CN113299475B - Water-based magnetofluid and in-situ growth preparation method and application thereof - Google Patents
Water-based magnetofluid and in-situ growth preparation method and application thereof Download PDFInfo
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- CN113299475B CN113299475B CN202110599209.4A CN202110599209A CN113299475B CN 113299475 B CN113299475 B CN 113299475B CN 202110599209 A CN202110599209 A CN 202110599209A CN 113299475 B CN113299475 B CN 113299475B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/481—Treatment of water, waste water, or sewage with magnetic or electric fields using permanent magnets
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/484—Treatment of water, waste water, or sewage with magnetic or electric fields using electromagnets
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- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/44—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of magnetic liquids, e.g. ferrofluids
- H01F1/445—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of magnetic liquids, e.g. ferrofluids the magnetic component being a compound, e.g. Fe3O4
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/006—Radioactive compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a water-based magnetic fluid and an in-situ growth preparation method and application thereof, belonging to the field of magnetic nano materials. Magnetic nano particles grow in situ in a solution containing polyethyleneimine, and the magnetic nano particles are subjected to ultracentrifugation cleaning and deionized water resuspension to prepare the magnetic fluid. The prepared magnetic fluid has the characteristics of uniform particle size, strong electropositivity, high amino content and the like. The magnetic fluid prepared by the invention has higher amino content and stronger electropositivity, so that enough space repulsive force can be provided between adjacent magnetic nanoparticles to prevent aggregation and form a stable magnetic fluid state. The magnetic fluid prepared by the invention can adjust the stability by adding alkali liquor, and can be completely recovered by an external magnetic field, thereby reducing the requirement of an external magnetic field and being widely applied to the fields of sewage treatment, biomedicine and the like.
Description
Technical Field
The invention belongs to the field of magnetic nano materials, and particularly relates to a water-based magnetic fluid and an in-situ growth preparation method and application thereof.
Background
The magnetic fluid is also called magnetic liquid, and is a two-phase colloidal solution formed by magnetic particles, a surfactant and a carrier liquid. The magnetic fluid has good fluidity and superparamagnetism, so the magnetic fluid has wide application in the fields of medical treatment, environmental protection, machinery, transportation and the like.
The magnetic particles as the important component of the magnetic fluid determine the magnetic performance of the magnetic fluid, and the carrier liquid as the main component of the magnetic fluid determines the application scenario of the magnetic fluid. In the conventional magnetic fluid, the magnetic particles are generally metal oxides, ferrites, ferromagnetic iron nitrides, metals, and the like. According to different application scenes of the magnetic fluid, the magnetic fluid can be divided into two categories of water-based magnetic fluid and oil-based magnetic fluid, and the carrier liquid is usually hydrocarbon, silicone oil, kerosene, water and polyphenylene ether.
In water-based magnetofluids, it is more common to use Fe3O4The preparation method of the nano-particles used as magnetic particles can be mainly divided into two main categories, namely a solid phase method and a liquid phase method. The solid phase method mainly includes a plasma method, a ball milling method, a thermal decomposition method, and the like. The plasma method is characterized in that an anode is an iron block, electric arc between electrodes generates high temperature, the iron block of the anode is ionized and is combined with particles formed by ionization in an air medium to form plasma, and simultaneously, redox reaction is generated to generate Fe3O4Nanoparticles. The ball milling method is to mix Fe of micron grade3O4Adding the granules into a ball mill, and grinding the granules for a long time by medium balls to obtain larger-granule Fe3O4Mechanically crushed into nano-scale particles. The thermal decomposition method generally uses ferric oxalate as raw material, in the heating process, the ferric oxalate is partially converted into ferrous oxalate, and the ferric oxalate and the ferrous oxalate are successively decomposed to generate Fe3O4Nanoparticles. Liquid phase methods are mainly classified into precipitation methods, hydrothermal methods, solvothermal methods, sol-gel methods, and the like. Wherein the precipitation method refers to that a precipitator is used for precipitating Fe in a solution2+And Fe3+Precipitating according to the molar ratio of 1:2, and washing, drying and other processes to obtain nano-grade Fe3O4And (3) granules. The precipitation method can be further classified into a coprecipitation method, an oxidation precipitation method and a reduction precipitation method. The coprecipitation method is to add Fe with a molar ratio of 1:2 directly into the solution2+And Fe3+Then adding precipitant to react Fe2+And Fe3+And precipitating out. The oxidation precipitation method is that firstly the ferrous salt solution is precipitated by using precipitant to form ferrous hydroxide, then the ferrous hydroxide is added with oxidant to be oxidized to generate Fe3O4. The reduction precipitation method is to make part of Fe in iron salt solution3+Reduction of iron to Fe2+Adding precipitant to generate Fe3O4. The hydrothermal method is to mix Fe2+And Fe3+According to the following steps of 1:2, adding alkali liquor to adjust the pH, transferring the reaction system into a high-pressure reaction kettle, reacting at a high temperature for a period of time, and separating and washing to obtain Fe3O4. Like the precipitation method, the aqua-thermal methodCan be subdivided into hydrothermal precipitation, hydrothermal oxidation and hydrothermal reduction. The solvothermal method is to replace the reaction medium in the aqua-thermic method with a non-aqueous solvent. The sol-gel method is to mix Fe2+And Fe3+According to the following steps of 1:2, adding a proper amount of organic acid, adjusting pH to form gel, removing organic residues, and performing high-temperature treatment to obtain Fe3O4. Fe prepared by the above method3O4After the nano particles are combined with the surfactant, the nano particles are dispersed in water to form the water-based magnetofluid.
However, the magnetic fluid prepared by the above method has great disadvantages, such as wide particle size distribution range and uneven particle dispersion of the magnetic particles prepared by the ball milling method. The thermal decomposition method generates CO, and is not suitable for large-scale production. The sol-gel method has harsh preparation conditions, is not easy to control, and has long treatment time. Simultaneously, a surfactant and Fe are adopted3O4When the nanoparticles are combined, the surfactant is not only present in Fe3O4The surface of the nanoparticles may also be present in the carrier liquid. Because the surfactant is generally alkane or organic acid, impurities or pollution can be introduced when the surfactant is applied to the fields of biomedicine, sewage treatment, magnetic separation and the like, and the application scene of the magnetic fluid is greatly limited.
The existing wastewater treatment methods are mainly divided into physical methods, coagulation methods, physical and chemical methods and the like, and the main principle and the defects are as follows:
(1) the physical method is a method for purifying sewage by physical or mechanical action, and the treatment process does not change the chemical properties of pollutants. Generally comprises operations of filtration, sedimentation, centrifugal separation and the like, and mainly aims at insoluble pollutants in a suspended state in the sewage, such as inorganic suspended particles such as sand and stones. The method is simple to operate, has small purification range and low efficiency, and is often used together with other methods.
(2) The coagulation method is to destabilize and aggregate colloidal pollutants and fine suspended matters in water under the dissociation and hydrolysis effects of a coagulant, thereby accelerating the sedimentation of particles and realizing solid-liquid separation. However, the organic flocculant can increase the water viscosity and increase the content of ammonia nitrogen, and the inorganic coagulant can introduce metal ions into the water body, has certain corrosivity and can easily cause the chromaticity of the water body to increase.
(3) The physical chemical method is a technical method for treating or recycling wastewater by using a mass transfer principle, and generally comprises an adsorption method, an ion exchange method, a membrane separation method, a stripping method, an extraction method, an evaporation method, a crystallization method and the like. The typical product comprises porous materials such as activated carbon and the like, and when the porous materials are contacted with sewage, pollutant components in the sewage can be adsorbed through intermolecular force, but the porous materials are often weak in binding force to the pollutants and easy to desorb, and most of the porous materials have the defects of low adsorption capacity, inconvenience in separation and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a water-based magnetic fluid, and an in-situ growth preparation method and application thereof, wherein the magnetic fluid is constructed by dispersing polyethyleneimine modified magnetic nanoparticles in a water base. Meanwhile, the content of polyethyleneimine modified by the magnetic nanoparticles in the magnetic fluid provided by the invention is high, and the surface of the polyethyleneimine is provided with positive charges, so that strong spatial repulsion among the magnetic nanoparticles can be achieved, and the magnetic fluid is kept stable.
According to a first aspect of the present invention, there is provided a method for in situ growth preparation of a water-based magnetic fluid, comprising the steps of:
(1) adding ferrous salt and ferric salt into a solution containing polyethyleneimine, continuously introducing non-oxidative protective gas, combining the polyethyleneimine with ferrous ions and ferric ions by electrostatic interaction force, then dropwise adding alkali liquor and heating to react the ferrous ions and ferric ions with hydroxyl to generate magnetic nanoparticles, wherein the magnetic nanoparticles are ferroferric oxide nanoparticles modified with polyethyleneimine;
(2) and (2) centrifuging the reaction system in the step (1), removing supernatant, and resuspending the black precipitate with deionized water to obtain the magnetic fluid dispersed in the water base.
Preferably, the ratio of the amount of the materials of the ferrous and ferric salts is 1 (1.5-2).
Preferably, the ratio of the amount of the polyethyleneimine substance to the amount of the iron element substance is (0.001-0.12): 1.
Preferably, the polyethyleneimine has a molecular weight of 800Da to 100 kDa.
Preferably, the rotation speed of the centrifugation in the step (2) is not lower than 30000 rpm.
According to another aspect of the invention, there is provided a water-based magnetic fluid prepared by any one of the methods described herein.
Preferably, the mass fraction of the modified polyethyleneimine on the magnetic nanoparticles in the magnetic fluid is 15% -30%; the particle size of the magnetic nanoparticles in the magnetic fluid is 80-100 nm, and the electromotive potential of the magnetic nanoparticles is 35-50 mV.
According to another aspect of the invention there is provided the use of a water-based magnetic fluid as described for the removal of contaminants capable of binding to amino groups.
Preferably, the method comprises the following steps:
(1) adding the water-based magnetic fluid into pollutants to be treated, and applying a radial magnetic field, wherein the magnetic field direction of the radial magnetic field is the horizontal direction; magnetic nano particles in the magnetic fluid are combined with pollutants to form radial chain-shaped aggregates under the action of a radial magnetic field;
(2) removing the radial magnetic field and applying an axial magnetic field, wherein the magnetic field direction of the axial magnetic field is vertical to that of the radial magnetic field; the radial chain-shaped aggregate forms an axial aggregate under the action of an axial magnetic field and is settled under the action of the magnetic field; and (4) sucking out the magnetic nano particles combined with the pollutants by using a permanent magnet to remove the pollutants.
Preferably, the contaminant is a negatively charged contaminant, a contaminant containing a heavy metal ion, or a contaminant containing a radionuclide;
preferably, the negatively charged contaminants are negatively charged dye waste water, negatively charged microalgae or negatively charged bacteria.
In general, compared with the prior art, the above technical solution conceived by the present invention has the following technical advantages:
(1) the invention modifies polyethyleneimine on the surface of magnetic nanoparticles by an in-situ growth preparation method and disperses the polyethyleneimine in water base to form magnetic fluid. More polyethyleneimine can be modified on the surfaces of the magnetic nanoparticles by adopting an in-situ growth preparation method, and the polyethyleneimine surfaces have positive charges, so that stronger spatial repulsion force can be generated among the magnetic nanoparticles, and the magnetic fluid is kept stable.
(2) Preferably, the proportion of ferrous salt and ferric salt is adjusted in the process of preparing the water-based magnetofluid by in-situ growth, compared with the prior art, the amount ratio of ferrous salt to ferric salt is adjusted from 1:2 to 1:1.5-2, because of Fe2+Is easily oxidized into Fe in the reaction process3+So adjusted to prevent Fe3+An excessive amount of impurities is produced.
(3) Compared with other magnetic nanoparticles and a magnetic fluid preparation method, the method for preparing the water-based magnetic fluid provided by the invention has the characteristics of simple preparation process, short time consumption, mild reaction conditions and the like. The prepared magnetic nanoparticles do not need to be modified by a surfactant or other ions to keep the space stability of the magnetic nanoparticles, and the surfactant cannot be remained in the carrier liquid during application. The magnetic nanoparticles in the magnetic fluid prepared by the method have higher saturation magnetization, can be completely recovered by an external magnetic field, and does not introduce secondary pollution.
(4) The magnetic fluid prepared by in-situ growth has high polyethyleneimine content and high amino content. When being applied to the sewage treatment field, the device can combine more pollutants, and has better treatment effect.
(5) The magnetic fluid prepared by the invention has higher amino content and stronger electropositivity, so that enough space repulsive force can be provided between adjacent magnetic nanoparticles to prevent aggregation, a stable magnetic fluid state is formed, the stability can be kept in a wider pH range, and the stability can be weakened by adding excessive alkali liquor to facilitate recovery.
(6) The magnetic fluid prepared by the invention can be completely recovered through an external magnetic field, and the stability of the magnetic fluid can be adjusted by adding alkali liquor, so that the requirement of the external magnetic field is reduced, and the magnetic fluid can be widely applied to the fields of sewage treatment, biomedicine and the like.
(7) The application method provided by the invention has a wider application range, and can be used for treating various pollutants which are charged with negative electricity, heavy metal particles, radioactive nuclides and the like and can be combined with amino. Meanwhile, the invention decouples the agglomeration and sedimentation behaviors in the process of removing the pollutants, and can adjust the agglomeration time according to the actual requirements, so that more particles are subjected to the agglomeration behaviors, and the aim of fully removing the pollutants in the solution is fulfilled.
Drawings
Fig. 1 is a flow chart of the water-based magnetic fluid and the preparation method thereof.
FIG. 2 is a schematic diagram of the steps of the method for removing sewage by using the water-based magnetic fluid prepared by the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The in-situ growth preparation method of the water-based magnetic fluid is characterized in that fig. 1 is a flow chart of the water-based magnetic fluid and the preparation method thereof, and the method comprises the following steps:
(1) adding ferrous salt and ferric salt into a solution containing polyethyleneimine, continuously introducing non-oxidative protection gas, combining polyethyleneimine with ferrous ions and ferric ions by electrostatic interaction force, dropwise adding alkali liquor, stirring after dropwise adding, and heating in a water bath to react the ferrous ions and the ferric ions with hydroxyl groups to generate magnetic nanoparticles, wherein the magnetic nanoparticles are ferroferric oxide nanoparticles modified with polyethyleneimine;
(2) and (3) after the reaction is finished, ultracentrifuging the treatment solution to remove supernatant, and resuspending the black substance at the bottom by using deionized water to obtain the polyethyleneimine modified magnetic fluid.
In some embodiments, the speed and time of the ultracentrifugation can be adjusted according to actual requirements, preferably the centrifugation speed is 30000rmp, and the centrifugation time is 60 min.
The invention also provides an application method of the magnetic fluid in sewage treatment, which decouples the agglomeration and sedimentation behaviors in the pollutant removal process, can adjust the agglomeration time according to actual requirements, enables more particles to have the agglomeration behaviors, and achieves the purpose of fully removing the pollutant dye in the solution. The method comprises the following steps:
(1) the water-based magnetic fluid prepared by the invention is added into the wastewater to be treated, and a radial magnetic field is applied. The magnetic nano particles and the pollutants are combined with each other to form radial chain-shaped aggregates under the action of a radial magnetic field.
(2) The state was kept standing for a while. The aggregate is used as a particle with larger relative particle size, has larger acting force on the single particle combined with the pollutant, and can enable the single particle combined with the pollutant to overcome the influence caused by Brownian motion so as to be combined with the aggregate, thereby achieving the purpose of fully removing the pollutant in the solution.
(3) The radial magnetic field is removed and an axial magnetic field is applied. The radial aggregate forms axial aggregate under the action of an axial magnetic field and is settled under the action of the magnetic field. The agglomeration time can be adjusted according to actual requirements, and the purpose of fully removing pollutants in the solution is achieved.
(4) The particles combined with the pollutants are sucked out by adopting the permanent magnet, so that the aim of removing the pollutants is fulfilled.
In some embodiments, the contaminants are negatively charged contaminants, heavy metal particles, radionuclides, and the like, which can bind to the amino group.
In some embodiments, the radial magnetic field may be generated by a permanent magnet or an electromagnet.
In some embodiments, the axial magnetic field may be generated by a permanent magnet or an electromagnet.
Example 1
The invention relates to a method for preparing magnetic fluid by in-situ growth, which comprises the following steps:
a. pouring 140mL of deionized water into a 500mL three-neck flask, introducing nitrogen, and stirring at 800rpm for 15 min; 10mL of polyethyleneimine solution (0.05g/mL) was added to a three-necked flask.
b. 0.556g of FeSO4·7H2O and 0.945g FeCl3·6H2O was placed in a three-necked flask, nitrogen was introduced, and the mixture was stirred at 800rpm for 10 min.
c. Slowly adding 10mL of ammonia water solution dropwise, continuously introducing nitrogen in the process, and stirring at 800 rpm.
d. After the dropwise addition is finished, stirring at 800rpm, and heating in water bath at 80 ℃ for 60 min;
e. and (3) after the reaction is finished, ultracentrifuging the solution for 60min by using 30000rmp, removing supernatant, and resuspending the black substance at the bottom by using deionized water to obtain the magnetic fluid formed by dispersing the polyethyleneimine modified magnetic nanoparticles in the water base.
Example 2
The application of the in-situ growth prepared magnetic fluid in treating pollutants is shown as a schematic diagram in figure 2 and comprises the following steps:
(1) adding the magnetic nano particles into the anionic dye wastewater to be treated, and applying a radial magnetic field. The polyethyleneimine contained on the magnetic nanoparticles is combined with anionic dye through electrostatic interaction, and a radial chain-like aggregate is formed under the action of a radial magnetic field.
(2) The state was kept standing for a while. The aggregate is used as a particle with larger relative particle size, has larger acting force on the single particle combined with the dye, and can enable the single particle combined with the dye to overcome the influence caused by Brownian motion and be combined with the aggregate, thereby achieving the purpose of fully removing the anionic dye in the solution.
(3) The radial magnetic field is removed and an axial magnetic field is applied. The radial aggregate forms axial aggregate under the action of an axial magnetic field and is settled under the action of the magnetic field.
(4) The particles combined with the anionic dye are separated out by adopting a permanent magnet, so that the aim of removing the anionic dye is fulfilled.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. An in-situ growth preparation method of a water-based magnetofluid is characterized by comprising the following steps:
(1) adding ferrous salt and ferric salt into a solution containing polyethyleneimine, wherein the mass ratio of the ferrous salt to the ferric salt is 1:1.5, continuously introducing non-oxidative protective gas, combining the polyethyleneimine with ferrous ions and ferric ions by electrostatic interaction force, then dropwise adding alkali liquor and heating to react the ferrous ions and ferric ions with hydroxide radicals to generate magnetic nanoparticles, wherein the magnetic nanoparticles are ferroferric oxide nanoparticles modified with polyethyleneimine;
(2) and (2) centrifuging the reaction system in the step (1), removing supernatant, and resuspending the black precipitate with deionized water to obtain the magnetic fluid dispersed in the water base.
2. The in situ growth preparation method of a water-based magnetic fluid according to claim 1, wherein the ratio of the amount of polyethyleneimine species to the amount of iron species is (0.001-0.12): 1.
3. The in situ growth preparation method of water-based magnetic fluid according to claim 1, wherein the molecular weight of the polyethyleneimine is 800Da to 100 kDa.
4. The in-situ growth preparation method of water-based magnetic fluid according to claim 1, wherein the rotation speed of the centrifugation in the step (2) is not lower than 30000 rpm.
5. A water-based magnetic fluid prepared by the method according to any one of claims 1 to 4.
6. The water-based magnetic fluid according to claim 5, wherein the mass fraction of polyethyleneimine modified on magnetic nanoparticles in the magnetic fluid is 15% -30%; the particle size of the magnetic nanoparticles in the magnetic fluid is 80-100 nm, and the electromotive potential of the magnetic nanoparticles is 35-50 mV.
7. Use of a water-based magnetic fluid according to claim 5 or 6 for removing contaminants capable of binding to amino groups.
8. Use according to claim 7, characterized in that it comprises the following steps:
(1) adding the water-based magnetic fluid into pollutants to be treated, and applying a radial magnetic field, wherein the magnetic field direction of the radial magnetic field is the horizontal direction; magnetic nano particles in the magnetic fluid are combined with pollutants to form radial chain-shaped aggregates under the action of a radial magnetic field;
(2) removing the radial magnetic field and applying an axial magnetic field, wherein the magnetic field direction of the axial magnetic field is vertical to that of the radial magnetic field; the radial chain-shaped aggregate forms an axial aggregate under the action of an axial magnetic field and is settled under the action of the magnetic field; and (4) sucking out the magnetic nano particles combined with the pollutants by using a permanent magnet to remove the pollutants.
9. The use of claim 7, wherein the contaminant is a negatively charged contaminant, a contaminant containing a heavy metal ion, or a contaminant containing a radionuclide.
10. The use of claim 9, wherein the negatively charged contaminant is negatively charged dye wastewater, negatively charged microalgae, or negatively charged bacteria.
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| CN101763930A (en) * | 2010-01-21 | 2010-06-30 | 上海大学 | Improved ferroferric oxide magnetic fluid and method for preparing same |
| CN104528837A (en) * | 2014-12-15 | 2015-04-22 | 沈阳药科大学 | Preparation method of stable nano ferroferric oxide magnetofluid |
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| CN1747078A (en) * | 2005-10-14 | 2006-03-15 | 中山大学 | Modified water-base magnetic liquid of polymer and production thereof |
| CN101593593A (en) * | 2009-04-10 | 2009-12-02 | 江苏工业学院 | Handle the preparation method of the magnetic Nano material of organic wastewater |
| CN101719407A (en) * | 2010-01-25 | 2010-06-02 | 上海交通大学 | Preparation method of water-based biological magnetic fluid |
| CN104319054A (en) * | 2014-10-11 | 2015-01-28 | 昆明理工大学 | Manometer magnetofluid and application thereof to purification of pollutants |
| CN111063502A (en) * | 2019-12-19 | 2020-04-24 | 华中科技大学 | Magnetic fluid with adjustable stability and preparation and recovery method thereof |
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