CN116913639A - Preparation method of nonpolar solvent-based magnetic fluid with high stability - Google Patents
Preparation method of nonpolar solvent-based magnetic fluid with high stability Download PDFInfo
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- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 13
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
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- 238000005406 washing Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910001447 ferric ion Inorganic materials 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- 239000013067 intermediate product Substances 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
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- 239000005639 Lauric acid Substances 0.000 claims description 2
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- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
-
- 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
Abstract
The invention relates to a preparation method of nonpolar solvent-based magnetic fluid with high stability, and belongs to the technical field of magnetic fluid preparation. Compared with the traditional separation and purification methods such as ultracentrifugation and drying, the method fully utilizes the influence of a third-party solvent on a particle dispersion system after preparing the highly dispersed magnetic nanoparticles modified by a high-molecular compound with long-chain groups, guides the particles to moderately agglomerate to perform magnetic separation and cleaning to remove product impurities, and prepares the magnetic fluid formed by highly dispersing the magnetic nanoparticles in a carrier liquid through a phase transfer and phase separation strategy under the condition of removing an agglomeration induction factor. The method has the advantages of simple operation, low cost, no need of precise instruments, strong product stability, high purity, adjustable concentration and wide application prospect.
Description
Technical Field
The invention belongs to the technical field of magnetic fluid preparation, and particularly relates to a preparation method of nonpolar solvent-based magnetic fluid with high stability.
Background
Magnetic fluid, also called ferrofluid, generally refers to a colloidal solution formed by dispersing magnetic nanoparticles in a carrier liquid. As a special liquid functional composite material, the magnetic fluid has both the magnetic property of the magnetic material and the fluid property of the liquid material, and also has a plurality of unique physicochemical properties under the action of an externally applied magnetic field, thereby having wide application prospects in the fields of scientific researches and engineering application.
Because of strong interaction such as magnetic dipole interaction and Van der Waals force among the magnetic nano particles, the magnetic nano particles dispersed in the carrier liquid tend to be agglomerated, are easy to settle under the action of gravity and magnetic force, and further precipitate the carrier liquid. Therefore, the key to preparing high performance magnetic fluids is how to properly modify the magnetic particle surface to improve its stability in the carrier liquid. The macromolecular compound with long chain groups, such as oleic acid, can prevent aggregation of magnetic nanoparticles by introducing steric repulsion between the magnetic nanoparticles through the steric hindrance effect between the groups, and is often used as a surface modifier of the magnetic nanoparticles in magnetic fluid.
The specific preparation method of the magnetic fluid comprises the following steps. In 1965, NASA engineer S.S.Papell developed ball milling to prepare magnetic fluid for the first time. Adding magnetic particles, a surfactant and a carrier liquid into a ball mill together, performing ball milling for a long time (1 to 3 months), and centrifuging to remove large particles to obtain the magnetic fluid. However, this method is very time-consuming and laborious and the product stability is poor. Chinese patent (CN 110277235B) discloses a method for preparing a ferroferric oxide fluid, comprising: a. mixing the raw materials: feCl is added 2 ·4H 2 O and FeCl 3 ·6H 2 Mixing O in a reaction device, adding quantitative water and mixing the mixed solution, filtering the mixed solution, and removing impurities in the solution; b. the reaction proceeds: adding ammonia water into the mixed solution to generate Fe in the solution 3 O 4 Adding ammonia water continuously into the colloidal particle until Fe 3 O 4 No longer generates, and stops introducing ammonia water; c. heating: to Fe 3 O 4 Adding activator oleic acid and base liquid kerosene into the colloid, and heating the mixture to remove excessive ammonia water; d. taking: standing the solution for a certain time to make the solution delaminateThe phenomenon that the lower water layer is pumped away, and then the upper Fe layer is treated 3 O 4 Is collected. The method is simple and convenient to operate, but because the oleic acid has smaller density and is difficult to dissolve in water, the oleic acid is difficult to fully react with magnetic nano particles in a water phase, a large amount of raw materials are wasted, the product stability is poor, particles are easy to separate out, and the oleic acid contains unreacted oleic acid molecules and other impurities.
Disclosure of Invention
Aiming at the defects or improvement demands of the prior art, the invention aims to provide a preparation method of nonpolar solvent-based magnetic fluid with strong stability and high purity. Firstly, a macromolecular compound with long chain groups is added as a surface modifier in the process of synthesizing the magnetic nano particles by a coprecipitation method, and stirring and ultrasonic are carried out to promote the coupling of the modifier and the magnetic nano particles and the dispersion of the modified magnetic nano particles, so that the highly dispersed oleic acid modified magnetic nano particles are obtained. In the leading-edge scientific research, there are also many cases of preparing highly dispersed magnetic nanoparticles using pyrolysis method or the like. However, the method has higher experimental condition requirements, smaller yield and difficulty in meeting application requirements. Most importantly, the particles with stronger dispersibility are difficult to separate and purify, and especially the repulsive force of the particle surface modifier before each other further aggravates the separation difficulty. In the conventional method, researchers often separate and clean the materials by using an ultracentrifugation method. However, the method has high requirements on instruments and equipment, long separation time and low efficiency, and is difficult to be applied to large-scale industrial production. Researchers also often dry the harvested particles to remove the solvent contained therein and dissolve them into the desired carrier liquid. However, the drying process causes the particles to adhere and impairs the dispersibility of the particles.
In this case, the present invention adds a solvent compatible with the magnetic nanoparticle product solution but incompatible with the polymer compound having long chain groups modified on the surface thereof to promote the agglomeration of the magnetic nanoparticles, and further can clean and purify the magnetic nanoparticles by magnetic separation. Then, the invention adds in solvent which can be compatible with the solvent for guiding agglomeration and incompatible with the macromolecule compound modified on the surface of the magnetic nanometer particle, and then removes the solvent for guiding agglomeration through magnetic separation and cleaning. Finally, nonpolar carrier liquid compatible with the macromolecular compound modified on the surface of the magnetic nano particles is added, and ultrasonic and stirring are carried out, so that microemulsion can be formed, and phase transfer of the magnetic nano particles and dispersion of the magnetic nano particles in the carrier liquid are promoted. After the phase transfer is completed, a demulsifier is added into the microemulsion, so that the magnetic fluid formed by highly dispersing the magnetic nanoparticles modified by the high molecular compound with long chain groups in the carrier liquid can be promoted to be separated from other solvents, and the magnetic fluid can be obtained after the other solvents are simply removed.
According to a first aspect of the present invention there is provided a method of preparing a non-polar solvent-based magnetic fluid comprising the steps of:
(1) Preparing dispersed magnetic nano particles modified by a high molecular compound with long chain groups, wherein the number of carbon atoms of the long chain groups is more than or equal to 12;
(2) Adding a solvent which is compatible with the magnetic nanoparticle carrier liquid modified by the macromolecular compound and incompatible with the macromolecular compound modified by the surface of the magnetic nanoparticle carrier liquid to the dispersed magnetic nanoparticle obtained in the step (1) so as to promote the agglomeration of the magnetic nanoparticle, and then cleaning and purifying through magnetic separation;
(3) Adding a solvent which is compatible with the solvent for guiding agglomeration and incompatible with the macromolecular compound modified on the surface of the magnetic nano particles into the intermediate product obtained in the step (2), and removing the solvent for guiding agglomeration through magnetic separation and cleaning;
(4) Adding nonpolar carrier liquid compatible with the macromolecular compound modified on the surface of the magnetic nano particles into the intermediate product obtained in the step (3), and performing ultrasonic treatment and stirring to form microemulsion so as to promote the phase transfer of the magnetic nano particles and the dispersion of the magnetic nano particles in the nonpolar carrier liquid;
(5) And (3) adding a demulsifier which can be dissolved in the nonpolar carrier liquid added in the step (3) into the microemulsion obtained in the step (4) to promote the phase separation of the magnetic fluid formed by dispersing the magnetic nanoparticles modified by the high molecular compound in the carrier liquid, thus obtaining the nonpolar solvent-based magnetic fluid.
Preferably, the polymer compound having a long chain group in the step (1) may be oleic acid or lauric acid.
Preferably, the magnetic nanoparticle in the step (1) may be Fe 3 O 4 Nanoparticles or MFe 2 O 4 Nanoparticles wherein M is Ni, co, mn or Zn.
Preferably, the magnetic nanoparticle modified by the polymer compound having long chain groups dispersed in the step (1) is prepared by the following method: in a nitrogen environment, adding ferric salt and ferrous salt into water, starting stirring, dissolving into a mixed solution of ferrous ions and ferric ions, dropwise adding ammonia water, and reacting to obtain ferroferric oxide nano particles; adding oleic acid, and starting ultrasonic to promote coupling of the oleic acid and the magnetic nanoparticles and dispersion of the modified magnetic nanoparticles, so as to obtain dispersed oleic acid modified magnetic nanoparticles;
preferably, the ratio of the amount of ferrous ions to ferric ions in the mixed solution is 0.5-2, the stirring speed is 100-3000 rpm, and the stirring and ultrasonic treatment time is 0.5-10 h.
Preferably, in the step (2), the solvent that is compatible with the magnetic nanoparticle carrier liquid modified by the polymer compound and incompatible with the polymer compound modified by the surface of the magnetic nanoparticle carrier liquid is ethanol, methanol or acetone.
Preferably, in the step (2), the volume ratio of the added solvent to the magnetic nanoparticles prepared in the step (1) is 0.1-10.
Preferably, in the step (3), the solvent compatible with the agglomeration-guiding solvent and incompatible with the polymer compound surface-modified with the magnetic nanoparticle is water.
Preferably, in the step (4), the nonpolar carrier liquid compatible with the macromolecular compound modified on the surface of the magnetic nanoparticle is kerosene, cyclohexane or n-hexane.
Preferably, in the step (4), the volume ratio of the added nonpolar carrier liquid to the magnetic nanoparticle suspension after the washing in the step (3) is 0.1-100.
Preferably, in the step (5), the demulsifier is ferric chloride solution, magnesium chloride solution or ferrous sulfate solution;
preferably, the concentration of the demulsifier is 0.1 to 100 moles per liter.
Preferably, the volume ratio of the demulsifier in the step (5) to the microemulsion formed in the step (4) is 0.1-100.
In general, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
(1) The invention comprises a preparation method of highly dispersed magnetic nanoparticles, namely, the surface modifier is used for fully modifying the magnetic nanoparticles after nucleation by a coprecipitation method so as to promote the highly dispersed magnetic nanoparticles and inhibit agglomeration of the magnetic nanoparticles.
(2) Compared with the traditional separation and purification methods such as ultracentrifugation and drying, the method utilizes the influence of the third-party solvent on the particle dispersion system, firstly guides the moderate agglomeration of particles to perform magnetic separation and cleaning to remove product impurities, and then prepares the magnetic fluid through phase transfer and phase separation strategies under the condition of removing agglomeration induction factors. The method is simple to operate, low in cost, free of precise instruments, strong in product stability, high in purity and adjustable in concentration, and can play an important role in various application scenes.
(3) The magnetic fluid prepared by the preparation method provided by the invention can adjust the concentration according to the actual application requirements, and can meet different application scenes. Firstly, the volume ratio of the oleic acid modified magnetic nanoparticle aqueous solution to the oily carrier liquid can be flexibly adjusted during preparation, and the concentration is adjustable during preparation; second, after the preparation is completed, the concentration thereof can be adjusted by increasing the amount of the oily carrier liquid.
Drawings
FIG. 1 is a flow chart of a method for preparing nonpolar solvent-based magnetic fluid with high stability and high purity.
Fig. 2 is a photograph of a non-polar solvent-based magnetic fluid with high stability and purity in deionized water, which is prepared in example 1 of the present invention, controlled by a permanent magnet.
FIG. 3 shows the results of particle size analysis of a magnetic solid material in a highly stable, highly pure, nonpolar solvent-based magnetic fluid prepared in example 1 of the present invention.
FIG. 4 shows the results of thermogravimetric analysis of a magnetic solid material in a highly stable, highly pure, nonpolar solvent-based magnetic fluid prepared in example 1 of the present invention.
FIG. 5 shows the magnetic test results of a magnetic solid material in a highly stable, highly pure, nonpolar solvent-based magnetic fluid prepared in example 1 of the present invention.
FIG. 6 is a Fourier infrared spectrum of a magnetic solid material in a nonpolar solvent-based magnetic fluid with high stability and high purity prepared in example 1 of the present invention.
FIG. 7 is an X-ray diffraction spectrum of a magnetic solid material in a nonpolar solvent-based magnetic fluid with high stability and high purity prepared in example 1 of the present invention.
FIG. 8 is the stability test data of a highly stable, highly pure nonpolar solvent-based magnetic fluid prepared in example 1 of the present invention.
FIG. 9 is a Fourier infrared spectrum of a magnetic solid material in a nonpolar solvent-based magnetic fluid with high stability and high purity prepared in example 2 of the present invention.
FIG. 10 is an X-ray diffraction spectrum of a magnetic solid material in a nonpolar solvent-based magnetic fluid with high stability and high purity prepared in example 2 of the present invention.
FIG. 11 is the stability test data of a highly stable, highly pure nonpolar solvent-based magnetic fluid prepared in example 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The invention relates to a preparation method of nonpolar solvent-based magnetic fluid with strong stability, and fig. 1 is a flow chart of the preparation method, and the preparation method comprises the following steps:
(1) Preparing highly dispersed magnetic nano particles modified by high molecular compounds with long chain groups (the number of carbon atoms is more than or equal to 12);
(2) Adding a solvent which is compatible with the carrier liquid and incompatible with the high molecular compound with long chain groups modified on the surface of the carrier liquid into the product obtained in the step (1) to promote the agglomeration of the magnetic nano particles, and further cleaning and purifying the magnetic nano particles through magnetic separation;
(3) Adding a solvent which is compatible with the solvent for guiding agglomeration and incompatible with the macromolecular compound modified on the surface of the magnetic nano particles into the product obtained in the step (2), and removing the solvent for guiding agglomeration through magnetic separation and cleaning;
(4) Adding nonpolar carrier liquid compatible with the macromolecular compound modified on the surface of the magnetic nano particles into the product obtained in the step (3), and carrying out ultrasonic treatment and stirring to form microemulsion, so as to promote the phase transfer of the magnetic nano particles and the dispersion of the magnetic nano particles in the carrier liquid;
(5) And (3) adding a demulsifier dissolved in the solvent added in the step (3) into the product obtained in the step (4) to promote the phase separation of the magnetic fluid formed by highly dispersing the magnetic nanoparticles modified by the high molecular compound with long chain groups in the carrier liquid and other solvents, and simply removing the other solvents to obtain the magnetic fluid.
In some embodiments, step (1) comprises adding ferric ion salt and ferrous ion salt into ultrapure water, and continuously stirring to prepare a mixed solution with the concentration of the ferrous ion and the ferric ion of 0.1-10 mol/L, wherein the mol ratio of the ferrous ion and the ferric ion is 0.5-2; then dropwise adding ammonia water, wherein the molar ratio of the ammonia water to ferrous ions is 5-100; after the dripping is finished, turning on ultrasound, and then dropwise adding oleic acid, wherein the mol ratio of the oleic acid to ferrous ions is 5-100, and the volume ratio of the oleic acid to ammonia water is 0.1-10; after the dripping is finished, stirring and ultrasonic treatment are continuously carried out for 0.5 to 10 hours. In this step, the oleic acid added dropwise can gradually react with the excessive ammonia water in the original solution to generate oleic acid ions dissolved in water, which is convenient for the combination with the magnetic nanoparticles on a microscopic scale. The added ultrasound not only promotes the reaction of oleic acid and ammonia water, but also promotes the generation of coordination bonds between oleic acid molecules and magnetic nanoparticles, thereby being beneficial to the production of high-performance magnetic fluid.
After the reaction is finished, the oleic acid modified magnetic nano particles are difficult to separate through magnetic separation or centrifugation, and ethanol is added to promote agglomeration and sedimentation of the oleic acid modified magnetic nano particles as described in the step (2), the purity of the ethanol is 50% -100%, the ratio of the volume of the added ethanol to the volume of the product solution is 0.1-5, and the washing times of the added ethanol is 1-20. In this step, since the prepared oleic acid-modified magnetic nanoparticles are highly dispersed in the carrier liquid, they are difficult to separate from the carrier liquid to remove impurities or transfer into a desired carrier liquid. The addition of the ethanol molecules can promote the collision, agglomeration and sedimentation of the oleic acid modified magnetic nano particles, pave the subsequent cleaning and transferring, and can not influence the structure and stability modification of the oleic acid modified magnetic nano particles, ensure that the oleic acid modified magnetic nano particles can still be highly dispersed after cleaning and re-suspending, and realize highly stable magnetic fluid by mutually rejecting modified long-chain molecules to resist agglomeration.
In some embodiments, in step (3), the product is washed with pure water, the ratio of the volume of pure water added to the volume of the product is 1-100, and the washing times are 1-20 with the aid of magnetic separation. And (3) repeatedly cleaning the product with pure water to remove impurity ions in the product, and removing ethanol introduced in the step (II). Impurity ions are removed, so that the purity degree of the magnetic fluid of the product can be guaranteed, and the magnetic fluid is beneficial to application in various scenes. The ethanol also has the effect of promoting agglomeration in the magnetic fluid carrier liquid, and the ethanol and water are highly mutually soluble and volatile, and can achieve good removal effect by repeated washing with water. In addition, the oleic acid modified magnetic nano particles have strong hydrophobicity, and can keep an agglomerated state in a pure water cleaning process after being agglomerated by ethanol promotion, so that loss is avoided.
In some embodiments, the step (4) is specifically to add an oily carrier liquid into the magnetic nanoparticle aqueous solution obtained in the step (3), wherein the volume ratio is 0.1-10; stirring and ultrasonic treatment are continuously applied for 0.5-5 h, the stirring rotation speed is 100-3000 rpm, the aqueous phase solution and kerosene are fully and uniformly mixed to form microemulsion, and the transfer of the oleic acid modified magnetic nano particles from the aqueous phase to the oil phase is promoted. Preferably, the magnetic carrier liquid may be kerosene. In the step, the aqueous phase solution and kerosene form microemulsion under the action of ultrasonic and stirring, so that the water-oil interface area can be greatly increased, the oleic acid modified magnetic nano particles can be ensured to be in full contact with the kerosene phase, the transfer efficiency from the aqueous phase to the kerosene phase is greatly improved, the raw material loss is reduced, and meanwhile, the dispersibility of the oleic acid modified magnetic nano particles can be enhanced.
In some embodiments, the step (5) specifically comprises adding a demulsifier to the microemulsion obtained in the step (4), wherein the volume ratio is 0.1-10; stirring or centrifuging the mixed solution to make the demulsifier fully play a role in promoting the separation of the water phase and the oil phase; preferably, the demulsifier can be an iron trichloride solution with a concentration ranging from 10 to 1000 mg/mL. Since the microemulsion formed in step (4) may be very stable, it is difficult for the aqueous phase and the kerosene phase to separate themselves under the influence of gravity. In the step (5), the demulsifier can fully react with the original microemulsion under the stirring action, and collide with the interfacial film of the original microemulsion, so that the stability of the emulsion is greatly reduced, and the separation of the water phase and the coal oil phase under the centrifugal force action can be promoted. Absorbing the water phase layer in the obtained mixed solution with the water phase and the oil phase being layered, and collecting the residual oil phase layer to obtain the magnetic fluid.
The following are specific examples
Example 1
The nonpolar solvent-based magnetic fluid with strong stability in the embodiment is prepared by the following steps:
a) 800mL of deionized water is added into a 2000mL three-necked flask, and the mixture is vigorously stirred, and one end is continuously introduced with nitrogen;
b) Adding FeSO 4 ·7H 2 O (13.9 g) and FeCl 3 ·6H 2 O(27.0g)；
c) Dropwise adding 100mL of ammonia water;
d) After the dripping is finished, turning on ultrasonic waves, and dropwise adding 100mL of oleic acid;
e) After the dripping is finished, continuing ultrasonic and intense stirring for 1h;
f) Adding ethanol into the solution to promote agglomeration of the magnetic nano particles to perform magnetic separation and cleaning so as to remove unreacted raw materials in the solution;
g) And adding water into the product, and washing for multiple times with the aid of magnetic separation to further remove impurities and remove ethanol introduced in the previous step.
h) 50mL of kerosene was added to the magnetic nanoparticle solution prepared above;
i) Ultrasonic and violent stirring for 1h;
j) To the solution was added 50mL of FeCl 3 ·6H 2 O solution (100 mg/mL), stirring was continued for 10min;
k) And (3) layering the solution, and taking the magnetic fluid layer.
The effect of the nonpolar solvent-based magnetic fluid with high stability and high purity in deionized water controlled by the permanent magnet is shown in figure 2, and the nonpolar solvent-based magnetic fluid has good magnetic control performance.
The analysis result of the particle size of the magnetic solid material in the nonpolar solvent-based magnetic fluid with high stability and purity is shown in figure 3, and the average particle sizes of the magnetic solid material are 43.81nm respectively, and the magnetic solid material has good dispersibility and no agglomeration.
The thermal weight result of the magnetic solid material in the nonpolar solvent-based magnetic fluid with strong stability and high purity prepared by the invention is shown in figure 4, and is shown in N 2 Under the atmosphere, the sample is heated from 30 ℃ to 850 ℃ at a heating rate of 20 ℃/min, and a thermogravimetric analysis experiment is carried out, wherein the weight loss of the sample below 200 ℃ is 1.39% respectively, which can be attributed to the evaporation of water adsorbed in the sample, and the weight loss between 200 ℃ and 850 ℃ is 27.65% respectively, which corresponds to the decomposition of oleic acid in the magnetic solid material, which proves that the oleic acid modified on the magnetic solid material has higher content, and can endow particles with extremely strong mutual repulsive force to prevent aggregation.
The magnetic test result of the magnetic solid material in the nonpolar solvent-based magnetic fluid with strong stability and high purity is shown in figure 5, the sample has no remanence and coercive force, shows good superparamagnetism, and has saturation magnetization of 58.5emu/g, and good magnetic performance.
The Fourier infrared spectrum of the magnetic solid material in the nonpolar solvent-based magnetic fluid with strong stability and high purity prepared by the invention is shown in figure 6, which is 580cm -1 The absorption peak at the position corresponds to Fe 3 O 4 Fe-O bending vibrations at 2918 and 2850cm -1 The absorption peak at which corresponds to-CH in oleic acid 3 and-CH 2 -generated telescopic vibrations 1632 and 1404cm -1 The absorption peak at the position corresponds to Fe 3 O 4 Stretching vibration of surface hydroxyl group at 1523 and 1428cm -1 An asymmetric stretching vibration peak and a symmetric stretching vibration peak of an absorption peak-COOH at 885cm -1 The absorption peak corresponds to the vibration of the OH-out-of-plane band, which proves that Fe in the product 3 O 4 And oleic acid, and no other impurities.
The X-ray diffraction spectrum of the magnetic solid material in the nonpolar solvent-based magnetic fluid with strong stability is shown in figure 7, and the strong diffraction peaks appear at 6 positions of 30.0 degrees, 35.5 degrees, 43.3 degrees, 53.6 degrees, 57.2 degrees and 62.9 degrees of 2 theta, and the strong diffraction peaks are similar to Fe in a powder diffraction card 3 O 4 Is matched with the standard data of (79-0418), the positions of the peaks respectively correspond to Fe 3 O 4 The (220), (311), (400), (422), (511) and (440) planes indicating that the product contains Fe 3 O 4 And the purity of the product is higher.
The stability test data of the nonpolar solvent-based magnetic fluid with high stability is shown in figure 8, the absorbance of the prepared magnetic fluid is measured by an ultraviolet-visible spectrophotometer after the magnetic fluid is diluted for several times, and the absorbance is kept at a higher level for a longer time, so that the magnetic fluid has extremely high stability and no sedimentation.
Example 2
The nonpolar solvent-based magnetic fluid with strong stability and high purity in the embodiment is prepared by the following steps:
a) 800mL of deionized water is added into a 2000mL three-necked flask, and the mixture is vigorously stirred, and one end is continuously introduced with nitrogen;
b) Adding FeSO 4 ·7H 2 O (27.8 g) and FeCl 3 ·6H 2 O(54.0g)；
c) 200mL of ammonia water is added dropwise;
d) After the dripping is finished, turning on ultrasonic waves, and dropwise adding 160mL of oleic acid;
e) After the dripping is finished, continuing ultrasonic and intense stirring for 1h;
f) Adding ethanol into the solution to promote agglomeration of the magnetic nano particles to perform magnetic separation and cleaning so as to remove unreacted raw materials in the solution;
g) And adding water into the product, and washing for multiple times with the aid of magnetic separation to further remove impurities and remove ethanol introduced in the previous step.
h) 80mL of kerosene was added to the magnetic nanoparticle solution prepared above;
i) Ultrasonic and violent stirring for 0.5h;
j) To the solution was added 50mL of FeCl 3 ·6H 2 O solution (50 mg/mL), stirring was continued for 10min;
k) And (3) layering the solution, and taking the magnetic fluid layer.
The Fourier infrared spectrum of the magnetic solid material in the nonpolar solvent-based magnetic fluid with strong stability and high purity, which is prepared by the invention, is shown in figure 9, which is 585cm -1 The absorption peak at the position corresponds to Fe 3 O 4 Fe-O bending vibrations at 2920 and 2850cm -1 The absorption peak at which corresponds to-CH in oleic acid 3 and-CH 2 -generated telescopic vibration 1632cm -1 The absorption peak at the position corresponds to Fe 3 O 4 Stretching vibration of surface hydroxyl group at 1525 and 1428cm -1 An asymmetric stretching vibration peak and a symmetric stretching vibration peak of an absorption peak-COOH at 885cm -1 The absorption peak corresponds to the vibration of the OH-out-of-plane band, which proves that Fe in the product 3 O 4 And oleic acid, and no other impurities.
The X-ray diffraction spectrum of the magnetic solid material in the nonpolar solvent-based magnetic fluid with strong stability prepared by the invention is shown in figure 10Stronger diffraction peaks appear at 6 positions of 30.1 degrees, 35.5 degrees, 43.4 degrees, 53.6 degrees, 57.2 degrees and 62.9 degrees, and the diffraction peaks are matched with Fe in a powder diffraction card 3 O 4 Is matched with the standard data of (79-0418), the positions of the peaks respectively correspond to Fe 3 O 4 The (220), (311), (400), (422), (511) and (440) planes indicating that the product contains Fe 3 O 4 And the purity of the product is higher.
The stability test data of the nonpolar solvent-based magnetic fluid with high stability is shown in figure 11, the absorbance of the prepared magnetic fluid is measured by an ultraviolet-visible spectrophotometer after the magnetic fluid is diluted for several times, and the absorbance is kept at a high level for a long time, so that the magnetic fluid has no sedimentation and high stability.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The preparation method of the nonpolar solvent-based magnetic fluid is characterized by comprising the following steps of:
(1) Preparing dispersed magnetic nano particles modified by a high molecular compound with long chain groups, wherein the number of carbon atoms of the long chain groups is more than or equal to 12;
(2) Adding a solvent which is compatible with the magnetic nanoparticle carrier liquid modified by the macromolecular compound and incompatible with the macromolecular compound modified by the surface of the magnetic nanoparticle carrier liquid to the dispersed magnetic nanoparticle obtained in the step (1) so as to promote the agglomeration of the magnetic nanoparticle, and then cleaning and purifying through magnetic separation;
(3) Adding a solvent which is compatible with the solvent for guiding agglomeration and incompatible with the macromolecular compound modified on the surface of the magnetic nano particles into the intermediate product obtained in the step (2), and removing the solvent for guiding agglomeration through magnetic separation and cleaning;
(4) Adding nonpolar carrier liquid compatible with the macromolecular compound modified on the surface of the magnetic nano particles into the intermediate product obtained in the step (3), and performing ultrasonic treatment and stirring to form microemulsion so as to promote the phase transfer of the magnetic nano particles and the dispersion of the magnetic nano particles in the nonpolar carrier liquid;
(5) And (3) adding a demulsifier which can be dissolved in the nonpolar carrier liquid added in the step (3) into the microemulsion obtained in the step (4) to promote the phase separation of the magnetic fluid formed by dispersing the magnetic nanoparticles modified by the high molecular compound in the carrier liquid, thus obtaining the nonpolar solvent-based magnetic fluid.
2. The method for preparing a nonpolar solvent-based magnetic fluid according to claim 1, wherein the polymer compound having a long chain group in the step (1) is oleic acid or lauric acid.
3. The method for preparing a nonpolar solvent-based magnetic fluid according to claim 1, wherein the magnetic nanoparticles in step (1) are Fe 3 O 4 Nanoparticles or MFe 2 O 4 Nanoparticles wherein M is Ni, co, mn or Zn.
4. The method for preparing a nonpolar solvent-based magnetic fluid according to claim 1, wherein the magnetic nanoparticles modified with the polymer compound having long chain groups dispersed in the step (1) are prepared by: in a nitrogen environment, adding ferric salt and ferrous salt into water, starting stirring, dissolving into a mixed solution of ferrous ions and ferric ions, dropwise adding ammonia water, and reacting to obtain ferroferric oxide nano particles; adding oleic acid, and starting ultrasonic to promote coupling of the oleic acid and the magnetic nanoparticles and dispersion of the modified magnetic nanoparticles, so as to obtain dispersed oleic acid modified magnetic nanoparticles;
preferably, the ratio of the amount of ferrous ions to ferric ions in the mixed solution is 0.5-2, the stirring speed is 100-3000 rpm, and the stirring and ultrasonic treatment time is 0.5-10 h.
5. The method for preparing a nonpolar solvent-based magnetic fluid according to claim 1, wherein in the step (2), the solvent that is compatible with the magnetic nanoparticle carrier liquid modified by the polymer compound and incompatible with the polymer compound modified by the surface thereof is ethanol, methanol or acetone;
in the step (2), the volume ratio of the added solvent to the magnetic nano particles prepared in the step (1) is 0.1-10.
6. The method for preparing a nonpolar solvent-based magnetic fluid according to claim 1, wherein the solvent compatible with the solvent for guiding agglomeration and incompatible with the polymer compound for surface modification of the magnetic nanoparticles in the step (3) is water.
7. The method for preparing a nonpolar solvent-based magnetic fluid according to claim 1, wherein in the step (4), the nonpolar carrier liquid compatible with the polymer compound modified on the surface of the magnetic nanoparticle is kerosene, cyclohexane or n-hexane.
8. The method for preparing a non-polar solvent-based magnetic fluid according to claim 1, wherein the volume ratio of the non-polar carrier liquid added in the step (4) to the magnetic nanoparticle suspension after the washing in the step (3) is 0.1-100.
9. The method for preparing a nonpolar solvent-based magnetic fluid according to claim 1, wherein in the step (5), the demulsifier is a ferric chloride solution, a magnesium chloride solution or a ferrous sulfate solution;
preferably, the concentration of the demulsifier is 0.1 to 100 moles per liter.
10. The method for preparing a nonpolar solvent-based magnetic fluid according to claim 9, wherein the volume ratio of the demulsifier in step (5) to the microemulsion formed in step (4) is 0.1-100.
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