CN1539793A - Method for preparing composite submicron magnetic particles by coating organic microspheres with nano magnetic iron oxide particles - Google Patents
Method for preparing composite submicron magnetic particles by coating organic microspheres with nano magnetic iron oxide particles Download PDFInfo
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- CN1539793A CN1539793A CNA031098002A CN03109800A CN1539793A CN 1539793 A CN1539793 A CN 1539793A CN A031098002 A CNA031098002 A CN A031098002A CN 03109800 A CN03109800 A CN 03109800A CN 1539793 A CN1539793 A CN 1539793A
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- 239000002245 particle Substances 0.000 title claims abstract description 35
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000004005 microsphere Substances 0.000 title claims abstract description 20
- 239000006249 magnetic particle Substances 0.000 title claims description 6
- 238000000576 coating method Methods 0.000 title abstract description 11
- 239000011248 coating agent Substances 0.000 title abstract description 10
- 239000002131 composite material Substances 0.000 title abstract description 9
- 239000004793 Polystyrene Substances 0.000 claims abstract description 14
- 229920002223 polystyrene Polymers 0.000 claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 32
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 16
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 235000010333 potassium nitrate Nutrition 0.000 claims description 15
- 239000004323 potassium nitrate Substances 0.000 claims description 15
- 150000002505 iron Chemical class 0.000 claims description 14
- 239000000839 emulsion Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 9
- 238000010790 dilution Methods 0.000 claims description 9
- 239000012895 dilution Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical group Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- LNOZJRCUHSPCDZ-UHFFFAOYSA-L iron(ii) acetate Chemical compound [Fe+2].CC([O-])=O.CC([O-])=O LNOZJRCUHSPCDZ-UHFFFAOYSA-L 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000002347 injection Methods 0.000 abstract description 15
- 239000007924 injection Substances 0.000 abstract description 15
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 abstract 2
- 239000011258 core-shell material Substances 0.000 abstract 1
- 238000004945 emulsification Methods 0.000 abstract 1
- 229910052742 iron Inorganic materials 0.000 abstract 1
- 239000011257 shell material Substances 0.000 description 15
- 239000012153 distilled water Substances 0.000 description 14
- 239000011246 composite particle Substances 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
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- 239000000463 material Substances 0.000 description 6
- 239000011805 ball Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 229960002089 ferrous chloride Drugs 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002159 nanocrystal Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000011553 magnetic fluid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 229920000867 polyelectrolyte Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
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- 238000010521 absorption reaction Methods 0.000 description 1
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- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
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- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
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- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 239000004038 photonic crystal Substances 0.000 description 1
- 208000007578 phototoxic dermatitis Diseases 0.000 description 1
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- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
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- 239000011232 storage material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention belongs to the technical field of fast coating organic submicron particles by an iron sol hydrolysis method, and particularly relates to a method for preparing composite submicron particles by coating organic microspheres with nano magnetic iron oxide particles. The invention adopts a soap-free emulsion method to obtain organic microspheres such as polystyrene with different particle sizes, uses a ferrous salt solution, and controls the concentration of the ferrous salt solution in a microsphere coating system by a slow injection method to obtain magnetic composite microspheres with different shell thicknesses and a core/shell structure, and the magnetic core-shell size of the composite microspheres can be effectively controlled.
Description
Invention field
The invention belongs to the technical field that is covered with the machine submicron particles with ferrum collosol hydrolysis method Fast Packet, particularly coat the method that organic microballoon prepares compound submicron particles with the nano magnetic iron oxide particle.
Background technology
Recently, people are obtaining very big progress aspect the design of being devoted to have the specific function nano structural material and the research, the value of nano material is that it has character such as light, electricity, magnetic, mechanics, chemistry, and these character are because the ordered structure of the size of nano material, composition determines.Magnetic Nano material is because its distinctive magnetic property at first is used to biological field, as the biochemical drug and the magnetic guiding medicine of isolated genes; Also be used for the information storage material in a large number now.Therefore magnetic nanometer composite material is extensively used in fields such as Communication Engineering, pharmacy, biology.Generally be to be core with the sub-micron ball, nanocrystal is coated on outside the ball as shell, forms compound sub-micron ball with this.The nuclear that pattern, size, structure can arbitrarily be controlled over past ten years/hull shape magnetic Nano material has begun to be applied in fields such as telecommunications, catalysis, bioseparation, medical images diagnosis, magnetic cooling and magnetic fluid.
The technology of preparing that coats microballoon with nanoparticle is how relevant with particle surface physics and chemical property, there are many complicated factors to influence coating technology, as the change in electrical charge of outer shell, the chemical reaction ability of nuclear surface chemistry functional group, the dispersiveness of nuclear and stable.The physical properties of coating layer has also determined the dispersion stabilization of composite particles, and influences the magnetic of composite particles, photosensitiveness, catalytic.The problem that present people are concerned about most is how to improve the homogeneity of coating layer and the controllability of dispersion stabilization and coating.Recent years, scientific research group is arranged in the world also making up photonic crystal and three-dimensional porous material, in the hope of obtaining up-to-date optical communication material with this magnetic composite.In the past the research of complex microsphere was focused mostly on and be masterplate with the polystyrene, preparing them as shell material with silicon-dioxide and metallic oxide nanocrystal body.As clad nano silicon-dioxide, titanium dioxide, yttrium oxide or ferric oxide on polystyrene microsphere.Make polymer microballoon in many fields of hi-tech, obtain application like this.
People such as U.S. J.Ughelstad disclose 2.8 microns synthesis techniques to 4.5 microns magnetic polymer particles in US Patent PCT/NO83/00014, it is resulting to be the inside that magnetic-particle irregularly is distributed in polymer drops.Coating organic ball at preparation nano magnetic iron oxide particle recently prepares in the technology of compound sub-micro ball, upward (see also Frank Caruso with people such as Frank Caruso " chemical material " (calendar year 2001s 13 are rolled up 109 pages) and " science " (volume was 1111 pages in 1998 282) with layer-layer coating method, Marina Spasova, Andrei Susha.Chem.Mater..2001,13,109-116.and Caruso, F.; Caruso, R.A.; Mohwald, H.Science 1998,282, and 1111), and the even polymerization of magnetic grain of Benedikt Lindlar (sees also " material progress ", rolled up 1656 pages in 2002 14; Benedikt Lindlar, Monica Boldt, StefanieEiden-Assmann, Georg Maret, Adv.Mater.2002,14,1656.) be fresh approach.The former is the surface charge that changes polystyrene microsphere with polyelectrolyte, form by electrostatic attraction absorption nano magnetic iron oxide particle and coat shell, but repeated multiple times coats the control shell thickness like this.But in the method, the nano magnetic iron oxide granules preparation need be carried out in advance; And when control coats the thickness of shell, need many times carry out modification to the surface of microballoon, changing its surface charge property repeatedly, thereby make cladding process and step very loaded down with trivial details, can't use in practice with different polyelectrolyte.The latter adopts the even polymerization process of magnetic grain, need prepare nano magnetic particle in advance equally, and magnetic-particle is distributed evenly at composite particles inside; This loaded down with trivial details technology also can't obtain the outside evenly composite particles of coated magnetic housing.In a word, loaded down with trivial details preparation technology will make these ferric oxide coating technologies can't effectively be used in practice.
Summary of the invention
The object of the present invention is to provide with the nano magnetic iron oxide particle and coat the method that organic microballoon prepares compound submicron particles.The technology of this method is simple, and effective controlling packet coating layer ranges in thickness.
The objective of the invention is to be achieved through the following technical solutions:
The present invention is to use divalent iron salt solution control hydrolysis method to prepare magnetic iron oxide particle it is coated on organic microballoons such as polystyrene, thereby obtains the martial ethiops complex microsphere of core/shell structure.
The present invention controls the concentration of divalent iron salt solution in these microballoon coating systems by slow injecting method, can obtain the complex microsphere of different shell thicknesses, and the nucleocapsid size of complex microsphere can obtain effectively control like this.
The step of concrete grammar comprises:
Coat the preparation compound ball: take from system or the commercially available organic microballoon emulsion of copolymerization, adding is the deionized water dilution of 8~15 times of polystyrene microsphere emulsion volumes and stirs, add saltpetre, hexamethylenetetramine and deionized water then, stir and mix, under protection of inert gas, drip divalent iron salt solution with syringe pump, slowly be warming up to 70~120 ℃, 1~a few hours of successive reaction, obtain ferrum collosol; Centrifugation, washing and drying promptly obtains the compound submicron particles with organic microballoon of nano magnetic iron oxide particle coating.
The concentration of described polystyrene microsphere emulsion is 10~15wt%.
Divalent iron salt in the described ferrum collosol: saltpetre: hexamethylenetetramine: the mol ratio of water is 0.01~0.16: 0.003~0.01: 0.001~0.01: 50~170; Preferred divalent iron salt: saltpetre: hexamethylenetetramine: the mol ratio of water is 0.05~0.12: 0.005~0.01: 0.005~0.01: 55~160; Preferred divalent iron salt: saltpetre: hexamethylenetetramine: the mol ratio of water is 0.05~0.12: 0.004~0.009: 0.005~0.01: 60~150.
The particle diameter of described nano magnetic iron oxide crystal grain is 10~130 nanometers; The particle diameter of preferred nano crystal particles is 30~80 nanometers.
The particle diameter of the submicron particles of described polystyrene is 80~900 nanometers, is preferably 100~260 nanometers.
The rate of addition of described syringe pump is 0.01~1.0 ml/min, is preferably 0.1~0.5 ml/min.
Described divalent iron salt is iron protochloride or Iron diacetate etc.
Described rare gas element is nitrogen, argon gas or helium.
Raw material used in the present invention and technological process all do not have detrimentally affect to environment, and method of the present invention time-saving and efficiency is simple, are easy to apply, and can effectively control the thickness of compound submicron particles coating layer.
Purposes of the present invention: end-use of the present invention is extensive, be the basic raw material of high function magnetic fluid, magnetic refrigeration, information storage and bioseparation and catalytic material, can be applicable to fields such as catalystic material, high-performance stirring sealing, bio-pharmaceuticals and magnetic conductance electricity slurry.
Method of the present invention not only energy consumption is low, the product purity height, and good dispersity, and polymer microballoon surface magnetic particulate coated state can be controlled by changing reaction conditions.
Adopt method of the present invention to obtain the polymer microballoon/magnetic granules composite material of multiple coated state, as shown in Figures 1 and 2.
Description of drawings
Fig. 1. the polymer microballoon of embodiments of the invention 1/magnetic granules composite material electromicroscopic photograph.
Fig. 2. the polymer microballoon of embodiments of the invention 4/magnetic granules composite material electromicroscopic photograph.
Embodiment
Embodiment 1:
Get 60~80 milliliters of 240 nano pipe/polyhenylethylene microballoon emulsions, add the dilution of 1.5 liters of distilled waters and stir.30~100mmol saltpetre is added wherein, under agitation slowly be warming up to 80~100 ℃; 10~100mmol hexamethylenetetramine and 10~160mmol iron protochloride are respectively charged in the syringe, and the injection speed with 0.1~0.5 ml/min under feeding nitrogen protection slowly is added to it in system successive reaction.Injection finishes the back and continues reaction 30~90 minutes.Centrifugation then, rotating speed are 1000~6000 rev/mins; After removing supernatant liquor, add 1.5 milliliters of distilled water washings again, recentrifuge separates.Toasted 24 hours down at 70 ℃ at last, the particle diameter that promptly obtains examining is that 240 nanometers, shell are the composite particles of 40~60 nanometers.
Embodiment 2:
Get 80~100 milliliters of the polystyrene microsphere emulsions of 340 nanometers, add 2.0 liters of distilled waters dilutions and stir.50~80mmol saltpetre is added wherein, under agitation slowly be warming up to 80~100 ℃; 10~100mmol hexamethylenetetramine and 50~120mmol ferrous chloride are respectively charged in the syringe, and the injection speed with 0.1~0.5 ml/min under feeding nitrogen protection slowly is added to it in system successive reaction.Injection finishes the back and continues reaction 30 minutes.Centrifugation then, rotating speed are 1000~4000 rev/mins; After removing supernatant liquor, add 2.0 liters of distilled water washings again, recentrifuge separates.Toasted 24 hours down at 70 ℃ at last, the particle diameter that promptly obtains examining is that 340 nanometers, shell are the composite particles of 50~120 nanometers.
Embodiment 3:
Get 80~110 milliliters of the polystyrene microsphere emulsions of 320~380 nanometers, add 2800 milliliters of distilled waters dilutions and stir.50~80mmol saltpetre is added wherein, under agitation slowly be warming up to 80 ℃; 10~100mmol hexamethylenetetramine and 50~90mmol ferrous chloride are respectively charged in the syringe, and the injection speed with 0.3~0.6 ml/min under feeding nitrogen protection slowly is added to it in system successive reaction.Injection finishes the back and continues reaction 30~90 minutes.Centrifugation then, rotating speed are 1000~2000 rev/mins; After removing supernatant liquor, add 3000 milliliters of distilled water washings again, recentrifuge separates.Toasted 24 hours down at 70 ℃ at last, the particle diameter that promptly obtains examining is that 320~380 nanometers, shell are the composite particles of 30~60 nanometers.
Embodiment 4:
Get 80 milliliters of 300 nano pipe/polyhenylethylene microballoon emulsions, add the dilution of 3.0 liters of distilled waters and stir.50~80mmol saltpetre is added wherein, under agitation slowly be warming up to 70~95 ℃; 10~100mmol hexamethylenetetramine and 60~120mmol ferrous chloride are respectively charged in the syringe, and the injection speed with 0.1~0.5 ml/min under feeding nitrogen protection slowly is added to it in system successive reaction.Injection is respectively charged into 10~50mmol hexamethylenetetramine and 30~50mmol ferrous chloride in the syringe after finishing again, injects with the speed of 0.1~0.5 ml/min, has annotated the back and has continued reaction 30~40 minutes.Centrifugation then, rotating speed are 1000~3000 rev/mins; After removing supernatant liquor, add 3.0 liters of distilled water washings again, recentrifuge separates.Toasted 24 hours down at 70 ℃ at last, the particle diameter that promptly obtains examining is that 300 nanometers, shell are the composite particles of 80~150 nanometer thickness.
Embodiment 5:
Get 30~40 milliliters of 160 nano pipe/polyhenylethylene microballoon emulsions, add the dilution of 1.5 liters of distilled waters and stir.20~60mmol saltpetre is added wherein, under agitation slowly be warming up to 80~100 ℃; 10~60mmol hexamethylenetetramine and 10~100mmol iron protochloride are respectively charged in the syringe, and the injection speed with 0.1~0.5 ml/min under feeding nitrogen protection slowly is added to it in system successive reaction.Injection finishes the back and continues reaction 30~90 minutes.Centrifugation then, rotating speed are 1000~6000 rev/mins; After removing supernatant liquor, add 1.5 milliliters of distilled water washings again, recentrifuge separates.Toasted 24 hours down at 70 ℃ at last, the particle diameter that promptly obtains examining is that 160 nanometers, shell are the composite particles of 20~50 nanometers.
Embodiment 6:
Get 60~80 milliliters of 240 nano pipe/polyhenylethylene microballoon emulsions, add the dilution of 1.5 liters of distilled waters and stir.30~100mmol saltpetre is added wherein, under agitation slowly be warming up to 80~100 ℃; 10~100mmol hexamethylenetetramine and 10~160mmol Iron diacetate are respectively charged in the syringe, and the injection speed with 0.1~0.5 ml/min under feeding nitrogen protection slowly is added to it in system successive reaction.Injection finishes the back and continues reaction 30~90 minutes.Centrifugation then, rotating speed are 1000~6000 rev/mins; After removing supernatant liquor, add 1.5 milliliters of distilled water washings again, recentrifuge separates.Toasted 24 hours down at 70 ℃ at last, the particle diameter that promptly obtains examining is that 240 nanometers, shell are the composite particles of 40~60 nanometers.
Embodiment 7:
Get 60~80 milliliters of 240 nano pipe/polyhenylethylene microballoon emulsions, add the dilution of 1.5 liters of distilled waters and stir.30~100mmol saltpetre is added wherein, under agitation slowly be warming up to 80~100 ℃; 10~100mmol hexamethylenetetramine and 10~180mmol Iron diacetate are respectively charged in the syringe, and the injection speed with 1.0~2.5 ml/min under feeding nitrogen protection slowly is added to it in system successive reaction.Injection finishes the back and continues reaction 30~90 minutes.Centrifugation then, rotating speed are 1000~6000 rev/mins; After removing supernatant liquor, add 1.5 milliliters of distilled water washings again, recentrifuge separates.Toasted 24 hours down at 70 ℃ at last, the particle diameter that promptly obtains examining is that 240 nanometers, shell are the composite particles of 20~60 nanometers.
Claims (10)
1. one kind coats the method that organic microballoon prepares compound submicron magnetic-particle with the nano magnetic iron oxide particle, it is characterized in that:
Get the polystyrene microsphere emulsion, adding is the deionized water dilution of 8~15 times of polystyrene microsphere emulsion volumes and stirs, adds saltpetre, hexamethylenetetramine and deionized water then, stir, drip divalent iron salt solution, slowly be warming up to 70~120 ℃, successive reaction obtains ferrum collosol; Centrifugation, washing and drying promptly obtains core/shell structure, the compound submicron particles of the organic microballoon that coats with the nano magnetic iron oxide crystal grain;
The concentration of described polystyrene microsphere emulsion is 10~15wt%;
Divalent iron salt in the described ferrum collosol: saltpetre: hexamethylenetetramine: the mol ratio of water is 0.01~0.16: 0.003~0.01: 0.001~0.01: 50~170.
2. the method for claim 1, it is characterized in that: the divalent iron salt in the described ferrum collosol: saltpetre: hexamethylenetetramine: the mol ratio of water is 0.05~0.12: 0.005~0.01: 0.005~0.01: 55~160.
3. method as claimed in claim 2 is characterized in that: the divalent iron salt in the described ferrum collosol: saltpetre: hexamethylenetetramine: the mol ratio of water is 0.05~0.12: 0.004~0.009: 0.005~0.01: 60~150.
4. the method for claim 1 is characterized in that: described dropping divalent iron salt solution carries out feeding under the protection of inert gas.
5. method as claimed in claim 4 is characterized in that: described rare gas element is nitrogen, argon gas or helium.
6. the method for claim 1, it is characterized in that: described nano magnetic iron oxide particle grain size is 10~130 nanometers.
7. method as claimed in claim 6 is characterized in that: described nano magnetic iron oxide particle grain size is 30~80 nanometers.
8. the method for claim 1, it is characterized in that: described dropping divalent iron salt solution speed is 0.01~1.0 ml/min.
9. as claim 1,2,3,4 or 8 described methods, it is characterized in that: described divalent iron salt is iron protochloride or Iron diacetate.
10. the method for claim 1, it is characterized in that: described polystyrene microsphere particulate is of a size of 80~900 nanometers.
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CN1303136C (en) * | 2004-11-18 | 2007-03-07 | 同济大学 | Method for preparing hollow magnetic composite particulate for magnetic rheologic liquid by using polystyrene microsphere |
CN100505116C (en) * | 2004-11-19 | 2009-06-24 | 南京大学 | Fe/(SiO-[2]+C) core-shell composite nanometer particle with high stability and method for preparing same |
CN1971780B (en) * | 2005-11-23 | 2010-04-21 | 北京化工大学 | Preparing method of nano-Fe3O4 coating carbon nanoube magnetic composite material |
CN101735367B (en) * | 2008-11-24 | 2011-05-25 | 中国石油天然气股份有限公司 | Preparation method of nano magnetic polymer composite microspheres |
CN101555166B (en) * | 2009-05-12 | 2012-07-04 | 东北大学 | Method for preparing ferric oxide ceramic thin film on the surface of three-dimensional network silicon carbide |
CN103134926A (en) * | 2013-02-27 | 2013-06-05 | 上海交通大学 | Magnetic microsphere carrier and its making method |
CN110187104A (en) * | 2019-06-13 | 2019-08-30 | 华中农业大学 | Preparation method, sensor and its application of lateral relaxation time immunosensor based on bio-orthogonal reaction |
CN110187104B (en) * | 2019-06-13 | 2021-09-14 | 华中农业大学 | Preparation method of transverse relaxation time immunosensor based on bioorthogonal reaction, sensor and application thereof |
TWI782633B (en) * | 2021-07-21 | 2022-11-01 | 竹笙化奈米科技有限公司 | Magnetic metal shell layer coated with polymer particles and method for producing the same for anti-electromagnetic wave textile yarn |
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