CN101169998A - Method for making magnetic nano particle based on solution co-deposition - Google Patents
Method for making magnetic nano particle based on solution co-deposition Download PDFInfo
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- CN101169998A CN101169998A CNA2006101139746A CN200610113974A CN101169998A CN 101169998 A CN101169998 A CN 101169998A CN A2006101139746 A CNA2006101139746 A CN A2006101139746A CN 200610113974 A CN200610113974 A CN 200610113974A CN 101169998 A CN101169998 A CN 101169998A
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Abstract
The invention belongs to powder preparation field, more particularly relates to a method for preparing spherical magnetic Fe3O4 nanoparticles by using the coprecipitation method of a solution layer. The method comprises the steps of: forming a solution layer from the mixed alcohol solution of ferric salt and ferrous salt on a stainless steel band in a sealed container, and adding ammonia gas as precipitant to react with reactant in the solution layer to generate spherical Fe3O4 particles. In the reaction, the presence of water molecules is reduced to effectively obviate particle agglomeration. The thickness of the solution layer can be adjusted by applying the solution, and the diameter of the Fe3O4 particle can be controlled to a range from several nanometers to dozens of nanometers by controlling the concentration of the reactant alcohol solution and the thickness of the solution layer, thereby achieving good dispersivity.
Description
Technical field
The invention belongs to the powder preparing field, particularly a kind of employing based on solution co-deposition prepares spherical magnetic nanoparticle Fe
3O
4Method.
Technical background
Magnetic nanoparticle especially has the nanometer Fe of superparamagnetism
3O
4Particle, people's attention extremely always in recent years.Magnetic Nano Fe
3O
4Have the characteristics of magnetic material and nano material concurrently, be widely used in many fields such as information, biology, medical science, lubricated and magnetic fluid.
Research thinks that one of the reunion most important reason of nano particle is the existence of water in the course of reaction, forms hydrogen bond between particle and the hydrone.Nano magnetic particle is owing to magnetic effect, and agglomeration is stronger.Present Fe
3O
4The preparation method mainly contain physical method, chemical method and biogenic method.Physical method mainly contains polishing, sprays high-temperature decomposition and laser high-temperature decomposition etc.The time that polishing needs is long; High-temperature decomposition has the advantages that to change preparation rapidly, continuously, but needs special complex apparatus.Chemical method is simple, uses at most, mainly contains coprecipitation, microemulsion method, elevated temperature heat decomposition organic precursor method, electrochemical process and sonochemical method etc.Coprecipitation prepares magnetic Fe
3O
4Simple and convenient, do not need complicated instrument and equipment, be maximum a kind of method of studying at present.Coprecipitation is with molysite and ferrous salt wiring solution-forming by a certain percentage, selects suitable alkaline precipitating agent such as NaOH for use, NH
3.H
2O etc. carry out co-precipitation, obtain the magnetic Fe of function admirable by the control process conditions
3O
4Particle.Though coprecipitation has above advantage, the difficult control of its process conditions, the Fe that obtains
3O
4Still there are defective in particle grain size and dispersiveness.
Summary of the invention
It is spherical to the purpose of this invention is to provide the preparation of a kind of based on solution co-deposition, and particle diameter is little, the magnetic Nano Fe that is evenly distributed
3The method of O particle.Adopting absolute ethyl alcohol is that solvent is made into a certain proportion of solution with molysite and ferrous salt, and ammonia is as the precipitation reagent of reaction, thereby has effectively reduced the existence of water in the system.Adopt based on solution co-deposition effectively to reduce grain diameter, avoid the Fe that generates
3O
4Particle is further reunited.
The objective of the invention is to realize that by based on solution co-deposition the method for making magnetic nano particle based on solution co-deposition may further comprise the steps:
(1) under the nitrogen protection, the preparation mass percent concentration is that the alcoholic solution of 1%～15% iron chloride and mass percent concentration are the alcoholic solution of 0.5%～6% frerrous chloride; The alcoholic solution of iron chloride is mixed with the alcoholic solution of frerrous chloride, guarantee Fe in the mixed liquor
3+With Fe
2+Mol ratio be 2: 1; Described alcohol is absolute ethyl alcohol;
(2) in closed container, feed nitrogen, get rid of the oxygen in the closed container; The reactant mixed liquor of step (1) is placed closed container, and hierarchy of control temperature is 25～75 ℃; Reactant mixed liquor with step (1) is coated on the smooth stainless steel band that rotates then, makes the reactant mixed liquor become solution layer in stainless steel band upper berth spread, and it is 10 that stainless steel band upper berth spread becomes the thickness of solution layer
7～10
-4Mm; The thickness of solution layer can be by applying control;
(3) logical ammonia in the closed container in step (2), the reactant reaction in the solution layer on the stainless steel band of ammonia and rotation generates the Fe of black
3O
4Particle;
(4) Fe that obtains on the stainless steel band that step (3) is rotated
3O
4Particle is collected in the groove, with ethanol solution wash-out Fe
3O
4Particle; Fe
3O
4Particle is through absolute ethanol washing, and vacuumize is to constant weight, and particle is spherical in shape, and particle size range is 3～20nm.
The device of enforcement the inventive method can be device as shown in Figure 1, comprises ammonia bottle 1, nitrogen cylinder 2, ammonia inlet 3, nitrogen inlet 4, sample solution groove 5, top pulley 6, nitrogen discharge mouth 7, closed container 8, stainless steel strip 9, division board 10, below pulley 11, sample feeder 12, ammonia emission mouth 13;
Be divided into two containers up and down 8 li of closed containers by division board 10, in the container sample feeder 12 is being arranged down, pulley 11 below being equipped with one in the sample feeder, below be equipped with one in the upper container above the pulley above pulley 6, top pulley 6 is connected with below pulley 11 usefulness one stainless steel strip 9, and stainless steel band is by the pulley driven rotary; One sample solution tank 5 is fixed on the pulley 6 of top;
Have ammonia emission mouth 13 on the sidewall of the bottom of closed container 8, top has nitrogen discharge mouth 7; Have ammonia inlet 3 and nitrogen inlet 4 on another upper portion side wall, the ammonia inlet communicates with ammonia source (ammonia bottle 1) by pipeline, and nitrogen inlet communicates with source nitrogen (nitrogen cylinder 2) by pipeline.
Form solution layer on the stainless steel band of mixed alcohol solution in closed container of the present invention with molysite and ferrous salt, ammonia generates Fe as the reactant reaction in precipitation reagent and the solution layer
3O
4, the Fe that obtains
3O
4Particle is spherical in shape.Owing to reduced the existence of hydrone in the reaction, thereby avoided the reunion of particle effectively.Regulate (as the distance control between outlet of embodiment 1 solution tank and stainless steel band) when the thickness of solution layer can be by coating solution, can regulate and control Fe by the thickness of control reactant alcoholic solution concentration and solution layer
3O
4Grain diameter, scope to tens nanometers, and have good dispersiveness in several nanometers.
Description of drawings
Fig. 1. the method equipment therefor schematic diagram of the making magnetic nano particle based on solution co-deposition of the embodiment of the invention 1.
Fig. 2. Fe in the Comparative Examples of the present invention
3O
4The TEM photo of particle.
Fig. 3. Fe in the embodiment of the invention 1
3O
4The TEM photo of particle.
Reference numeral
1. ammonia bottle 2. nitrogen cylinders 3. ammonias enter the mouth
4. nitrogen inlet 5. sample solution grooves 6. top pulleys
7. nitrogen discharge mouth 8. closed containers 9. stainless steel strips
10. division board 11. below pulleys 12. sample feeders
13. ammonia emission mouth
Embodiment
Comparative Examples. coprecipitation prepares magnetic Fe
3O
4Particle
In the 2L of 800ml deionized water stirring reactor, add 40.0gFeCl
3.6H
2O and 14.7gFeCl
2.4H
2O is warming up to 80 ℃ under nitrogen protection, the about 80ml of impouring, and mass concentration is 25% concentrated ammonia liquor, is cooled to room temperature behind the constant temperature 30min.Product is after magnet separates, and through the deionized water cyclic washing, vacuumize 12 hours obtains average grain diameter and be 5～20 black powder shape particle.
Embodiment 1.
Adopt device as shown in Figure 1.Comprise ammonia bottle 1, nitrogen cylinder 2, ammonia inlet 3, nitrogen inlet 4, sample solution groove 5, top pulley 6, nitrogen discharge mouth 7, closed container 8, stainless steel strip 9, division board 10, below pulley 11, sample feeder 12, ammonia emission mouth 13;
Be divided into two containers up and down 8 li of closed containers by division board 10, in the container sample feeder 12 is being arranged down, pulley 11 below being equipped with one in the sample feeder, below be equipped with one in the upper container above the pulley above pulley 6, top pulley 6 is connected with below pulley 11 usefulness one stainless steel strip 9, and stainless steel band is by the pulley driven rotary; One sample solution tank 5 is fixed on the pulley 6 of top;
Have ammonia emission mouth 13 on the sidewall of the bottom of closed container 8, top has nitrogen discharge mouth 7; Have ammonia inlet 3 and nitrogen inlet 4 on another upper portion side wall, the ammonia inlet communicates with ammonia bottle 1 by pipeline, and nitrogen inlet communicates with nitrogen cylinder 2 by pipeline.
(1) under the nitrogen protection, in the 200ml absolute ethyl alcohol, adds 10.0gFeCl
3.6H
2O and 3.7gFeCl
2.4H
2O preparation reactant alcoholic solution guarantees Fe
3+With Fe
2+Mol ratio be 2: 1.
(2) in closed container 8, feed the nitrogen that provides by nitrogen cylinder 2, get rid of the oxygen in the closed container; The reactant mixed liquor of step (1) is placed being fixed on the solution tank 5 on the pulley 6 of top of closed container, and hierarchy of control temperature is 45 ℃; Smooth stainless steel band 9 is opened the solution tank switch by the pulley driven rotary, and reactant solution becomes solution layer in stainless steel band upper berth spread.Stainless steel band upper berth spread becomes solution layer by between solution tank outlet and stainless steel band being 10-7～10-4mm apart from control thickness;
(3) logical ammonia (being provided by ammonia bottle 1) in the closed container in step (2), the reactant reaction in the solution layer on the stainless steel band of ammonia and rotation generates the Fe of black
3O
4Particle;
(4) Fe that obtains on the stainless steel band that step (3) is rotated
3O
4Particle is taken in the sample feeder 12 by stainless steel band, with ethanol solution wash-out Fe
3O
4Particle; Fe
3O
4Particle is through absolute ethanol washing, and vacuumize is to constant weight, and particle is spherical in shape, and particle size range is 3～20nm.
Claims (5)
1. the method for a making magnetic nano particle based on solution co-deposition is characterized in that, this method may further comprise the steps:
(1) under the nitrogen protection, the alcoholic solution of preparation iron chloride and the alcoholic solution of frerrous chloride; The alcoholic solution of iron chloride is mixed Fe in the mixed liquor with the alcoholic solution of frerrous chloride
3+With Fe
2+Mol ratio be 2: 1;
(2) in closed container, feed nitrogen, get rid of the oxygen in the closed container; The reactant mixed liquor of step (1) is placed closed container, and hierarchy of control temperature is 25～75 ℃; Reactant mixed liquor with step (1) is coated on the smooth stainless steel band that rotates then, makes the reactant mixed liquor become solution layer in stainless steel band upper berth spread;
(3) logical ammonia in the closed container in step (2), the reactant reaction in the solution layer on the stainless steel band of ammonia and rotation generates the Fe of black
3O
4Particle;
(4) Fe that obtains on the stainless steel band that step (3) is rotated
3O
4Particle is collected in the groove, with ethanol solution wash-out Fe
3O
4Particle; Fe
3O
4Particle is through absolute ethanol washing, and vacuumize is to constant weight.
2. method according to claim 1 is characterized in that: the mass percent concentration of the alcoholic solution of the described iron chloride of step (1) is 1%～15%, and the mass percent concentration of the alcoholic solution of frerrous chloride is 0.5%～6%.
3. method according to claim 1 and 2 is characterized in that: described alcohol is absolute ethyl alcohol.
4. method according to claim 1 is characterized in that: step (2) is described, and to become the thickness of solution layer in stainless steel band upper berth spread be 10
-7～10
-4Mm.
5. method according to claim 1 is characterized in that: the described Fe that obtains
3O
4Particle is spherical in shape, and particle size range is 3～20nm.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830691A (en) * | 2009-03-13 | 2010-09-15 | 中国科学院福建物质结构研究所 | Method for synthesizing nano ferrite soft magnetic material |
| CN101935069A (en) * | 2010-09-10 | 2011-01-05 | 西北师范大学 | Method for ultrasonically preparing Fe3O4 nano-particle through ammonia dispersion |
| CN102211930A (en) * | 2011-05-12 | 2011-10-12 | 上海电力学院 | Preparation method of nano crystal MnZn ferrite with high saturation magnetization intensity |
| CN102850599A (en) * | 2012-09-18 | 2013-01-02 | 厦门大学 | Magnetic chitosan/nano Fe3O4 composite and preparation method and application thereof |
| CN103086706A (en) * | 2013-01-16 | 2013-05-08 | 陕西科技大学 | Preparation method for Zr-Mn-Co multi-doped barium ferrite wave-absorbing material |
| CN103112903A (en) * | 2013-02-01 | 2013-05-22 | 西北师范大学 | Preparation method of hydrophobic material with surface modified by Fe3O4 nanoflower |
| CN104876281A (en) * | 2015-06-10 | 2015-09-02 | 郭秋丰 | Production method for preparing iron oxide black by ferrous ammonia oxidizing method |
| CN110156090A (en) * | 2019-06-28 | 2019-08-23 | 中国科学院合肥物质科学研究院 | One kind being used to prepare Fe3O4The fluid of magnetic nanoparticle is synthetically prepared device and its control method |
| CN111592047A (en) * | 2020-05-27 | 2020-08-28 | 东南大学 | Fluid method for continuously preparing iron oxide nanoparticles |
Family Cites Families (4)
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| JP4284984B2 (en) * | 2002-12-03 | 2009-06-24 | Ｎｏｋ株式会社 | Production method of magnetic fluid |
| CN1168665C (en) * | 2002-12-24 | 2004-09-29 | 华中科技大学 | Prepn process of nanometer granular Fe3O4 |
| CN1195305C (en) * | 2003-08-13 | 2005-03-30 | 武汉理工大学 | High specific saturated magnetizing strengh Fe3O4 micro particles and its preparing method |
| CN1803634A (en) * | 2006-01-23 | 2006-07-19 | 浙江大学宁波理工学院 | Method for preparing nanometer porous magnetic composite ferroferric oxide material |
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2006
- 2006-10-23 CN CNB2006101139746A patent/CN100487831C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830691A (en) * | 2009-03-13 | 2010-09-15 | 中国科学院福建物质结构研究所 | Method for synthesizing nano ferrite soft magnetic material |
| CN101935069A (en) * | 2010-09-10 | 2011-01-05 | 西北师范大学 | Method for ultrasonically preparing Fe3O4 nano-particle through ammonia dispersion |
| CN102211930A (en) * | 2011-05-12 | 2011-10-12 | 上海电力学院 | Preparation method of nano crystal MnZn ferrite with high saturation magnetization intensity |
| CN102850599A (en) * | 2012-09-18 | 2013-01-02 | 厦门大学 | Magnetic chitosan/nano Fe3O4 composite and preparation method and application thereof |
| CN103086706B (en) * | 2013-01-16 | 2014-07-02 | 陕西科技大学 | Preparation method for Zr-Mn-Co multi-doped barium ferrite wave-absorbing material |
| CN103086706A (en) * | 2013-01-16 | 2013-05-08 | 陕西科技大学 | Preparation method for Zr-Mn-Co multi-doped barium ferrite wave-absorbing material |
| CN103112903A (en) * | 2013-02-01 | 2013-05-22 | 西北师范大学 | Preparation method of hydrophobic material with surface modified by Fe3O4 nanoflower |
| CN103112903B (en) * | 2013-02-01 | 2015-01-07 | 西北师范大学 | Preparation method of hydrophobic material with surface modified by Fe3O4 nanoflower |
| CN104876281A (en) * | 2015-06-10 | 2015-09-02 | 郭秋丰 | Production method for preparing iron oxide black by ferrous ammonia oxidizing method |
| CN110156090A (en) * | 2019-06-28 | 2019-08-23 | 中国科学院合肥物质科学研究院 | One kind being used to prepare Fe3O4The fluid of magnetic nanoparticle is synthetically prepared device and its control method |
| CN110156090B (en) * | 2019-06-28 | 2021-08-10 | 中国科学院合肥物质科学研究院 | For preparing Fe3O4Fluid synthesis preparation device of magnetic nanoparticles and control method thereof |
| CN111592047A (en) * | 2020-05-27 | 2020-08-28 | 东南大学 | Fluid method for continuously preparing iron oxide nanoparticles |
| CN111592047B (en) * | 2020-05-27 | 2022-03-11 | 东南大学 | Fluid method for continuously preparing iron oxide nanoparticles |
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| CN100487831C (en) | 2009-05-13 |
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