102173461A CN102173461A CN2010106223912A CN201010622391A CN102173461A CN 102173461 A CN102173461 A CN 102173461A CN 2010106223912 A CN2010106223912 A CN 2010106223912A CN 201010622391 A CN201010622391 A CN 201010622391A CN 102173461 A CN102173461 A CN 102173461A
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Abstract
The invention provides a method for preparing MxR1-xFe2O4 nanometer powder quickly, which is characterized by comprising the following steps of: (1) mixing ferrous sulfate heptahydrate and one or more of crystal water-containing metal sulfates according to a molar ratio of M<2+> to R<2+> to Fe<3+> of x:(1-x):2 in a chemical structural formula MxR1-xFe2O4, and putting the mixture in a planet mill, and mixing and grinding for 3 to 5 minutes, wherein x is equal to 0.5 to 1; (2) adding a NaOH solid according to a molar ratio of Fe<2+> to OH<-> of 1:3, performing dry grinding by using the planet mill at two stages, wherein the dry grinding is performed for 8 to 10 minutes at the first stage, and is performed for 5 to 10 minutes at the second stage; and (3) adding deionized water, so that the mass ratio concentration of slurry is between 40 and 50 percent, performing wet grinding by using the planet mill for 5 to 10 minutes, and performing centrifugal separation, washing and drying sequentially to obtain the MxR1-xFe2O4 nanometer powder. In the method, the MxR1-xFe2O4 nanometer powder with an excellent crystal structure and high purity can be synthesized directly without calcining, so the method is high in operability and repeatability, the phenomenon of unstable hand lapping process of mortars in the conventional low-temperature solid-phase reaction method is prevented, energy consumption is reduced, and the method is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of M
xR
1-xFe
2O
4The fast preparation method of nano-powder belongs to the soft magnetic ferrite technical field of nano material.
Background technology
Low-temperature solid phase reaction prepares the soft magnetic ferrite nano-powder at present, is the method that adopts underhand polish, makes reactant finish the part solid state reaction in agate mortar, generates precursor.And in the process of grinding preparation, can there be a phenomenon of intensive bonded abrasive wall, cause reaction can't carry out or carry out incomplete phenomenon, so adopt follow-up low temperature heat-treatment process that presoma is carried out heat treated usually, thoroughly carry out preparing required product fully to promote solid state reaction.This also is to cause traditional low-temperature solid phase reaction technology of preparing to adopt the convenient reason of handling wall sticking phenomenon and not adopting mechanical mill of controlling of underhand polish.But owing to be underhand polish, can have more error in experimentation, and the single treatment amount is few, there is certain difference in different operator's gained experiment conclusion, and circulation ratio is bad, causes the product performance instability, can not suitability for industrialized production.And follow-up heat treatment process can cause particulate to reunite and grow up, and causes granularity inhomogeneous, increases energy consumption.It then is to adopt Fe that traditional high-energy ball milling prepares the soft magnetic ferrite nano-powder
2O
3With other oxide powder as raw material, usually need the long high-energy ball milling time, be generally more than 10 hours, just can make reactant generation size reduction machinery power chemical effect, generate target product, increased energy consumption, and product purity is not high.
Summary of the invention
Problem to be solved by this invention provides and a kind ofly can overcome above-mentioned defective, workable, favorable reproducibility, technology is simple, suitable batch is produced M
xR
1-xFe
2O
4The fast preparation method of nano-powder.Its technical scheme is:
A kind of M
xR
1-xFe
2O
4The fast preparation method of nano-powder is characterized in that adopting following steps: (1) contains the metal sulfate of crystal water with ferrous sulfate and one or more, presses chemical structural formula M
xR
1-xFe
2O
4In mol ratio M
2+: R
2+: Fe
3+=x: 1-x: 2 mix, and wherein x=0.5～1 places planetary mills mixed grinding 3～5min; (2) press Fe
2+: OH
-Mol ratio is 1: 3 adding NaOH solid, adopts planetary mills to divide two sections dry grinding 8～10min and 5～10min; (3) add deionized water, making the pulp quality specific concentration is 40%-50%, adopts planetary mills wet-milling 5～10min, gets M successively after centrifugation, washing, drying
xR
1-xFe
2O
4Nano-powder.
Described M
xR
1-xFe
2O
4The fast preparation method of nano-powder, in the step (1), the metal sulfate that contains crystal water comprises NiSO
46H
2O, ZnSO
47H
2O, MgSO
47H
2O and MnSO
4H
2O, the divalent-metal ion that M, R represent a kind of metal sulfate respectively and provided in the structural formula, but two kinds of divalent-metal ion differences that metal sulfate provided.
Described M
xR
1-xFe
2O
4The fast preparation method of nano-powder, in the step (2), first section is ground 8～10min, will grind jar grinding medium and the material of the inside then and take out simultaneously, dries naturally and carries out second section dry grinding after 8～10 hours again, grinds 5～10min.
Described M
xR
1-xFe
2O
4The fast preparation method of nano-powder, in step (1), step (2) and the step (3), the planetary mills grinding medium adopts alumina balls or zirconia ball, and wherein big, the little spherical diameter of neutralization is respectively 12mm, 10mm and 5mm, and number is respectively 60～90,30～70 and 100～160.
Described M
xR
1-xFe
2O
4The fast preparation method of nano-powder, in the step (2), planetary mills grinding technics ratio of grinding media to material is 2～5: 1.
Described M
xR
1-xFe
2O
4The fast preparation method of nano-powder in the step (3), is used deionized water wash after the product centrifugation, removes Na
2SO
4, until detecting Na in the filtrate with the FP640 flame photometer
+Content be less than 0.5wt%, 100～120 ℃ of dryings, promptly get M again
xR
1-xFe
2O
4Nano-powder.
The present invention compared with prior art, its advantage is:
1, adopts planetary mills to replace hand lapping,, can avoid because the experimental error that underhand polish caused, workable, favorable reproducibility and the single treatment amount is many, suitable batch production by adjusting grinding technics.
2, the planetary mills grinding technics divides two sections to carry out, the strong sticking wall that can effectively avoid occurring in the process of lapping and phenomenon that solid state reaction can't be carried out just can generate M fully thereby make solid state reaction need not subsequent heat treatment technology
xR
1-xFe
2O
4Nano-powder, energy efficient.
3, adopting the metal sulfate and the sodium hydroxide that contain crystal water is raw material, replaces oxide raw material in traditional high-energy ball milling, can significantly reduce milling time, makes reaction can generate M at short notice fully
xR
1-xFe
2O
4Nano-powder, product purity is higher, and energy efficient.
Description of drawings
Fig. 1 is the embodiment of the invention 1 gained NiFe
2 O
4700 ℃ of forward and backward XRD figure of thermal treatment of nano-powder;
Fig. 2 is the embodiment of the invention 1 gained NiFe
2O
4SEM figure before 700 ℃ of thermal treatments of nano-powder.
Among the figure: Fig. 1 (a) is without 700 ℃ of resulting NiFe of thermal treatment among the embodiment 1
2O
4The XRD figure spectrum of nano-powder, Fig. 1 (b) is through 700 ℃ of resulting NiFe of thermal treatment among the embodiment 1
2O
4The XRD figure spectrum of nano-powder.
Embodiment
Embodiment 1: the planetary mills grinding medium adopts alumina balls, and big ball, middle ball and little spherical diameter are respectively 12mm, 10mm and 5mm, and number is respectively 68,40 and 160, and its concrete steps are:
(1) with FeSO
47H
2O and NiSO
46H
2O is Ni in molar ratio
2+: Fe
2+Take by weighing place planetary mills mixed grinding 5min at=1: 2;
(2) press Fe
2+: OH
-Mol ratio is 1: 3 adding NaOH solid, and ratio of grinding media to material is 3: 1, divides two sections to adopt the planetary mills dry mill process, and first section grinding 8min takes out a grinding medium and a material inside the mill jar simultaneously, dries naturally 10 hours, carries out second section grinding 10min again;
(3) add deionized water, preparation slip quality is 40% than concentration, adopts planetary mills wet-grinding technology and relative device grinding 5min; To use deionized water wash after the slip centrifugation, remove Na
2SO
4, until detecting Na in the filtrate with the FP640 flame photometer
+Content be less than 0.5wt%, 120 ℃ down dry, prepare NiFe
2O
4Nano-powder.
Through X-ray diffraction analysis (XRD) and scanning electron microscope analysis (SEM) as can be known, before the thermal treatment and all generate NiFe after the thermal treatment
2O
4Spinel structure, the powder degree of crystallinity before the thermal treatment is good as can be seen, compares with powder diffraction result after the thermal treatment, and its characteristic peak diffracted intensity slightly reduces, and the diffraction peak width increases, and illustrates that grain-size is less.Granule-morphology is sheet structure, and the particle diameter size is about 50nm, thickness 10～20nm.The above results shows, adopts preparation technology of the present invention can save subsequent heat treatment technology and just can prepare even particle size, form rule, the NiFe that degree of crystallinity is good
2O
4Nano-powder.
Embodiment 2: the planetary mills grinding medium adopts alumina balls, and big ball, middle ball and little spherical diameter are respectively 12mm, 10mm and 5mm, and number is respectively 90,30 and 100, and its concrete steps are:
(1) with FeSO
47H
2O, NiSO
46H
2O and ZnSO
47H
2O is Ni in molar ratio
2+: Zn
2+: Fe
2+=0.5: take by weighing at 0.5: 2 and to place planetary mills mixed grinding 5min;
(2) press Fe
2+: OH
-Mol ratio is 1: 3 adding NaOH solid, and ratio of grinding media to material is 4: 1, divides two sections to adopt the planetary mills dry mill process, and first section grinding 10min takes out a grinding medium and a material inside the mill jar simultaneously, dries naturally 10 hours, carries out second section grinding 5min again;
(3) add deionized water, preparation slip quality is 45% than concentration, adopts planetary mills wet-grinding technology and relative device grinding 8min; To use deionized water wash after the slip centrifugation, remove Na
2SO
4, until detecting Na in the filtrate with the FP640 flame photometer
+Content be less than 0.5wt%, 120 ℃ down dry, prepare Ni
0.5Zn
0.5Fe
2O
4Nano-powder.
Through X-ray diffraction analysis (XRD) and scanning electron microscope analysis (SEM) as can be known, the Ni of two sections grinding 5min
0.5Zn
0.5Fe
2O
4Grain-size is 8.8nm, the Ni of two sections grinding 10min
0.5Zn
0.5Fe
2O
4Grain-size is 10nm, and granule-morphology is sheet structure, and granular size is about 50nm.
Embodiment 3: the planetary mills grinding medium adopts alumina balls, and big ball, middle ball and little spherical diameter are respectively 12mm, 10mm and 5mm, and number is respectively 70,60 and 120, and its concrete steps are:
(1) with FeSO
47H
2O, NiSO
46H
2O and MnSO
4H
2O is Ni in molar ratio
2+: Mn
2+: Fe
3+=0.95: take by weighing at 0.05: 2 and to place planetary mills mixed grinding 3min;
(2) press Fe
2+: OH
-Mol ratio is 1: 3 adding NaOH solid, and ratio of grinding media to material is 3: 1, divides two sections to adopt the planetary mills dry mill process, and first section grinding 8min takes out a grinding medium and a material inside the mill jar simultaneously, dries naturally 10 hours, carries out second section grinding 10min again;
(3) add deionized water, preparation slip quality is 45% than concentration, adopts planetary mills wet-grinding technology and relative device grinding 8min; To use deionized water wash after the slip centrifugation, remove Na
2SO
4, until detecting Na in the filtrate with the FP640 flame photometer
+Content be less than 0.5wt%, 100 ℃ down dry, prepare Ni
0.95Mn
0.05Fe
2O
4Nano-powder.
Through X-ray diffraction analysis (XRD) and scanning electron microscope analysis (SEM) as can be known, Ni
0.95Mn
0.05Fe
2O
4Grain-size is 7.8nm, and granule-morphology is a sheet structure, and granular size is about 50nm.
Claims (6)
1. M
xR
1-xFe
2O
4The fast preparation method of nano-powder is characterized in that adopting following steps: (1) contains the metal sulfate of crystal water with ferrous sulfate and one or more, presses chemical structural formula M
xR
1-xFe
2O
4In mol ratio M
2+: R
2+: Fe
3+=x: 1-x: 2 mix, and wherein x=0.5～1 places planetary mills mixed grinding 3～5min; (2) press Fe
2+: OH
-Mol ratio is 1: 3 adding NaOH solid, adopts planetary mills to divide two sections dry grinding 8～10min and 5～10min; (3) add deionized water, making the pulp quality specific concentration is 40%-50%, adopts planetary mills wet-milling 5～10min, gets M successively after centrifugation, washing, drying
xR
1-xFe
2O
4Nano-powder.
2. M as claimed in claim 1
xR
1-xFe
2O
4The fast preparation method of nano-powder is characterized in that: in the step (1), the metal sulfate that contains crystal water comprises NiSO
46H
2O, ZnSO
47H
2O, MgSO
47H
2O and MnSO
4H
2O, the divalent-metal ion that M, R represent a kind of metal sulfate respectively and provided in the structural formula, but two kinds of divalent-metal ion differences that metal sulfate provided.
3. M as claimed in claim 1
xR
1-xFe
2O
4The fast preparation method of nano-powder is characterized in that: in the step (2), first section is ground 8～10min, will grind jar grinding medium and the material of the inside then and take out simultaneously, dries naturally and carries out second section dry grinding after 8～10 hours again, grinds 5～10min.
4. M as claimed in claim 1
xR
1-xFe
2O
4The fast preparation method of nano-powder, it is characterized in that: in step (1), (2) and (3), the planetary mills grinding medium adopts alumina balls or zirconia ball, and wherein big, the little spherical diameter of neutralization is respectively 12mm, 10mm and 5mm, and number is respectively 60～90,30～70 and 100～160.
5. M as claimed in claim 1
xR
1-xFe
2O
4The fast preparation method of nano-powder is characterized in that: in the step (2), planetary mills grinding technics ratio of grinding media to material is 2～5: 1.
6. M as claimed in claim 1
xR
1-xFe
2O
4The fast preparation method of nano-powder is characterized in that: in the step (3), use deionized water wash after the product centrifugation, remove Na
2SO
4, until detecting Na in the filtrate with the FP640 flame photometer
+Content be less than 0.5wt%, 100～120 ℃ of dryings, promptly get M again
xR
1-xFe
2O
4Nano-powder.
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|---|---|---|---|
| CN 201010622391 CN102173461B (en) | 2010-12-30 | 2010-12-30 | Method for preparing MxR1-xFe2O4 nanometer powder quickly |
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|---|---|---|---|
| CN 201010622391 CN102173461B (en) | 2010-12-30 | 2010-12-30 | Method for preparing MxR1-xFe2O4 nanometer powder quickly |
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| Publication Number | Publication Date |
|---|---|
| CN102173461A true CN102173461A (en) | 2011-09-07 |
| CN102173461B CN102173461B (en) | 2013-01-23 |
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112239356A (en) * | 2020-10-28 | 2021-01-19 | 南京新康达磁业股份有限公司 | Magnetic nickel-zinc ferrite material and preparation method thereof |
| CN113045304A (en) * | 2021-03-25 | 2021-06-29 | 桂林电子科技大学 | Ferrite wave-absorbing material with mixed spinel structure and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050249817A1 (en) * | 2004-05-10 | 2005-11-10 | Yousef Haik | Magnetic particle composition for therapeutic hyperthermia |
| CN101723655A (en) * | 2008-10-21 | 2010-06-09 | 兰州大学 | Preparation method of Mn-Zn ferrite cobalt-doped nano material |
| CN101747046A (en) * | 2009-10-15 | 2010-06-23 | 南京航空航天大学 | Method for preparing crystalline-state mesoporous CoFe204 with large specific surface area |
-
2010
- 2010-12-30 CN CN 201010622391 patent/CN102173461B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050249817A1 (en) * | 2004-05-10 | 2005-11-10 | Yousef Haik | Magnetic particle composition for therapeutic hyperthermia |
| CN101723655A (en) * | 2008-10-21 | 2010-06-09 | 兰州大学 | Preparation method of Mn-Zn ferrite cobalt-doped nano material |
| CN101747046A (en) * | 2009-10-15 | 2010-06-23 | 南京航空航天大学 | Method for preparing crystalline-state mesoporous CoFe204 with large specific surface area |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112239356A (en) * | 2020-10-28 | 2021-01-19 | 南京新康达磁业股份有限公司 | Magnetic nickel-zinc ferrite material and preparation method thereof |
| CN113045304A (en) * | 2021-03-25 | 2021-06-29 | 桂林电子科技大学 | Ferrite wave-absorbing material with mixed spinel structure and preparation method thereof |
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| CN102173461B (en) | 2013-01-23 |
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