CN109516503A - A kind of preparation method of high stability water-base nano magnetic fluid - Google Patents

A kind of preparation method of high stability water-base nano magnetic fluid Download PDF

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CN109516503A
CN109516503A CN201910025790.1A CN201910025790A CN109516503A CN 109516503 A CN109516503 A CN 109516503A CN 201910025790 A CN201910025790 A CN 201910025790A CN 109516503 A CN109516503 A CN 109516503A
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magnetic fluid
nano magnetic
water
preparation
high stability
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洪若瑜
武倩
杜淑敏
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Fuzhou University
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00Compounds of iron
    • C01G49/02Oxides; Hydroxides
    • C01G49/08Ferroso-ferric oxide (Fe3O4)
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K49/00Preparations for testing in vivo
    • A61K49/06Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/44Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of magnetic liquids, e.g. ferrofluids
    • H01F1/445Magnets 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00Apparatus 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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/04Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/64Nanometer sized, i.e. from 1-100 nanometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/42Magnetic properties

Abstract

The present invention relates to a kind of preparation methods of high stability water-base nano magnetic fluid.The water-base nano magnetic fluid is prepared using chemical coprecipitation: after molysite acid dissolution; it is added in the three-necked bottle of deionized water; stirring; under gas shield; alkali is rapidly added and continues to react after heating with molysite forerunner's precursor reactant, the subsequent surfactant that macromolecular is added; and obtained magnetic nanoparticle is subjected to ultrasonic wave dispersion, obtain water-base nano magnetic fluid.The invention has the advantages that preparation-obtained water-base nano magnetic fluid has excellent stability, being statically placed in room temperature condition and magnetic field can keep stabilization not precipitate for a long time;Since the surfactant biocompatibility used in preparation process is preferable, prepared water-base nano magnetic fluid no biotoxicity, and saturation magnetization with higher, it can be used as magnetic resonance imaging T2The contrast medium of signal has high practicability in field of biomedicine.

Description

A kind of preparation method of high stability water-base nano magnetic fluid
Technical field
The invention belongs to field of material technology, and in particular to a kind of preparation side of high stability water-base nano magnetic fluid Method.
Background technique
Nanometer magnetic fluid is a kind of novel functional material, it had not only had the mobility of liquid but also had had solid magnetic material The ferromagnetism of material is mixed by magnetic retention particle, base load liquid and interfacial agent three that diameter is nanometer scale A kind of stable colloidal liquid.The most significant feature of nanometer magnetic fluid is exactly superparamagnetism, i.e., magnetic nanoparticle is outside It is magnetized under magnetic field, it is whole not show magnetism when there is no external magnetic field.Exactly because the unique property of nanometer magnetic fluid, it It is widely used in the various fields such as aerospace, biological medicine, machinery, environmental protection, is physics, chemical, material supply section Learn the hot spot with area researches such as engineering and biological medicines.
Water-base nano magnetic fluid has extremely important application in biomedical magnetic resonance radiography (MRI), magnetic The MRI of nano-particle reinforcement is a kind of very promising diagnosis new technology, can be spy with metabolic disorder with diagnosing tumour and discovery Property early lesion, be conducive to disease screening, Treatment decsion and observation of curative effect.The research of water-base nano magnetic fluid and application tool There is important realistic meaning.
Thus how to prepare stability more preferably, the nanometer magnetic fluid of good biocompatibility become focus.At present The method for preparing nanometer magnetic fluid is mainly chemical coprecipitation, thermal decomposition method etc..Chemical coprecipitation prepares nano-magnetic Fluid reaction process is easy to operate, at low cost, can produce in enormous quantities, and gained magnetic-particle easily reaches a nanometer ruler Degree, and component is uniform, product purity is high.But there is also certain disadvantages for this method, if particle size distribution range is wide, produce Object is easy to reunite etc..Thermal decomposition method can prepare the nano-magnetic stream that particle diameter distribution is relatively narrow, saturation magnetization is high, stability is good Body, but yield is less, is unfavorable for producing in batches;Reaction needs to carry out under conditions of high temperature and pressure, the high requirements on the equipment;Together When, also to avoid Fe at high temperature3O4Nano particle is oxidized, and which in turns increases the difficulty of experiment.
The present invention uses the preferable molecules surfactant of biocompatibility, such as glucan, chitosan modified Nano Particle, and optimize preparation condition, the water-base nano magnetic fluid with excellent stability and good biocompatibility has successfully been obtained. The preparation method have easy to operate, mild condition, be not necessarily to high temperature and pressure, it is at low cost the advantages that.
Summary of the invention
It is easy to reunite the purpose of the present invention is being directed to the nano particle of existing chemical coprecipitation preparation, it proposes and uses biofacies The preferable molecules surfactant of capacitive is modified nano particle, prepares with high stability, and strong saturated magnetization is strong It is simultaneously applied to the magnetic resonance imaging method in field of biomedicine by degree and the water-base nano magnetic fluid of no biotoxicity (MRI).
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of preparation method of high stability water-base nano magnetic fluid, includes the following steps that (following steps are in nitrogen protection Lower progress):
(1) deionized water is added in three-necked flask under nitrogen protection, heating;
(2) FeCl being dissolved in acid3·6H2O and FeSO4·7H2O is added in the three-necked flask in (1), is vigorously stirred Under, ammonia spirit is quickly adding into above-mentioned solution, ferriferrous oxide nano magnetic-particle is prepared with chemical coprecipitation;
(3) then, it is modified to the ferriferrous oxide nano magnetic-particle progress surface of generation that molecules surfactant is added, rises Temperature, the reaction was continued certain time;
(4) it is cooled to room temperature, modified ferroferric oxide nano granules is washed, remove unreacted Fe2+、Fe3+And Ammonium hydroxide etc.;
(5) deionized water is added into the ferriferrous oxide nano magnetic-particle after washing, macromolecular table is added in ultrasonic wave dispersion Face activating agent continues ultrasound, is then dialysed in bag filter with deionized water, remove remaining reactant, is made and stablizes The good water base ferriferrous oxide nano magnetic fluid of property, in prepared water base ferriferrous oxide nano magnetic fluid, four oxygen Change three-iron nano-particle content is 0.8-3wt%, and molecules surfactant content is 0.7-2.5wt%.
40-80 DEG C of temperature of deionized water in step (1).
Acid is non-oxidizing acid in step (2), includes but are not limited to HCl, dilute sulfuric acid etc., the NH of ammonium hydroxide used3Content < 25wt%,
The dosage of ammonium hydroxide is the 30-50%, FeSO of deionized water volume4·7H2O and FeCl3·6H2The molar ratio range of O is 1: 1.5 between 1:2.
Molecules surfactant is the preferable long-chain substances of biocompatibilities such as chitosan, glucan in step (3), The mass ratio of the dosage of middle molecules surfactant and ferriferrous oxide nano magnetic-particle is 0.2:1-2:1, and macromolecular Surfactant need to divide 1-10 times in 20min have been added, and reaction temperature is 60-90 DEG C, and the reaction time is 30-120 min.
Washing, which is adopted, in step (4) is washed with deionized, and carries out Magneto separate, is repeated several times, the solution after washing It is lower than 0.01 S/m for neutral and conductivity.
Molecules surfactant in step (5) is chitosan or glucan, dosage and ferriferrous oxide nano magnetic Property particle mass ratio be 0.2:1-1:1, total sonication time be 40-60 min, dialysis time be 72 h.
Chemical coprecipitation is easy to operate, and surfactant biocompatibility is preferable, obtained Fe3O4Water-base nano magnetic Property fluid stability it is good, saturation magnetization is high.Wherein stability is indicated by index of stability I, I=(ρ1w)/(ρ-ρw), ρ1Magnetic Property fluid continues for some time the density on rear upper layer;The density for the fresh magnetic fluid that ρ-has just been prepared;ρwThe density of water.
Compared with prior art, the present invention having an advantage that
The surface for carrying out water-base nano magnetic fluid as surface modifier using glucan, chitosan is modified, prepared to obtain Nanometer magnetic fluid no biotoxicity, have splendid biocompatibility;And compared with the sample tool being prepared under existence conditions Standby more excellent stability, good stability can be kept in 60 days by being statically placed in room temperature condition and magnetic field, be much higher than Nanometer magnetic fluid can keep basic stability after 50 days, 60 days documented by document;Prepared water-base nano magnetic Property fluid saturation magnetization with higher, in field of biomedicine have high practicability.
Detailed description of the invention
Fig. 1 is the index of stability curve graph of nanometer magnetic fluid in the embodiment of the present invention 1;
Fig. 2 is the index of stability curve graph of nanometer magnetic fluid in the embodiment of the present invention 2;
Fig. 3 is the index of stability curve graph of nanometer magnetic fluid in the embodiment of the present invention 3;
Fig. 4 is the index of stability curve graph of nanometer magnetic fluid in the embodiment of the present invention 4;
Fig. 5 is the TEM figure of the ferroferric oxide nano granules of preparation, in which: (a) embodiment 1, (b) embodiment 2, (c) embodiment 3, embodiment 4 (d).
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, those skilled in the art will manage Solution, following embodiment are merely a preferred embodiment of the present invention, and to more fully understand the present invention, but protection scope of the present invention is simultaneously It is not limited to following Examples.
Embodiment 1
Deionized water is added in 250 mL three-necked flasks under nitrogen protection, is warming up to 60 DEG C;Then it is dissolved in dilute hydrochloric acid 2.35 g FeCl3·6H2O、1.2 g FeSO4·7H2O is added in above-mentioned three-necked flask, is slowly stirred 5 min;Acutely stir It mixes down, 50 mL ammonia spirits (concentration 23wt%) is quickly adding into iron salt solutions, solution quickly becomes black, obtains 1g Ferroferric oxide nano granules;Then, 10 glucans are added in 20 min, adds 0.1 g every time, aoxidize three to the four of generation It is modified that iron nano-particle carries out surface, and reaction temperature is increased to 70 DEG C, the reaction was continued 60 min;Heating is closed, black is hanged Supernatant liquid is cooled to room temperature, and the ferroferric oxide nano granules of preparation are washed with deionized, and carries out Magneto separate, repeat number It is secondary, until solution is that neutral and conductivity is smaller, remove unreacted Fe2+、Fe3+And the impurity such as ammonium hydroxide;To receiving after washing 100 mL deionized waters are added in rice magnetic-particle, and ultrasonic wave disperses 25 min, and 0.2 g glucan is added, and continue 30 min of ultrasound, Ferriferrous oxide nano magnetic fluid is obtained, then carries out 72 h of dialysis with deionized water in bag filter, is removed remaining anti- Object is answered, is made the ferroso-ferric oxide water-base nano magnetic fluid that has good stability, in ferroso-ferric oxide water-base nano magnetic fluid, The content of the content of water, ferroso-ferric oxide and surfactant is respectively 97.8wt%, 0.978wt%, 1.222wt%.It measures and receives Rice magnetic fluid stability curve, nano particle saturation magnetization and pattern, (a) in the result is shown in Figure 1, table 1 and Fig. 5;? The nanometer magnetic fluid being prepared under this condition is with good stability, and stabilization can be kept not precipitate in 60 days, and its Particle diameter distribution is uniform, and reunion situation is less, and saturation magnetization is higher.
Embodiment 2
Deionized water is added in 250 mL three-necked flasks under nitrogen protection, is warming up to 50 DEG C;Then it is dissolved in dilute hydrochloric acid 2.35 g FeCl3·6H2O、1.2 g FeSO4·7H2O is added in above-mentioned three-necked flask, is slowly stirred 5 min;Acutely stir It mixes down, 45 mL ammonia spirits (concentration 24wt%) is quickly adding into iron salt solutions, solution quickly becomes black, obtains 1g Ferroferric oxide nano granules;Then, 10 glucans are added in 20 min, adds 0.1 g every time, aoxidize three to the four of generation It is modified that iron nano-particle carries out surface, and reaction temperature is increased to 70 DEG C, the reaction was continued 90 min;Heating is closed, black is hanged Supernatant liquid is cooled to room temperature, and the ferroferric oxide nano granules of preparation are washed with deionized, and carries out Magneto separate, repeat number It is secondary, until solution is that neutral and conductivity is smaller, remove unreacted Fe2+、Fe3+And the impurity such as ammonium hydroxide;To receiving after washing 100 mL deionized waters are added in rice magnetic-particle, and ultrasonic wave disperses 25 min, and 0.2 g glucan is added, and continue 30 min of ultrasound, Ferriferrous oxide nano magnetic fluid is obtained, then carries out 72 h of dialysis with deionized water in bag filter, is removed remaining anti- Object is answered, is made the ferroso-ferric oxide water-base nano magnetic fluid that has good stability, in ferroso-ferric oxide water-base nano magnetic fluid, The content of the content of water, ferroso-ferric oxide and surfactant is respectively 97.8wt%, 0.978wt%, 1.222wt%.It measures and receives Rice magnetic fluid stability curve, nano particle saturation magnetization and pattern, are as a result shown in (b) in Fig. 2, table 1 and Fig. 5;? The nanometer magnetic fluid being prepared under this condition is with good stability, and stabilization can be kept not precipitate in 60 days, and its Particle diameter distribution is uniform, and reunion situation is less, and saturation magnetization is higher.
Embodiment 3
Deionized water is added in 250 mL three-necked flasks under nitrogen protection, is warming up to 60 DEG C;Then it is dissolved in dilute hydrochloric acid 2.35 g FeCl3·6H2O、1.2 g FeSO4·7H2O is added in above-mentioned three-necked bottle, is slowly stirred 5 min;It is vigorously stirred Under, 45 mL ammonia spirits (mass concentration 24wt%) are quickly adding into iron salt solutions, solution quickly becomes black, obtains 1g ferroferric oxide nano granules;Then, 10 glucans are added in 20 min, 0.14 g is added every time, to four oxygen of generation Changing three iron nano-particles, to carry out surface modified, and reaction temperature is increased to 70 DEG C, the reaction was continued 60 min;Heating is closed, it will be black Color suspension is cooled to room temperature, and the ferroferric oxide nano granules of preparation are washed with deionized, and carries out Magneto separate, is repeated For several times, smaller for neutral and conductivity until solution, remove unreacted Fe2+、Fe3+And the impurity such as ammonium hydroxide;To after washing 100 mL deionized waters are added in nano magnetic particle, and ultrasonic wave disperses 25 min, and 0.4 g glucan is added, and continue ultrasound 30 Min obtains ferriferrous oxide nano magnetic fluid, then carries out 72 h of dialysis, removal residual with deionized water in bag filter Reactant, the ferroso-ferric oxide water-base nano magnetic fluid that has good stability, ferroso-ferric oxide water-base nano magnetic flow is made In body, the content of water, the content of ferroso-ferric oxide are respectively 97.28wt%, 0.973wt%, 1.747wt%.Measure nano-magnetic stream As a result body stability curve, nano particle saturation magnetization and pattern are shown in (c) in Fig. 3, table 1 and Fig. 5;Under this condition The nanometer magnetic fluid being prepared is with good stability, stabilization can be kept not precipitate in 50 days, and its particle diameter distribution Uniformly, reunion situation is less, and saturation magnetization is higher.
Embodiment 4
Deionized water is added in 250 mL three-necked flasks under nitrogen protection, is warming up to 40 DEG C;Then it is dissolved in dilute hydrochloric acid 2.04g FeCl3·6H2O、1.2 g FeSO4·7H2O is added in above-mentioned three-necked bottle, is slowly stirred 5 min;It is vigorously stirred Under, 40 mL ammonia spirits (concentration 20wt%) are quickly adding into iron salt solutions, solution quickly becomes black, obtains 0.9g Ferroferric oxide nano granules;Then, 10 glucans are added in 20 min, adds 0.1 g every time, aoxidize three to the four of generation It is modified that iron nano-particle carries out surface, and reaction temperature is increased to 70 DEG C, the reaction was continued 90 min;Heating is closed, black is hanged Supernatant liquid is cooled to room temperature, and the ferroferric oxide nano granules of preparation are washed with deionized, and carries out Magneto separate, repeat number It is secondary, until solution is that neutral and conductivity is smaller, remove unreacted Fe2+、Fe3+And the impurity such as ammonium hydroxide;To receiving after washing 100 mL deionized waters are added in rice magnetic-particle, and ultrasonic wave disperses 25 min, and 0.2 g glucan is added, and continue 30 min of ultrasound, Ferriferrous oxide nano magnetic fluid is obtained, then carries out 72 h of dialysis with deionized water in bag filter, is removed remaining anti- Object is answered, is made the ferroso-ferric oxide water-base nano magnetic fluid that has good stability, in ferroso-ferric oxide water-base nano magnetic fluid, The content of water, the content of ferroso-ferric oxide are respectively 97.94wt%, 0.88wt%, 1.18wt%.Nanometer magnetic fluid is measured to stablize As a result linearity curve, nano particle saturation magnetization and pattern are shown in (d) in Fig. 4, table 1 and Fig. 5, are prepared under this condition The nanometer magnetic fluid arrived is with good stability, stabilization can be kept not precipitate in 50 days, and its particle diameter distribution is uniform, group Poly- situation is less, and saturation magnetization is higher.
Table 1 is the saturation magnetization of nano magnetic particle made from embodiment
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with repair Decorations, are all covered by the present invention.

Claims (10)

1. a kind of preparation method of high stability water-base nano magnetic fluid, which comprises the following steps:
(1) deionized water is added in three-necked flask under nitrogen protection, heating;
(2) FeCl being dissolved in acid3·6H2O and FeSO4·7H2O is added in the three-necked flask in (1), is vigorously stirred Under, ammonia spirit is quickly adding into above-mentioned solution, ferriferrous oxide nano magnetic-particle is prepared with chemical coprecipitation;
(3) then, it is modified to the ferriferrous oxide nano magnetic-particle progress surface of generation that molecules surfactant is added, rises Temperature, the reaction was continued certain time;
(4) it is cooled to room temperature, modified ferroferric oxide nano granules is washed, remove unreacted Fe2+、Fe3+And Ammonium hydroxide;
(5) deionized water is added into the ferriferrous oxide nano magnetic-particle after washing, macromolecular table is added in ultrasonic wave dispersion Face activating agent continues ultrasound, is then dialysed in bag filter with deionized water, remove remaining reactant, is made and stablizes The good water base ferriferrous oxide nano magnetic fluid of property;In prepared water base ferriferrous oxide nano magnetic fluid, four oxygen Change three-iron nano-particle content is 0.8-3wt%, and molecules surfactant content is 0.7-2.5wt%.
2. a kind of preparation method of high stability water-base nano magnetic fluid according to claim 1, it is characterised in that: step Suddenly the warming temperature in (1) is 40-80 DEG C.
3. a kind of preparation method of high stability water-base nano magnetic fluid according to claim 1, it is characterised in that: step Suddenly acid is non-oxidizing acid in (2), includes but are not limited to HCl, dilute sulfuric acid, the NH of ammonium hydroxide used3Content < 25wt%, dosage For the 30-50% of deionized water volume.
4. a kind of preparation method of high stability water-base nano magnetic fluid according to claim 1, it is characterised in that: step Suddenly FeSO described in (2)4·7H2O and FeCl3·6H2The molar ratio range of O is between 1:1.5 to 1:2.
5. a kind of preparation method of high stability water-base nano magnetic fluid according to claim 1, it is characterised in that: step Suddenly molecules surfactant is chitosan or glucan, the wherein dosage of molecules surfactant and four oxidations three in (3) The mass ratio of iron nano magnetic particle is 0.2:1-2:1, and molecules surfactant need to divide 1-10 addition in 20min It is complete.
6. a kind of preparation method of high stability water-base nano magnetic fluid according to claim 1, it is characterised in that: Step (3) reaction temperature is 60-90 DEG C, and the reaction time is 30-120 min.
7. a kind of preparation method of high stability water-base nano magnetic fluid according to claim 1, it is characterised in that: Washing, which is adopted, in step (4) is washed with deionized, and carries out Magneto separate, is repeated several times, the solution after washing be it is neutral and Conductivity is lower than 0.01 S/m.
8. a kind of preparation method of high stability water-base nano magnetic fluid according to claim 1, it is characterised in that: step Suddenly molecules surfactant is chitosan or glucan, the quality of dosage and ferriferrous oxide nano magnetic-particle in (5) Than for 0.2:1-1:1.
9. a kind of preparation method of high stability water-base nano magnetic fluid according to claim 1, it is characterised in that: Total sonication time is 40-60 min in step (5), and dialysis time is 72 h.
10. a kind of preparation method of high stability water-base nano magnetic fluid according to claim 1, it is characterised in that: Step (1)-(5) carry out under nitrogen protection.
CN201910025790.1A 2019-01-11 2019-01-11 A kind of preparation method of high stability water-base nano magnetic fluid Pending CN109516503A (en)

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