CN101763930A - Improved ferroferric oxide magnetic fluid and method for preparing same - Google Patents
Improved ferroferric oxide magnetic fluid and method for preparing same Download PDFInfo
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- CN101763930A CN101763930A CN201010023129A CN201010023129A CN101763930A CN 101763930 A CN101763930 A CN 101763930A CN 201010023129 A CN201010023129 A CN 201010023129A CN 201010023129 A CN201010023129 A CN 201010023129A CN 101763930 A CN101763930 A CN 101763930A
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Abstract
The ferroferric oxide nano magnetic fluid prepared with the method has the particle size of 8-17 nm. The ferroferric oxide particles modified by trisodium citrate have negative electricity on the surfaces, and the Zeta potential measurement shows that the potential on the surfaces of the ferroferric oxide particles is -8.6 mV to -23.9 mV. The ferroferric oxide particles modified by nitric acid have positive electricity on the surface, and the Zeta potential measurement shows that the potential on the surfaces of the ferroferric oxide particles is +6.7 mV to +18.5 mV. Compared with the prior art, because the invention adopts lower synthesis temperature, and the nitrogen protection prevent the oxidation of divalent iron salt, the prepared magnetic particles have small and even size and electricity on surfaces, can disperse stably for a long time without agglomerating and are super paramagnetic particles which can move directionally under the condition that the magnetic field exists. The method for preparing the improved ferroferric oxide magnetic fluid comprises the following steps: adjusting the pH value of solution containing trivalent iron salt and bivalent iron salt solution to 9-10 with aqueous ammonia under the nitrogen protection, stirring the aqueous ammonia to the solution to make the aqueous ammonia react with the solution at 70-100 DEG C for 1-4h, washing the product of reaction with ethanol and deionized water repeatedly until the pH value of the product of reaction being neutral, dispersing the prepared nano magnetic ferroferric oxide in the trisodium citrate solution or the nitric acid solution, and washing the product of reaction with acetone and deionized water repeatedly to obtain the ferroferric oxide nano magnetic fluid with negative electricity or positive electricity.
Description
Technical field
The present invention relates to two kinds of method modified ferriferous oxide nanometer magnetofluids and preparation method thereof.
Background technology
In recent years, ferriferrous oxide nanometer material was owing to its synthetic size with pattern is controlled and compound has extensive use and becomes focus in the magnetic Nano material research in a lot of fields.Because of a series of special performances such as its superparamagnetism, high-coercive force, low Curie temperature, the strong absorptions of broadband, has application widely at aspects such as stealthy absorbing material, magnetic recording material, magnetic refrigerating materials.Deep, interdisciplinary intersection infiltration along with research, the preparation and the research of multi-functional magnetic composite microsphere that is applied to the carried out performance design of biomedicines such as medicine release, large biological molecule separation and separation engineering association area becomes focus, and the surface nature of magnetic nano-particle and dispersity have remarkable influence to the preparation and the functionalization process of magnetic composite microsphere.
In recent years, the researcher has been developed and multiple different synthetic method, as: coprecipitation, microemulsion method, ultrasonic radiation method, hydro-thermal organo-metallic compound thermal decomposition method etc.Prepared the nanometer magnetofluid of different size, but there are problems such as severe reaction conditions, particle diameter reunion bigger than normal, easy, product be impure in the magnetic particle prepared, has limited its application at biomedicine field.The present invention adopts than low reaction temperatures, later stage modification Processing of Preparation and obtains the magnetic fluid that can stablize preservation of particle diameter about tens nanometers, has further improved the application power of magnetic fluid.
Summary of the invention
Ferriferous oxide nanometer magnetofluid that provides modification band different surfaces electric charge and preparation method thereof is provided the object of the invention.
For achieving the above object, the present invention adopts following technical scheme:
A kind of ferriferous oxide nanometer magnetofluid is characterized in that component is a tri-iron tetroxide, and the magnetic particle diameter is 8-17nm.After adopting trisodium citrate and Nitric Acid Modified tri-iron tetroxide magnetic particle respectively, can make the magnetic particle surface be with negative electrical charge and positive charge respectively, thereby make magnetic particle stable dispersion in water become the magnetic fluid of superparamagnetism, adding under the action of a magnetic field and can directedly assemble.
A kind of preparation method of modified ferriferous oxide nanometer magnetofluid is characterized in that, the concrete steps of this method are as follows:
A. the solution that 10～100mL is contained trivalent iron salt and divalent iron salt changes in the there-necked flask, adds ammoniacal liquor and regulates pH to 9-10, charges into nitrogen protection after vacuumizing, and described solubility trivalent iron salt is FeCl
36H
2O, concentration is 0.8～5.2mol/L, divalent iron salt concentration is FeSO
47H
2O, concentration is 04mol/L～26mol/L, ammonia concn is 25～28% (mass percents).
B. obtain the tri-iron tetroxide particle that particle diameter is 8-17nm after reacting 1～4 hour under the 70-100 ℃ of stirring condition, product is separated and repeatedly washs to pH with ethanol, deionized water is neutral.
C. the tri-iron tetroxide particle is added in 100～300mL, the 0.5～3mol/L citric acid three sodium solution, behind stirring at room reaction 0.5～2h, it is neutral repeatedly washing to pH with ethanol, deionized water, obtains surperficial electronegative improved ferroferric oxide magnetic fluid; Perhaps, the tri-iron tetroxide particle is added in 100-300mL, the 0.4～6mol/L salpeter solution, behind stirring at room reaction 0.5～2h, it is neutral repeatedly washing to pH with ethanol, deionized water, obtains the improved ferroferric oxide magnetic fluid of surperficial positively charged.
The ferriferous oxide nanometer magnetofluid of the present invention's preparation, particle diameter is far smaller than existing magnetic particle at 8-17nm.With the tri-iron tetroxide particle of trisodium citrate modification, its surface is electronegative, Zeta potential measure surface potential-8.6～-23.9mV.With the tri-iron tetroxide particle of Nitric Acid Modified, its surperficial positively charged, Zeta potential measure surface potential+6.7～+ 18.5mV.
Compare with prior art; because the present invention adopts lower synthesis temperature; nitrogen protection has prevented the oxidation of divalent iron salt; the magnetic particle diameter for preparing is little and even; surface charging energy long-term stability is disperseed and is not reunited; be a kind of ultra paramagnetic particle that the energy orientation moves in the presence of magnetic field, owing to its excellent performance has been widened the application of ferriferous oxide magnetic fluid at biomedicine field.
Embodiment
Embodiment 1: 0.8mol/L trivalent iron salt and 0.4mol/L divalent iron salt are dissolved in the 45mL deionized water, and trivalent iron salt is FeCl
36H
2O, divalent iron salt are FeSO
47H
2O, be transferred to there-necked flask after, vacuumize and charge into nitrogen, add 25%～28% (mass percent) ammoniacal liquor regulation system pH to 9,100 ℃ of stirring reaction 1h, unnecessary unreacted molysite ion is removed in ethanol, deionized water eccysis.
The tri-iron tetroxide that reaction is obtained is divided into two parts, and first part is scattered in 200mL, the 3mol/L citric acid three sodium solution behind the 1h, and it is neutral repeatedly washing to pH with ethanol, deionized water, obtains the magnetic fluid of surface potential for-19.0mV.Second part is scattered in 200mL, the 6mol/L salpeter solution behind the 1h, and it is neutral repeatedly washing to pH with ethanol, deionized water, obtains the magnetic fluid of surface potential for+18.5mV.The magnetic fluid particle diameter that obtains after the modification is 8nm.
Embodiment 2: 1.4mol/L trivalent iron salt and 0.7mol/L divalent iron salt are dissolved in the 60mL deionized water, and trivalent iron salt is FeCl
36H
2O, divalent iron salt are FeSO
47H
2O, be transferred to there-necked flask after, vacuumize and charge into nitrogen, add 25%～28% (mass percent) ammoniacal liquor regulation system pH to 9,90 ℃ of stirring reaction 1h, unnecessary unreacted molysite ion is removed in ethanol, deionized water eccysis.
The tri-iron tetroxide that reaction is obtained is divided into two parts, and first part is scattered in 150mL, the 2.5mol/L citric acid three sodium solution behind the 1.5h, and it is neutral repeatedly washing to pH with ethanol, deionized water, obtains the magnetic fluid of surface potential for-15.6mV.Second part is scattered in 150mL, the 3.5mol/L salpeter solution behind the 1.5h, and it is neutral repeatedly washing to pH with ethanol, deionized water, obtains the magnetic fluid of surface potential for+13.3mV.The magnetic fluid particle diameter that obtains after the modification is 11nm.
Embodiment 3: 2.6mol/L trivalent iron salt and 1.3mol/L divalent iron salt are dissolved in the 25mL deionized water, and trivalent iron salt is FeCl
36H
2O, divalent iron salt are FeSO
47H
2O, be transferred to there-necked flask after, vacuumize and charge into nitrogen, add 25%～28% (mass percent) ammoniacal liquor regulation system pH to 9,95 ℃ of stirring reaction 1.5h, unnecessary unreacted molysite ion is removed in ethanol, deionized water eccysis.
The tri-iron tetroxide that reaction is obtained is divided into two parts, and first part is scattered in 300mL, the 2mol/L citric acid three sodium solution behind the 2h, and it is neutral repeatedly washing to pH with ethanol, deionized water, obtains the magnetic fluid of surface potential for-23.9mV.Second part is scattered in 300mL, the 4mol/L salpeter solution behind the 2h, and it is neutral repeatedly washing to pH with ethanol, deionized water, obtains the magnetic fluid of surface potential for+17.1mV.The magnetic fluid particle diameter that obtains after the modification is 12nm.
Embodiment 4: 4.0mol/L trivalent iron salt and 2.0mol/L divalent iron salt are dissolved in the 100mL deionized water, and trivalent iron salt is FeCl
36H
2O, divalent iron salt are FeSO
47H
2O, be transferred to there-necked flask after, vacuumize and charge into nitrogen, add 25%～28% (mass percent) ammoniacal liquor regulation system pH to 9,85 ℃ of stirring reaction 3h, unnecessary unreacted molysite ion is removed in ethanol, deionized water eccysis.
The tri-iron tetroxide that reaction is obtained is divided into two parts, and first part is scattered in 100mL, the 0.5mol/L citric acid three sodium solution behind the 0.5h, and it is neutral repeatedly washing to pH with ethanol, deionized water, obtains the magnetic fluid of surface potential for-8.6mV.Second part is scattered in 100mL, the 1.5mol/L salpeter solution behind the 0.5h, and it is neutral repeatedly washing to pH with ethanol, deionized water, obtains the magnetic fluid of surface potential for+9.7mV.The magnetic fluid particle diameter that obtains after the modification is 15nm.
Embodiment 5: 5.2mol/L trivalent iron salt and 2.6mol/L divalent iron salt are dissolved in the 80mL deionized water, and trivalent iron salt is FeCl
36H
2O, divalent iron salt are FeSO
47H
2O, be transferred to there-necked flask after, vacuumize and charge into nitrogen, add 25%～28% (mass percent) ammoniacal liquor regulation system pH to 9,70 ℃ of stirring reaction 4h, unnecessary unreacted molysite ion is removed in ethanol, deionized water eccysis.
The tri-iron tetroxide that reaction is obtained is divided into two parts, and first part is scattered in 150mL, the 1.0mol/L citric acid three sodium solution behind the 1h, and it is neutral repeatedly washing to pH with ethanol, deionized water, obtains the magnetic fluid of surface potential for-9.0mV.Second part is scattered in 100mL, the 0.4mol/L salpeter solution behind the 1h, and it is neutral repeatedly washing to pH with ethanol, deionized water, obtains the magnetic fluid of surface potential for+6.7mV.The magnetic fluid particle diameter that obtains after the modification is 17nm.
Claims (2)
1. improved ferroferric oxide magnetic fluid, it is characterized in that this magnetic fluid is magnetic particle stable dispersion in water, the component of magnetic particle is a tri-iron tetroxide, the magnetic particle diameter is 8～17nm, adopt trisodium citrate or Nitric Acid Modified tri-iron tetroxide magnetic particle respectively, after the modification, the magnetic particle surface is with negative electrical charge or positive charge respectively.
2. preparation method who is used for the described improved ferroferric oxide magnetic fluid of claim 1 is characterized in that the concrete steps of this method are as follows:
A. the solution that 10～100mL is contained trivalent iron salt and divalent iron salt changes in the there-necked flask, adds ammoniacal liquor and regulates pH to 9～10, charges into nitrogen protection after vacuumizing, and described trivalent iron salt is FeCl
36H
2O, concentration is 0.8～5.2mol/L, divalent iron salt is FeSO
47H
2O, concentration is 0.4～2.6mol/L, the mass percentage concentration of ammoniacal liquor is 25～28%;
B. obtain the tri-iron tetroxide particle that particle diameter is 8～17nm after reacting 1～4 hour under 70～100 ℃ of stirring condition, product is separated and repeatedly washs to pH with ethanol, deionized water is neutral;
C. the tri-iron tetroxide particle is added in 100～300mL, the 0.05～3mol/L citric acid three sodium solution, behind stirring at room reaction 0.5～2h, it is neutral repeatedly washing to pH with ethanol, deionized water, obtains surperficial electronegative improved ferroferric oxide magnetic fluid; Perhaps, the tri-iron tetroxide particle is added in 100～300mL, the 0.4～6mol/L salpeter solution, behind stirring at room reaction 0.5～2h, it is neutral repeatedly washing to pH with ethanol, deionized water, obtains the improved ferroferric oxide magnetic fluid of surperficial positively charged.
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| CN104445437A (en) * | 2014-12-08 | 2015-03-25 | 上海应用技术学院 | Preparation method of ferriferrous oxide magnetic nanoparticles |
| CN105597757A (en) * | 2015-12-23 | 2016-05-25 | 北京林业大学 | Magnetic graphene oxide catalyst as well as preparation method and application thereof |
| CN108893460A (en) * | 2018-06-29 | 2018-11-27 | 华侨大学 | A kind of method of the quick immobilized cell of magnetically fixed bed |
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2010
- 2010-01-21 CN CN201010023129A patent/CN101763930A/en active Pending
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| CN104445437B (en) * | 2014-12-08 | 2016-09-14 | 上海应用技术学院 | A kind of preparation method of ferroferric oxide magnetic nano-particles |
| CN104445437A (en) * | 2014-12-08 | 2015-03-25 | 上海应用技术学院 | Preparation method of ferriferrous oxide magnetic nanoparticles |
| CN105597757A (en) * | 2015-12-23 | 2016-05-25 | 北京林业大学 | Magnetic graphene oxide catalyst as well as preparation method and application thereof |
| CN105597757B (en) * | 2015-12-23 | 2018-01-02 | 北京林业大学 | Magnetic oxygenated graphen catalyst and preparation method thereof and its application |
| CN110454132B (en) * | 2018-05-08 | 2021-12-31 | 中国石油大学(华东) | Nano magnetofluid fracturing fluid imbibition oil increasing method for tight reservoir and modified nano magnetic particles |
| CN110454132A (en) * | 2018-05-08 | 2019-11-15 | 中国石油大学(华东) | A kind of compact reservoir nanometer magnetofluid fracturing fluid imbibition increases oily method and modified nanometer magnetic particle |
| CN108893460A (en) * | 2018-06-29 | 2018-11-27 | 华侨大学 | A kind of method of the quick immobilized cell of magnetically fixed bed |
| CN108950877A (en) * | 2018-08-23 | 2018-12-07 | 中玺（天津）枣业技术工程中心 | Pathogenic bacteria trapping filtering antibacterial membrane preparation method |
| CN109392904A (en) * | 2018-12-03 | 2019-03-01 | 黄美红 | A kind of efficiently quickly disintegrated cell member herbicide |
| CN112309669A (en) * | 2019-07-31 | 2021-02-02 | 北京化工大学 | Preparation method of water-based nano magnetic fluid |
| CN112309669B (en) * | 2019-07-31 | 2024-06-07 | 北京化工大学 | Preparation method of water-based nano magnetic fluid |
| CN111285507A (en) * | 2020-03-30 | 2020-06-16 | 上海氯德新材料科技有限公司 | Waste residue and waste water reutilization method and device for chlor-alkali plant |
| CN112390453A (en) * | 2020-11-25 | 2021-02-23 | 上海交通大学 | Modified magnetic Fe3O4Powder, method for the production thereof and use thereof |
| CN112390453B (en) * | 2020-11-25 | 2022-02-01 | 上海交通大学 | Modified magnetic Fe3O4Powder, method for the production thereof and use thereof |
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Open date: 20100630 |