CN1279554C - Magnetic iron oxide hollow microsphere particle having mesoporous structure and making method and uses thereof - Google Patents
Magnetic iron oxide hollow microsphere particle having mesoporous structure and making method and uses thereof Download PDFInfo
- Publication number
- CN1279554C CN1279554C CN 200310122436 CN200310122436A CN1279554C CN 1279554 C CN1279554 C CN 1279554C CN 200310122436 CN200310122436 CN 200310122436 CN 200310122436 A CN200310122436 A CN 200310122436A CN 1279554 C CN1279554 C CN 1279554C
- Authority
- CN
- China
- Prior art keywords
- particle
- iron oxide
- magnetic
- magnetic iron
- hollow microsphere
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The present invention belongs to the technical field of preparing inorganic hollow microsphere granules by using composite granules, particularly to magnetic iron oxide hollow granules with mesoporous structures and a method and a purpose for preparing the magnetic iron oxide hollow microsphere granules with the mesoporous structures by using magnetic iron oxide-organic composite granules with core / shell structures. The present invention controls hydrolysis by using ferrous iron salt solutions so as to prepare mesoporous magnetic iron oxide granules, and simultaneously, the mesoporous magnetic iron oxide granules are coated on organic microspheres, such as polystyrene, etc., and thus, mesoporous magnetic iron oxide composite microspheres with core / shell structures can be obtained. Organic cores in uniform composite granules can be sintered by slow temperature rise under the condition of no oxygen, and simultaneously, organic substances of shell layers in the iron oxide granules can also be sintered so as to obtain complete mesoporous magnetic iron oxide hollow microsphere granules. The wall thickness of the hollow granules can be effectively controlled by the thickness of different composite spherical shell layers.
Description
Technical field
The invention belongs to the technical field for preparing the inorganic hollow microsphere particle with composite particles, be particularly related to magnetic oxide hollow particle, reach the method and the purposes of the magnetic oxide hollow microsphere particle of mesoporous magnetic oxide-organic composite granulated preparation meso-hole structure of using core/shell structure with meso-hole structure.
Background technology
Inorganic porous material because have bigger specific area and adsorption capacity, and is widely used in catalyst and the absorption carrier.It is that the solid inorganic material of 1～10 nanometer is defined as mesoporous material that the aperture will be contained in International Union of Pure and Applied Chemistry.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.Over past ten years, the shell that pattern, size, structure can arbitrarily be controlled/nuclear magnetism nano material has begun to be applied in fields such as telecommunications, catalysis, bio-separation, medical images diagnosis, magnetic cooling and magnetic fluid.
Recently, people such as Frank Caruso upward (see also FrankCaruso with layer-layer coating method " Chemistry Material " (calendar year 2001s 13 are rolled up 109 pages) and " Science " (volume was 1111 pages in 1998 282), Marina Spasova, Andrei Susha.Chem.Mater.2001,13,109-116.and Caruso, F.; Caruso, R.A.; Mohwald, H.Science 1998,282, and 1111), the composite magnetic ball that obtains can obtain the magnetic hollow ball through oversintering again.People such as Srivastava have reported with the sonochemistry method in " Jounal.Physics.Chemistry.B " (volume was 1879 pages in 2002 108) and have prepared the mesoporous iron oxide particle.At present, the report that does not still have mesoporous magnetic hollow particle preparation both at home and abroad and use.
Summary of the invention
Main purpose of the present invention provide a kind ofly single disperse, particle diameter is controlled and narrowly distributing, have the magnetic oxide of meso-hole structure-organic composite granulated and have the magnetic oxide hollow particle of meso-hole structure.
A further object of the present invention is to provide the method with the mesoporous magnetic oxide-mesoporous magnetic oxide hollow microsphere of the organic composite granulated preparation particle of core/shell structure, and can effectively control the thickness of hollow ball wall.
Another order of the present invention is to provide the purposes with meso-hole structure magnetic oxide hollow particle.
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 mesoporous magnetic iron oxide particle it is coated on organic microballoons such as polystyrene, thereby obtains the mesoporous magnetic oxide complex microsphere of core/shell structure.
The present invention adopts organic microballoons such as polystyrene of different-grain diameter size; By the concentration of control divalent iron salt solution in these microballoon coating systems, can obtain the complex microsphere of different shell thicknesses, the nucleocapsid size of complex microsphere can obtain effectively control like this.
The present invention adopts under slow temperature-rising method and the oxygen free condition organic core sintering in the uniform composite particles is fallen, and the organic substance in the ferric oxide particles of shell also is sintered simultaneously, thereby obtains complete mesoporous magnetic oxide hollow microsphere particle.Adopt different composite balls shell thicknesses can effectively control the wall thickness of hollow particle.
Magnetic oxide hollow microsphere particle with meso-hole structure of the present invention, by particle size is that 10～180 nano magnetic iron oxides are formed, the hollow microsphere particle grain size is 120～500 nanometers, and wall thickness is 20～100 nanometers, and mesoporous aperture is 3～10 nanometers.
Described nano magnetic iron oxide particle grain size is preferably 30～80 nanometers.
The method that the magnetic oxide with meso-hole structure with core/shell structure of the present invention-organic composite granulated preparation has the magnetic oxide hollow microsphere particle of meso-hole structure may further comprise the steps:
(1). coat the preparation composite balls:
Get the organic microballoon emulsion of copolymerization, adding is 8～15 times of deionized water dilutions of emulsion and stirs, add ethylene glycol and hexamethylenetetramine then, stir and mix, feeding dropping divalent iron salt solution under the nitrogen protection, slowly be warming up to 70～120 ℃, 1～a few hours of successive reaction, obtain ferrum collosol; Centrifugation, washing and drying promptly obtains core/shell structure, the organic microballoon compound submicron particles that coats with the nano magnetic iron oxide particle;
(2). the preparation of hollow microsphere particle:
To have core/shell structure, the compound submicron particles of the organic microballoon that coats with the nano magnetic iron oxide particle joins in the porcelain crucible, and this porcelain crucible put into airtight sintering furnace, feed the high-purity inert protective gas then, slowly rise to sintering temperature after getting rid of the oxygen in the stove, and under this temperature, keep 3～5 hours; Slowly cool to room temperature afterwards again, obtain the mesoporous magnetic oxide hollow microsphere particle of forming by nano magnetic iron oxide.
Water in the described ferrum collosol: organic microballoon emulsion: ethylene glycol: divalent iron salt: the mol ratio of hexamethylenetetramine is 1000: 1～30: 100～300: 10～160: 1～200; Preferred water: organic microballoon emulsion: ethylene glycol: divalent iron salt: the mol ratio of hexamethylenetetramine is 1000: 2～20: 50～800: 20～120: 10～160.
Described organic microballoon is a polystyrene microsphere, and particle diameter is 120～500 nanometers; Preferable particle size is 200～300 nanometers.
Described nano magnetic iron oxide particle grain size is 10～180 nanometers; The particle diameter of preferred nano particle is 30～80 nanometers.
The particle diameter of the compound submicron particles of organic microballoon that described nano magnetic iron oxide particle coats is 120～900 nanometers, is preferably 260～460 nanometers.
Described mesoporous magnetic oxide hollow particle is that 10～180 nano magnetic iron oxides are formed by size, and the hollow microsphere particle grain size is 120～500 nanometers, and wherein mesoporous aperture is 3～10 nanometers.
Described divalent iron salt is frerrous chloride or ferrous nitrate.
Described sintering temperature is 320～780 ℃.
Described inert gas is nitrogen, argon gas or helium.
Programming rate during described sintering is 1～50 ℃/minute.
Cooling rate during described sintering is 1～50 ℃/minute.
The wall thickness of described hollow microsphere particle is 20～100 nanometers.
Raw material used in the present invention and preparation method's process all do not have harmful effect 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 hollow microsphere particle coating layer.
Hollow microsphere particle of the present invention is of many uses, is the base stock of high function magnetic fluid, magnetic refrigeration, information storage and bio-separation and catalysis material, also can be applicable to fields such as catalyst material, high-performance stirring sealing, bio-pharmaceuticals and magnetic conductance electricity slurry.
Can open up many new applications with the special nature that this high-performance magnetism fluid with magnetic hollow particle preparation of meso-hole structure is had, some insoluble engineering technology problems can be well solved, and potential application possibility are provided for many electronic components and complete machine.Introduce the application of several magnetic liquids below simply:
1. Dynamic Sealing sealing: magnetic liquid Dynamic Sealing Sealing Technology is that magnetic liquid also is one of most important applications than maturation, now has been widely used in the rotating shaft sealing that the X-ray changes precision instruments such as target diffractometer, single crystal growing furnace, high power laser, computer.Utilize external magnetic field magnetic liquid can be constrained in the sealing position and form magnetic liquid " O " type ring, have characteristics such as nothing leakage, no wearing and tearing, self-lubricating, life-span length.
2. ore dressing separates: the characteristics that the apparent specific gravity that utilizes magnetic liquid changes with the variation of external magnetic field, can be used to screen the different non magnetic ore of proportion, as be used for from the waste vapour car, reclaiming valuable non-ferrous metals such as copper, lead, aluminium, and from the alluvial gold gravity ore, reclaim free gold, it does not use mercury, is a kind of clean environment firendly beneficiation method that can use repeatedly.
3. magnetic liquid gyro: adopt liquid-bearing or simply cancel bearing and the magnetic liquid gyro made can be avoided gyrostatic drift and improve accuracy of navigation systems greatly.
4. magnetic developer: adopt magnetic liquid to do the domain structures such as domain shape, size and distribution that medium can not only be observed multiple magnetic material effectively, can also judge the quality of magnetic aligning, (without acid etching) records the size of grain size and the microphysics phenomenon of multiple material such as distribution mutually under the condition of not destroying sample.This developer can also show the particularly track part of video tape of tape.Combine with liquid crystalline phase with this developer and can be made into LCD, have the advantage that power consumption is little, price is low than common display.
5. magnetic liquid loud speaker: in the magnetic air gap of ventional loudspeakers, pour into magnetic liquid, make that it has the power output height, frequency characteristic is good, dynamic range is big, can satisfy the requirement of the people to the sound equipment high-fidelity.
6. magnetic liquid transformer: the iron core of traditional transformer can be made into magnetic liquid and design the transformer that the circulation approach of liquid is done, have radiating efficiency height, core loss little, shorten hyper band man-hour and need not the characteristics of cold oil greatly.
The medical usage of 7 magnetic liquids: magnetic injection, processing thrombus, separation various types of cells, magnetic method processing blood and marrow, research morphology of virus and the X-ray radiography that can do high curative effect.
8 little application of looking character: magnetic particle has well little to look character in liquid and produces magneto optical effect, it can be as magnetic sensors and photoelectric cell, directly measure without amplifier as the photon signal that optical fiber is transmitted, can also prepare optical shutter and modulator.
Method of the present invention not only energy consumption is low, the product purity height, and good dispersion, and the coated state of polymer microballoon surface magnetic particle can be controlled by changing reaction condition.
Adopt method of the present invention to obtain mesoporous magnetic iron oxide particle electromicroscopic photograph and mesoporous magnetic oxide hollow microsphere particle electromicroscopic photograph, as shown in Figures 1 and 2.
Description of drawings
Fig. 1. the mesoporous magnetic iron oxide particle electromicroscopic photograph of embodiments of the invention 2.
Fig. 2. the mesoporous magnetic oxide hollow microsphere particle electromicroscopic photograph of embodiments of the invention 3.
Embodiment
Embodiment 1:
Take from 80～100 milliliters of granules of polystyrene (240 nanometer) emulsions of system (or commercially available), add the ethylene glycol of 2.0 liters of distilled waters and 100～800 milliliters, and stir.Under agitation slowly be warming up to 80～100 ℃; 10～100mmol hexamethylenetetramine and 50～120mmol ferrous chloride slowly are added in the system successive reaction.Injection finishes the back and continues reaction 30 minutes.Centrifugation then, rotating speed are 1000～4000 rev/mins; After removing supernatant, add 2.0 liters of distilled water washings again, centrifugation once more, three times so repeatedly.At last 70 ℃ of down bakings 24 hours, promptly obtaining examining is that the compound submicron particles of organic microballoon that 240 nanometers, magnetic iron oxide particle coat be 320～380 nanometers, shell by particle diameter is that the magnetic iron oxide particle of 30～70 nanometers is formed, the mesoporous composite particles that is of a size of 3～7 nanometers.
Embodiment 2:
Take from 80～100 milliliters of granules of polystyrene (320～380 nanometer) emulsions of system (or commercially available), add the ethylene glycol of 2800 milliliters of distilled waters and 150～850 milliliters, and stir.Under agitation slowly be warming up to 80 ℃; 10～100mmol hexamethylenetetramine and 50～90mmol ferrous chloride solution slowly are added in the 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, add 3000 milliliters of distilled water washings again, centrifugation once more, three times so repeatedly.At last 70 ℃ of down bakings 24 hours, promptly obtaining examining is that the compound submicron particles of organic microballoon that 320～380 nanometers, magnetic iron oxide particle coat be 380～480 nanometers, shell by particle diameter is that the magnetic iron oxide particle of 30～80 nanometers is formed, the mesoporous composite particles that is of a size of 3～7 nanometers.
Embodiment 3:
Take from 80～100 milliliters of granules of polystyrene (300 nanometer) emulsions of system (or commercially available), add the ethylene glycol of 3.0 liters of distilled waters and 150～850 milliliters, and stir.Under agitation slowly be warming up to 70～95 ℃; 10～100mmol hexamethylenetetramine and 60～120mmol ferrous chloride slowly are added in the system successive reaction.Injection is respectively charged into 10～50mmol hexamethylenetetramine and 30～50mmol ferrous chloride in the injection-tube 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, add 3.0 liters of distilled water washings again, centrifugation once more.At last 70 ℃ of down bakings 24 hours, promptly obtaining examining is that the compound submicron particles of organic microballoon that 300 nanometers, magnetic iron oxide particle coat be 400～460 nanometers, shell by particle diameter is that the magnetic iron oxide particle of 40～80 nanometers is formed, the mesoporous composite particles that is of a size of 3～7 nanometers.
Embodiment 4
Getting embodiment 1 made (nucleocapsid) mesoporous magnetic oxide-organic complex microsphere 50～150 restrains, adds in the porcelain crucible, and put into 20 liters of airtight sintering furnaces.Feed the high-purity nitrogen protective gas then, the oxygen in the eliminating stove slowly rose to 550 ℃ sintering temperature with 10 ℃/minute speed, and keep 4～8 hours under this temperature after 30 minute; Slowly cool to room temperature with 10 ℃/minute speed more afterwards, the hollow structure, ball wall that obtains internal diameter size and be 220 nanometers, external diameter and be 310～370 nanometers is that the magnetic iron oxide particle of 30～70 nanometers is formed, the mesoporous magnetic microsphere particle that is of a size of 3～7 nanometers by particle diameter.Hollow microsphere in the accompanying drawing 1 is attracted on magnetic patch or the iron block easily, has shown magnetic.
Embodiment 5:
Getting embodiment 2 made (nucleocapsid) mesoporous magnetic oxide-organic complex microspheres 50～150 restrains, adds in the porcelain crucible, and put into 20 liters of airtight sintering furnaces.Feed the high purity argon protective gas then, the oxygen in the eliminating stove slowly rose to 550 ℃ sintering temperature with 10 ℃/minute speed, and keep 4～8 hours under this temperature after 30 minute; Slowly cool to room temperature with 10 ℃/minute speed more afterwards, the hollow structure, ball wall that obtains being of a size of 320～380 nanometers, external diameter and be 370～470 nanometers is that the magnetic iron oxide particle of 30～80 nanometers is formed, the mesoporous magnetic microsphere particle that is of a size of 3～7 nanometers by particle diameter.Mesoporous magnetic hollow microsphere in the accompanying drawing 2 is attracted on magnetic patch or the iron block easily, has shown magnetic.
Embodiment 6:
Getting embodiment 3 made (nucleocapsid) mesoporous magnetic oxide-organic complex microspheres 50～150 restrains, adds in the porcelain crucible, and put into 20 liters of airtight sintering furnaces.Feed the high-purity nitrogen protective gas then, the oxygen in the eliminating stove slowly rose to 550 ℃ sintering temperature with 20 ℃/minute speed, and keep 4～5 hours under this temperature after 30 minute; Slowly cool to room temperature with 20 ℃/minute speed more afterwards, the hollow structure, ball wall that obtains being of a size of 300 nanometers, external diameter and be 390～450 nanometers is that the magnetic iron oxide particle of 20～70 nanometers is formed, the mesoporous magnetic microsphere particle that is of a size of 3～7 nanometers by particle diameter.Made mesoporous magnetic hollow microsphere is attracted on magnetic patch or the iron block easily, has shown magnetic.
Claims (10)
1. magnetic oxide hollow microsphere particle with meso-hole structure, it is characterized in that: described hollow microsphere particle is that 10～180 nano magnetic iron oxides are formed by particle size, the hollow microsphere particle grain size is 120～500 nanometers, wall thickness is 20～100 nanometers, and mesoporous aperture is 3～10 nanometers.
2. hollow microsphere particle as claimed in claim 1 is characterized in that: described nano magnetic iron oxide particle grain size is 30～80 nanometers.
3. preparation method as each described hollow microsphere particle of claim 1～2, it is characterized in that: described method may further comprise the steps:
(1). coat the preparation composite balls:
Get the organic microballoon emulsion of copolymerization, adding is 8～15 times of deionized water dilutions of emulsion and stirs, adds ethylene glycol and hexamethylenetetramine then, stir and mix, feeding dropping divalent iron salt solution under the nitrogen protection, slowly be warming up to 70～120 ℃ of reactions, obtain ferrum collosol; Precipitation, washing and drying promptly obtains core/shell structure, the organic microballoon compound submicron particles that coats with the nano magnetic iron oxide particle;
(2). the preparation of hollow microsphere particle:
To have core/shell structure, the compound submicron particles of the organic microballoon that coats with the nano magnetic iron oxide particle joins in the container, and this container is put into airtight sintering furnace, feeds inert protective gas, slowly rises to sintering temperature after getting rid of the oxygen in the stove; Be cooled to room temperature, obtain the mesoporous magnetic oxide hollow microsphere particle of forming by nano magnetic iron oxide.
4. method as claimed in claim 3 is characterized in that: the water in the described ferrum collosol: organic microballoon emulsion: ethylene glycol: divalent iron salt: the mol ratio of hexamethylenetetramine is 1000: 1～30: 100～300: 10～160: 1～200.
5. method as claimed in claim 3 is characterized in that: the particle diameter of the compound submicron particles of organic microballoon that described nano magnetic iron oxide particle coats is 120～900 nanometers.
6. as claim 3,4 or 5 described methods, it is characterized in that: described organic microballoon is a polystyrene microsphere, and particle diameter is 120～500 nanometers.
7. as claim 3 or 5 described methods, it is characterized in that: described nano magnetic iron oxide particle grain size is 10～180 nanometers.
8. method as claimed in claim 3 is characterized in that: described divalent iron salt is frerrous chloride or ferrous nitrate.
9. method as claimed in claim 3 is characterized in that: described sintering temperature is 320～780 ℃.
10. purposes as each described hollow microsphere particle of claim 1～2, it is characterized in that: described hollow microsphere particle is applied to high function magnetic fluid, magnetic refrigeration, information storage, bio-separation, catalyst or high-performance and stirs encapsulant, and is applied to bio-pharmaceuticals and magnetic conductance electricity slurry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310122436 CN1279554C (en) | 2003-12-23 | 2003-12-23 | Magnetic iron oxide hollow microsphere particle having mesoporous structure and making method and uses thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310122436 CN1279554C (en) | 2003-12-23 | 2003-12-23 | Magnetic iron oxide hollow microsphere particle having mesoporous structure and making method and uses thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1632889A CN1632889A (en) | 2005-06-29 |
| CN1279554C true CN1279554C (en) | 2006-10-11 |
Family
ID=34844504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310122436 Expired - Fee Related CN1279554C (en) | 2003-12-23 | 2003-12-23 | Magnetic iron oxide hollow microsphere particle having mesoporous structure and making method and uses thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1279554C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101521067B (en) * | 2008-02-29 | 2012-03-07 | 桑迪亚医药技术（上海）有限责任公司 | Preparing method of core/shell type magnetic particle product and uses |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101077417B (en) * | 2006-05-26 | 2010-04-07 | 中国科学院理化技术研究所 | Magnetic target medicine sustained and controlled release carrier material and preparation method and application thereof |
| CN101236816B (en) * | 2007-12-11 | 2011-04-27 | 中国科学院上海硅酸盐研究所 | Making method for magnetic kernel medium hole hollow ball |
| CN102652729A (en) * | 2011-03-04 | 2012-09-05 | 香港中文大学 | Magnetic nanomaterials and methods for chemoembolisation |
| TWI482782B (en) | 2013-05-31 | 2015-05-01 | Univ Nat Chiao Tung | Antibody-conjugated double emulsion core-shell nano structure |
| CN104701137B (en) * | 2015-01-31 | 2018-06-15 | 华灿光电股份有限公司 | AlN buffer layers and with the buffer layer chip preparation method |
| CN106830095B (en) * | 2017-02-17 | 2018-08-24 | 中国市政工程中南设计研究总院有限公司 | A kind of meso-porous hollow iron oxide microballoon and preparation method thereof |
| CN109490524A (en) * | 2018-10-29 | 2019-03-19 | 东海县裕隆医学检验实验室有限公司 | A kind of immunomagnetic beads and preparation method thereof |
| CN109524192B (en) * | 2018-12-27 | 2020-05-22 | 华南理工大学 | Preparation method of high-coercivity magnetic nanoparticle suspension |
| CN113350520A (en) * | 2020-05-27 | 2021-09-07 | 复旦大学附属华山医院 | Hydrogen sulfide controlled-release brain targeting nano system for protecting nervous system after cardiac arrest and preparation method thereof |
-
2003
- 2003-12-23 CN CN 200310122436 patent/CN1279554C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101521067B (en) * | 2008-02-29 | 2012-03-07 | 桑迪亚医药技术（上海）有限责任公司 | Preparing method of core/shell type magnetic particle product and uses |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1632889A (en) | 2005-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Urchin-like GdPO 4 and GdPO 4: Eu 3+ hollow spheres–hydrothermal synthesis, luminescence and drug-delivery properties | |
| CN1279554C (en) | Magnetic iron oxide hollow microsphere particle having mesoporous structure and making method and uses thereof | |
| Mohan et al. | Fabrication of silver nanoparticles in hydrogel networks | |
| Wu et al. | Hematite hollow spheres with a mesoporous shell: controlled synthesis and applications in gas sensor and lithium ion batteries | |
| Chen et al. | Synthesis of core–shell micro/nanoparticles and their tribological application: a review | |
| Wang et al. | One-pot synthesis of nanotube-based hierarchical copper silicate hollow spheres | |
| Chen et al. | Magnetic nanofibers: unique properties, fabrication techniques, and emerging applications | |
| Ma et al. | Electrospinning preparation and properties of Fe 3 O 4/Eu (BA) 3 phen/PVP magnetic-photoluminescent bifunctional composite nanofibers | |
| Puglisi et al. | Monodisperse octahedral α-MnS and MnO nanoparticles by the decomposition of manganese oleate in the presence of sulfur | |
| JP2001513147A (en) | Materials based on porous metals and methods for their production | |
| EP1397243B1 (en) | Superparamagnetic nanostructured materials | |
| Liu et al. | Magnetic 3-D ordered macroporous silica templated from binary colloidal crystals and its application for effective removal of microcystin | |
| Parakhonskiy et al. | Magnetic and silver nanoparticle functionalized calcium carbonate particles—Dual functionality of versatile, movable delivery carriers which can surface-enhance Raman signals | |
| CN108249482B (en) | Magnetic Fe2O3Preparation method of nano particles and method for compounding nano particles with nano carbon material | |
| KR101683059B1 (en) | Fluorescent and magnetic core-shell nanochain structures and preparation method thereof | |
| CN109133189A (en) | The preparation method of carbon coated ferriferrous oxide nanoshell supported nano-gold particle | |
| Wang et al. | A simple route to form magnetic chitosan nanoparticles from coaxial-electrospun composite nanofibers | |
| Zhang et al. | Immobilization of penicillin G acylase on a novel paramagnetic composite carrier with epoxy groups | |
| Nguyen et al. | Analysis on development of magnetite hollow spheres through one‐pot solvothermal process | |
| Drag-Jarzabek et al. | Synthesis and structural characterization of a new molecular precursor for BaHfO3: a simple approach to Eu-based phosphors | |
| CN103923656A (en) | Preparation method of gadolinium oxide-coated ferroferric oxide magnetic fluorescent nano hollow spheres | |
| Hong et al. | Controlled synthesis of gadolinium fluoride upconversion nanoparticles capped with oleic acid or polyethylene glycol molecules via one-step hydrothermal method and their toxicity to cancer cells | |
| Liu et al. | Multifunctional PNIPAM/Fe3O4–ZnS hybrid hollow spheres: Synthesis, characterization, and properties | |
| CN110755383A (en) | Self-driven manganese dioxide nano motor and preparation method and application thereof | |
| CN106010500A (en) | Magnetic nano-luminescent material with core-shell structure and preparation method of magnetic nano-luminescent material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20061011 Termination date: 20161223 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |