CN104649334A - Preparation method of monodisperse super paramagnetic ferroferric oxide nanoparticles and ferroferric oxide nanoparticles - Google Patents
Preparation method of monodisperse super paramagnetic ferroferric oxide nanoparticles and ferroferric oxide nanoparticles Download PDFInfo
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 230000005298 paramagnetic effect Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 22
- 239000006249 magnetic particle Substances 0.000 claims abstract description 41
- 239000002245 particle Substances 0.000 claims abstract description 22
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 48
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000008187 granular material Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 229960004249 sodium acetate Drugs 0.000 claims description 9
- 235000017281 sodium acetate Nutrition 0.000 claims description 9
- 239000001632 sodium acetate Substances 0.000 claims description 9
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000010926 purge Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000005291 magnetic effect Effects 0.000 abstract description 18
- 238000012986 modification Methods 0.000 abstract description 8
- 230000004048 modification Effects 0.000 abstract description 8
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 230000001093 anti-cancer Effects 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 230000005389 magnetism Effects 0.000 abstract 1
- 230000005415 magnetization Effects 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 29
- 239000002122 magnetic nanoparticle Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000007789 sealing Methods 0.000 description 6
- 239000013543 active substance Substances 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011553 magnetic fluid Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
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- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
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- 238000013461 design Methods 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005293 ferrimagnetic effect Effects 0.000 description 1
- 230000005308 ferrimagnetism Effects 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000003018 immunoassay Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- 229910000859 α-Fe Inorganic materials 0.000 description 1
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Abstract
The invention discloses a preparation method of monodisperse super paramagnetic ferroferric oxide nanoparticles and the ferroferric oxide nanoparticles. The preparation method comprises the following steps: preparing the monodisperse super paramagnetic ferroferric oxide nanoparticles by using a solvothermal method; performing surfactant polyacrylic acid modification on the Fe3O4 magnetic particles by using a hydrothermal method; and finally, dispersing into deionized water to obtain the monodisperse super paramagnetic ferroferric oxide nanoparticles. The prepared monodisperse super paramagnetic ferroferric oxide nanoparticles are uniform in particle size distribution of magnetic particles with average particle size of 75 nm, uniform in features, high in magnetic property of the particles, high in dispersibility and high in superparamagnetism; moreover, the specific saturation magnetization intensity of the particles can reach 78 emu/g at a maximum. The preparation method of the monodisperse super paramagnetic ferroferric oxide nanoparticles is convenient and easy, low in production cost, can be widely applied to the fields of machines, electronics, optics, magnetism, chemical engineering, biology and the like, and particularly, has great prospect on application of anti-cancer medicines on transmission and releasing.
Description
Technical field
The present invention relates to preparation and the process for modifying surface of nano-powder, more specifically, relate to a kind of preparation method and monodisperse, ultra paramagnetic ferroferric oxide nano particle of monodisperse, ultra paramagnetic ferroferric oxide nano particle.
Background technology
Magnetic nanoparticle is one of study hotspot of world today's Material Field, is a class functional materials with wide application prospect.Magnetic nanoparticle is the magnetic Nano material be employed the earliest, is widely used in the field such as preparation and biomedicine of magnetic recording material, magnetic fluid.The magnetic Nano material wherein with biocompatibility and certain Biomedical function has the features such as small-size effect, good magnetic conductance tropism, biocompatibility, biological degradability and activity functional groups.Again due to the biological activity of magnetic bio nano material, affinity or reactive behavior, in conjunction with various functional molecular as enzyme, antibody, cell, DNA or RNA etc., therefore can be widely used in the field such as separation and classification of targeted drug, enzyme immobilizatio, immunoassay, cell.
Conventional magneticsubstance is divided into three major types: ferrite system, metal system and nitrided iron system.Wherein, nanometer Fe
3o
4magnetic-particle has the preparation feature such as simple, nontoxic, in the middle of the preparation being widely used in different sorts magnetic liquid and magnetic colloidal sol.The preparation method of nano magnetic particle mainly contains sol-gel method, pyrolysis method, microemulsion method, solvent-thermal method, chemical coprecipitation etc., and wherein solvent-thermal method prepares the fairly simple and effective means of monodisperse magnetic particle.
As used in biomedicine, in general the particle that aforesaid method prepares also will be distributed to further in carrier fluid and go normally to use, and namely modification, is distributed to magnetic nanoparticle in liquid.Ferromagnetic nano particle by tensio-active agent height to fill the air among certain liquid form stable colloid, nano particle in magnetic fluid is very little, so that in base fluid, present random pedesis, this thermal motion is enough to the settlement action of counteracting gravity and weakens interparticle magnetic cohesion, can stable existence under the effect in gravity and magnetic field, do not produce precipitation and cohesion.
Along with synthesis and the development of detection technique, the size of magnetic nanoparticle and morphology control are gradually improved.But for specific dimensions and the synthesis of the good particle of monodispersity remains a challenge.The magnetic-particle that existing solvent-thermal method prepares single-size is comparatively ripe, but exist control that particle size is too large, the reaction times how long with the deficiency such as energy consumption is large, limit it and further apply.And existing method is improved, the homogeneous controlled magnetic nanoparticle of particle size can well be synthesized.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the existing technical deficiency preparing ferroferric oxide magnetic nanoparticle, a kind of preparation method of monodisperse, ultra paramagnetic ferroferric oxide nano particle is provided, the ferroferric oxide nano granules of the method preparation synthesis single dispersing, grain diameter and morphology controllable, particle diameter is at about 70 ~ 80nm, sharp outline and stable performance, soilless sticking phenomenon, has good dispersive ability in water medium.
Object of the present invention is achieved by the following technical programs:
A kind of preparation method of monodisperse, ultra paramagnetic variable color ferroferric oxide nano granules is provided, adopts solvent-thermal method to prepare monodispersity Fe
3o
4magnetic-particle, then by hydrothermal method to product Fe
3o
4it is polyacrylic acid modified that magnetic-particle carries out tensio-active agent, is finally scattered in deionized water and get final product.
Particularly, the inventive method comprises the following steps:
S1. by FeCL
36H
2o is dissolved in ethylene glycol organic solvent, stir into settled solution, add and after sodium-acetate and quadrol fully dissolve, to be transferred in hydrothermal reaction kettle liner reacting by heating under air-proof condition, temperature of reaction is 180 DEG C ~ 200 DEG C, reaction times is 8 ~ 12 hours, cool to room temperature, can obtain nanometer Fe after several washed with de-ionized water
3o
4magnetic-particle;
S2. polyacrylic acid is dissolved in dimethyl formamide and obtains mixture 1, the nanometer Fe obtained by S1 step
3o
4magnetic-particle joins dimethyl formamide and obtains mixture 2 after supersound process, blend mixture 1 and mixture 2, reaction in hydrothermal reaction kettle lining container is transferred to after stirring, temperature of reaction is 150 DEG C ~ 180 DEG C, reaction times is 4 ~ 6 hours, add Virahol after being removed by solution after cooling and obtain mixed system, centrifugal treating after mixed system leaves standstill, collecting precipitation thing also can obtain monodisperse, ultra paramagnetic variable color ferroferric oxide nano granules after carrying out washing treatment.
Preferably, FeCL described in S1 step
36H
2the mass volume ratio of O and ethylene glycol is 1g:20 mL.By FeCL
36H
2o is dissolved in ethylene glycol organic solvent and stirs into settled solution.
Preferably, the add-on of sodium-acetate described in S1 step is according to FeCL
36H
2o: the mass ratio of sodium-acetate is
1: 3。
Preferably, the add-on of quadrol described in S1 step is according to FeCL
36H
2the mass volume ratio of O and ethylene glycol is 1g:10 mL.
Preferably, fully dissolving described in S1 step is sodium-acetate and quadrol are added rear vigorous stirring 30min and ultrasonic 10min makes it become orange-yellow settled solution, then proceeds in the Teflon liner of hydrothermal reaction kettle, sealed reaction.
Preferably, described in S1 step, the temperature of reaction of sealed reaction is 200 DEG C, and the reaction times is 8 hours.
Preferably, in mixture 1 described in S2 step, the mass volume ratio of polyacrylic acid and dimethyl formamide is 0.3g:10 mL.
Preferably, supersound process described in S2 step is process 30 minutes.
Preferably, in mixture 2 described in S2 step, the consumption 2 of dimethyl formamide is the volume of dimethyl formamide in mixture 1 doubly.
Preferably, temperature of reaction described in S2 step is 150 DEG C, and the reaction times is 5 hours.
Preferably, described in S2 step, cooling is cooled to 50 DEG C or following temperature.
Preferably, the consumption of Virahol described in S2 step is determined according to 2 times of volumes of the total consumption of dimethyl formamide.
Preferably, mixed system time of repose described in S2 step is 1 hour.The condition of described centrifugal treating is centrifugal treating 20 minutes under 6300rpm.
Preferably, described in S2 step, the concentration of polyacrylic acid (PAA) is 0.2g/mL, and its molecular weight is 3000.
Preferably, nanometer Fe described in S2 step
3o
4the washing of magnetic-particle is in nanometer Fe
3o
4add 70% ethanol purge in magnetic-particle, then add deionized water and get final product.
The present invention provides the monodisperse, ultra paramagnetic variable color ferroferric oxide nano granules adopting aforesaid method to prepare simultaneously, described monodisperse, ultra paramagnetic variable color ferroferric oxide nano granules single dispersing, grain diameter and morphology controllable, particle diameter is at about 70 ~ 80nm, sharp outline and stable performance, soilless sticking phenomenon, has good dispersive ability in water medium.
Beneficial effect of the present invention:
The present invention is based on solvent-thermal method and hydrothermal method principle, employ the tensio-active agent of polyacrylic acid as monodisperse, ultra paramagnetic ferroferric oxide nano particle of the present invention dexterously, compared with conventional water soluble surfactant active, polyacrylic acid have not easily oxidized, with water have the advantages such as good consistency, and the synthesis technique of low-molecular-weight polypropylene acid is simple and convenient, cost is low, through experiments a large amount of for a long time and analysis and summary, under present invention process condition, polyacrylic acid can be coated on nanometer Fe well
3o
4the surface of magnetic-particle, the polyhydric structure of polyacrylic acid also makes magnetic-particle have good wetting ability, form certain thickness solvated layer on surface and form stable sol system, the present invention adopts the technique of science, give full play to polyacrylic advantage, and its advantage and present invention process are combined closely, play synergy, the magnetic colloidal dispersion successfully utilizing polyacrylic acid to prepare as tensio-active agent is evenly and good stability.By the subsidiary of the instruments such as TEM, VSM, also demonstrate that in the solution, the particle diameter of each magnetic nanoparticle, distribution, meet the requirements really, and the water-based ferroferric oxide magnetic fluid that the present invention prepares can use in useful for drug delivery release.
Further, obtain the processing condition be suitable for through many experiments analysis and summary, the overall preparation process of scientific design of the present invention and crucial processing condition, first adopt solvent structure monodispersity Fe
3o
4magnetic-particle, then by hydrothermal method to product Fe
3o
4it is polyacrylic acid modified that magnetic-particle carries out tensio-active agent, is finally scattered in deionized water.Successfully prepare the magnetic nanoparticle that particle diameter is the monodisperse, ultra paramagnetic ferroferric oxide of about 70 ~ 80nm, for the applying of magnetic nanoparticle of Z 250 provides strong technical foundation.
The monodisperse, ultra paramagnetic ferroferric oxide nanometer grain preparation method prepared of the present invention is easy, and processing condition are gentle, and low production cost, can be widely used in the fields such as machinery, electronics, optics, magnetics, chemical industry and biology.
Accompanying drawing explanation
The scanning electron microscope (SEM) photograph of monodisperse, ultra paramagnetic ferroferric oxide magnetic nanoparticle prepared by Fig. 1 the present invention.
The transmission electron microscope picture of monodisperse, ultra paramagnetic ferroferric oxide magnetic nanoparticle prepared by Fig. 2 the present invention.
X ray powder diffraction (XRD) spectrogram of monodisperse, ultra paramagnetic ferroferric oxide magnetic nanoparticle prepared by Fig. 3 the present invention.
Fig. 4 magnetic hysteresis loop figure.Wherein, curve (a) magnetic hysteresis loop that is ferroferric oxide nano granules; Curve (b) is the magnetic hysteresis loop of polyacrylic acid modified ferroferric oxide nano granules.
Embodiment
The present invention is further illustrated below in conjunction with the drawings and specific embodiments.Unless stated otherwise, the reagent raw material that the embodiment of the present invention adopts is conventional commercial reagent raw material, and unless stated otherwise, the method equipment of employing is the method and apparatus of this area routine.
Embodiment 1 prepares monodisperse, ultra paramagnetic ferroferric oxide nano particle
S1.Fe
3o
4the synthesis of magnetic-particle
By 1g FeCL
36H
2o is dissolved in 20mL ethylene glycol organic solvent, stirs into settled solution.Then 3g sodium-acetate and 10mL quadrol is added, vigorous stirring 30min ultrasonic (ultrasonic cleaner) 10min makes it become orange-yellow settled solution, proceed in the Teflon liner of hydrothermal reaction kettle, sealing is placed in air dry oven reacts 8 hours at 200 DEG C.
After reaction terminates, cool to room temperature.After several washed with de-ionized water, nanometer Fe can be obtained
3o
4magnetic-particle.
S2. the surface modification of magnetic-particle
0.3g polyacrylic acid is dissolved in 10mL dimethyl formamide, by Fe
3o
4magnetic-particle joins in 20mL dimethyl formamide after 30min supersound process, both mixing are transferred to after stirring in hydrothermal reaction kettle lining container, sealing is placed in air dry oven reacts 5 hours at 150 DEG C, be cooled to 50 DEG C or following temperature, 60mL Virahol is added after being removed by solution, mixture transfers in whizzer the centrifugal 20min carrying out 6300rpm after placing 1 hour, collecting precipitation thing also uses 70% ethanol purge, finally adds deionized water and can obtain polyacrylic acid modified nanometer Fe
3o
4magnetic-particle, particle diameter is 70 ~ 80 nm, sharp outline and stable performance, and soilless sticking phenomenon, has good dispersive ability in water medium.
Embodiment 2 prepares monodisperse, ultra paramagnetic ferroferric oxide nano particle
S1.Fe
3o
4the synthesis of magnetic-particle
By 1g FeCL
36H
2o is dissolved in 20mL ethylene glycol organic solvent, stirs into settled solution.Then add 3g sodium-acetate and 10mL quadrol, vigorous stirring 30min ultrasonic 10min makes it become orange-yellow settled solution, proceed in the Teflon liner of hydrothermal reaction kettle, sealing is placed in air dry oven reacts 10 hours at 200 DEG C.
After reaction terminates, cool to room temperature.After several washed with de-ionized water, nanometer Fe can be obtained
3o
4magnetic
Property particle.
S2. the surface modification of magnetic-particle
0.3g polyacrylic acid is dissolved in 10mL dimethyl formamide, by Fe
3o
4magnetic-particle joins in 20mL dimethyl formamide after 30min supersound process, both mixing are transferred to after stirring in hydrothermal reaction kettle lining container, sealing is placed in air dry oven reacts 4 hours at 180 DEG C, be cooled to 50 DEG C or following temperature, 60mL Virahol is added after being removed by solution, mixture transfers in whizzer the centrifugal 20min carrying out 6300rpm after placing 1 hour, collecting precipitation thing also uses 70% ethanol purge, finally adds deionized water and can obtain polyacrylic acid modified nanometer Fe
3o
4magnetic-particle.Particle diameter is 70 ~ 80 nm, sharp outline and stable performance, and soilless sticking phenomenon, has good dispersive ability in water medium.
Embodiment 3 prepares monodisperse, ultra paramagnetic ferroferric oxide nano particle
S1.Fe
3o
4the synthesis of magnetic-particle
By 1g FeCL
36H
2o is dissolved in 20mL ethylene glycol organic solvent, stirs into settled solution.Then add 3g sodium-acetate and 10mL quadrol, vigorous stirring 30min ultrasonic 10min makes it become orange-yellow settled solution, proceed in the Teflon liner of hydrothermal reaction kettle, sealing is placed in air dry oven reacts 12 hours at 180 DEG C.After reaction terminates, cool to room temperature.After several washed with de-ionized water, nanometer Fe can be obtained
3o
4magnetic-particle.
S2. the surface modification of magnetic-particle
0.3g polyacrylic acid is dissolved in 10mL dimethyl formamide, by Fe
3o
4magnetic-particle joins in 20mL dimethyl formamide after 30min supersound process, both mixing are transferred to after stirring in hydrothermal reaction kettle lining container, sealing is placed in air dry oven reacts 6 hours at 150 DEG C, be cooled to 50 DEG C or following temperature, 60mL Virahol is added after being removed by solution, mixture transfers in whizzer the centrifugal 20min carrying out 6300rpm after placing 1 hour, collecting precipitation thing also uses 70% ethanol purge, finally adds deionized water and can obtain polyacrylic acid modified nanometer Fe
3o
4magnetic-particle.Particle diameter is 70 ~ 80 nm, sharp outline and stable performance, and soilless sticking phenomenon, has good dispersive ability in water medium.
By the nanometer Fe that above-described embodiment S1 step prepares
3o
4magnetic-particle carries out scanning electron microscopic observation, accompanying drawing 1 and attachedly Figure 2 shows that nanometer Fe of the present invention
3o
4magnetic-particle carries out the surface topography that on scanning electronic microscope and transmission electron microscope, scanning arrives, accompanying drawing 1 is the scanning electron microscope (SEM) photograph of the nano particle that S1 step prepares, find out from figure and synthesized a large amount of spherical nanoparticles, grain diameter is even, and diameter is about 75nm.Accompanying drawing 2 is transmission electron microscope pictures of above-mentioned particle, also can find out and synthesize a large amount of nano particles from figure, simultaneously and scanning electron microscope (SEM) photograph corresponding, evenly, diameter is about 75nm to grain diameter.
As shown in Figure 3, the crystal structure analysis XRD of product carries out on X-ray powder diffractometer (XRD), in the X ray powder diffraction spectrum spectrogram of gained, and Fe
3o
4particle is good anti-phase spinel structure.
Final product prepared by the present embodiment is Fe
3o
4magnetic-particle, Fe
3o
4magnetic-particle has ferrimagnetism, but can be dispersed in water well by suitable method of modifying, and has excellent stability.Accompanying drawing 4 is the magnetic hysteresis loop figure of magnetic-particle.Magnetic property measurement result shows, after magnetic-particle is dispersed in water formation colloidal sol, sample is superparamagnetism.Weaken intergranular magneticaction by suitable surface modification, ferrimagnetic particles just can rely on pedesis to destroy the chain-like structure of self magnetic moment induced synthesis in water, thus shows as superparamagnetism.
Other accompanying drawings can not repeat one by one at this, the experimental summary a large amount of for a long time from the present invention can be understood, the monodisperse, ultra paramagnetic variable color ferroferric oxide nano granules particle diameter that the present invention prepares and morphology controllable, particle diameter is at about 70 ~ 80 nm, sharp outline and stable performance, soilless sticking phenomenon, has good dispersive ability in water medium.
The above, it is only preferred embodiment of the present invention, not any pro forma restriction is done to the present invention, therefore everyly do not depart from technical solution of the present invention content, the any simple modification above embodiment done according to technical spirit of the present invention, equivalent variations and modification, all still belong to claims of the present invention limit in the scope of technical scheme.
Claims (10)
1. a preparation method for monodisperse, ultra paramagnetic ferroferric oxide nano particle, is characterized in that, comprises the following steps:
S1. by FeCL
36H
2o is dissolved in ethylene glycol organic solvent, stir into settled solution, add and after sodium-acetate and quadrol fully dissolve, to be transferred in hydrothermal reaction kettle liner reacting by heating under air-proof condition, temperature of reaction is 180 DEG C ~ 200 DEG C, reaction times is 8 ~ 12 hours, cool to room temperature, obtains nanometer Fe after washed with de-ionized water
3o
4magnetic-particle;
S2. polyacrylic acid is dissolved in dimethyl formamide and obtains mixture 1, the nanometer Fe obtained by S1 step
3o
4magnetic-particle joins dimethyl formamide and obtains mixture 2 after supersound process, blend mixture 1 and mixture 2, reaction in hydrothermal reaction kettle lining container is transferred to after stirring, temperature of reaction is 150 DEG C ~ 180 DEG C, reaction times is 4 ~ 6 hours, add Virahol after being removed by solution after cooling and obtain mixed system, centrifugal treating after mixed system leaves standstill, collecting precipitation thing also can obtain monodisperse, ultra paramagnetic variable color ferroferric oxide nano granules after carrying out washing treatment.
2. preparation method according to claim 1, is characterized in that, in S1 step, described temperature of reaction is 200 DEG C, and the reaction times is 8 hours.
3. preparation method according to claim 1, is characterized in that, in S1 step, by 1g FeCL
36H
2o joins in the ethylene glycol organic solution of 20mL, stirs into settled solution; Then add 3g sodium-acetate and 10mL quadrol, vigorous stirring 30min ultrasonic 10min makes it become orange-yellow settled solution, proceed in hydrothermal reaction kettle.
4. preparation method according to claim 1, is characterized in that, in S2 step, described temperature of reaction is 150 DEG C, and the reaction times is 5 hours.
5. preparation method according to claim 1, it is characterized in that, in S2 step, 0.3g polyacrylic acid is dissolved in 10mL dimethyl formamide, S1 step is obtained Fe3O4 magnetic-particle and join in 20mL dimethyl formamide after supersound process, both mixing are transferred to after stirring in hydrothermal reaction kettle lining container, react 5 hours at 150 DEG C, be cooled to 50 DEG C or following temperature, after being removed by solution, add 60mL Virahol, mixture places rear centrifugal treating, collecting precipitation thing.
6. preparation method according to claim 5, is characterized in that, described centrifugal treating is the centrifugal treating 20min at 6300rpm.
7. according to the preparation method described in claim 1, it is characterized in that, in S2 step, polyacrylic concentration is 0.2g/mL, and its molecular weight is 3000.
8. according to the preparation method described in claim 1, it is characterized in that, nanometer Fe in S2 step
3o
4the washing step of magnetic-particle comprises: in nanometer Fe
3o
4add 70% ethanol purge in magnetic-particle, then add deionized water wash.
9. the monodisperse, ultra paramagnetic variable color ferroferric oxide nano granules that the preparation method described in any one of claim 1 ~ 8 prepares.
10. monodisperse, ultra paramagnetic variable color ferroferric oxide nano granules according to claim 9, particle diameter is 70 ~ 80nm.
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|---|---|---|---|
| CN201510040342.0A CN104649334B (en) | 2015-01-27 | 2015-01-27 | The preparation method of monodisperse, ultra paramagnetic ferroferric oxide nano-particle and ferroferric oxide nano granules |
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|---|---|---|---|
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| CN104649334B CN104649334B (en) | 2017-01-04 |
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| CN106698524A (en) * | 2016-11-30 | 2017-05-24 | 兰州大学 | Method for modifying hydrophobic Fe3O4 into hydrophilic Fe3O4 |
| CN109261124A (en) * | 2018-10-30 | 2019-01-25 | 成都市水泷头化工科技有限公司 | A kind of acticarbon and preparation method going heavy metal ion in water removal |
| JP2019172905A (en) * | 2018-03-29 | 2019-10-10 | 株式会社フジミインコーポレーテッド | Polishing composition, manufacturing method thereof, and magnetic polishing method |
| CN110628760A (en) * | 2019-09-24 | 2019-12-31 | 中科瑞慈生物科技(深圳)有限责任公司 | Method for synthesizing washing-free and removal-free nano magnetic beads for nucleic acid extraction by one-step method |
| CN112390453A (en) * | 2020-11-25 | 2021-02-23 | 上海交通大学 | Modified magnetic Fe3O4Powder, method for the production thereof and use thereof |
| CN113247959A (en) * | 2021-06-09 | 2021-08-13 | 东北大学 | Method for preparing functional iron oxide nanoparticles by using machine head ash as raw material |
| CN115448374A (en) * | 2022-08-15 | 2022-12-09 | 国科温州研究院(温州生物材料与工程研究所) | Novel preparation method of magnetic nanoparticles |
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| CN106698524A (en) * | 2016-11-30 | 2017-05-24 | 兰州大学 | Method for modifying hydrophobic Fe3O4 into hydrophilic Fe3O4 |
| CN106698524B (en) * | 2016-11-30 | 2018-03-30 | 兰州大学 | It is a kind of by hydrophobic Fe3O4It is modified as hydrophilic method |
| JP2019172905A (en) * | 2018-03-29 | 2019-10-10 | 株式会社フジミインコーポレーテッド | Polishing composition, manufacturing method thereof, and magnetic polishing method |
| CN110317573A (en) * | 2018-03-29 | 2019-10-11 | 福吉米株式会社 | Composition for polishing and its manufacturing method and magnetic grinding method |
| JP7007973B2 (en) | 2018-03-29 | 2022-01-25 | 株式会社フジミインコーポレーテッド | Polishing composition, its manufacturing method, and magnetic polishing method |
| CN109261124A (en) * | 2018-10-30 | 2019-01-25 | 成都市水泷头化工科技有限公司 | A kind of acticarbon and preparation method going heavy metal ion in water removal |
| CN110628760A (en) * | 2019-09-24 | 2019-12-31 | 中科瑞慈生物科技(深圳)有限责任公司 | Method for synthesizing washing-free and removal-free nano magnetic beads for nucleic acid extraction by one-step method |
| CN112390453A (en) * | 2020-11-25 | 2021-02-23 | 上海交通大学 | Modified magnetic Fe3O4Powder, method for the production thereof and use thereof |
| CN113247959A (en) * | 2021-06-09 | 2021-08-13 | 东北大学 | Method for preparing functional iron oxide nanoparticles by using machine head ash as raw material |
| CN115448374A (en) * | 2022-08-15 | 2022-12-09 | 国科温州研究院(温州生物材料与工程研究所) | Novel preparation method of magnetic nanoparticles |
| CN115448374B (en) * | 2022-08-15 | 2024-04-05 | 国科温州研究院(温州生物材料与工程研究所) | Preparation method of magnetic nano particles |
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