CN105950148A - Preparation method for preparing ferroferric oxide hollow ball-based fluorescent magnetic composite material - Google Patents
Preparation method for preparing ferroferric oxide hollow ball-based fluorescent magnetic composite material Download PDFInfo
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Abstract
The present invention discloses a preparation method for preparing a ferroferric oxide hollow ball-based fluorescent magnetic composite material. According to the method, ferric chloride, urea, polystyrene beads, poly-N-vinyl pyrrolidone and water are mixed up, and then an obtained mixed solution A is aged. After that, the obtained solution is cooled, centrifuged, separated, washed and dried in the vacuum state to obtain ferric hydroxide-coated polystyrene bead particles. Yttrium oxide and europium oxide are dissolved in nitric acid to prepare a mixed solution B. The mixed solution B, water and urea are mixed and stirred until a clear solution is formed. After that, the ferric hydroxide-coated polystyrene bead particles are added and an obtained mixture is subjected to ultrasonic dispersion. The mixture is heated to 90-110 DEG C, stirred for 3-4 hours, cooled, centrifuged and washed to obtain a product. The product is subjected to vacuum drying and heat treatment twice to obtain a target product. The prepared composite material is high in specific surface area, good in cavity-carrying property, small in particle density, and good in dispersibility. Meanwhile, the composite material has a good application prospect in the fields of drug transmission, drug storage and drug release.
Description
Technical field
The present invention relates to the preparation field of nano composite material, be specifically related to a kind of empty based on ferroso-ferric oxide
The preparation method of the magnetic fluorescent composite material of bulbus cordis.
Background technology
In recent years, along with development and the progress of biotechnology, the performance of biomaterial is proposed more by people
High requirement, the biomaterial of simple function can not meet the need of clinical medicine and experimentation
Ask.Therefore, researcher begins to focus on and how to be realized by the way of certain combines by the material of simple function
The multifunction of biomaterial, this kind of multifunctional biomaterials can because possessing the multiformity of performance, structure
Particularity and be widely used in biomedical aspect.
Magnetic Fe under nanometer range3O4Material demonstrates superparamagnetism, under the effect of externally-applied magnetic field
There is good magnetic response degree, but magnetic nano-particle does not possess mark function.Additionally, in research
In fluorescent characteristic material, lanthanide series rare-earth doped it is considered in fluorescent biolabels the one of most Research Prospects
Class fluorescent material.Therefore, if combining in a composite nanoparticle by magnetic and fluorescence function, this will be big
Promote greatly its range of application at biomedical sector.
At present, some researcheres have been prepared the most by means of which and have been had magnetic and epipolic solid concurrently
The nano-complex particle of spherical looks, although can simultaneously realize targeted drug and fluorescent labeling, but
Cavity medicine carrying is not possessed owing to the nano-complex particle of medicine ball pattern exists low specific surface area
The shortcomings such as the big poor dispersion of particle density, also lack application in medicine transmission storage with release field
Prospect.
Application publication number is the Chinese invention of CN 103923656A (Application No. 201310013691.4)
The preparation method of patent application publication a kind of Gadolinia. coated ferroferric oxide magnetic fluorescence nano hollow ball,
Comprise the steps: 1) take nano SiO 2 particle 1.2～1.6g, add 10～25mL distilled water,
Prepare silica colloid solution；Take nine water ferric nitrates 0.200～0.268g and carbamide 0.200～0.300g is molten
In 20～25mL distilled water, prepare A mixed liquor；2) by above-mentioned prepared silica colloid solution
Mix with A mixed liquor, prepare B mixed liquor, add 40mL～80mL distilled water, at 80 DEG C～95 DEG C
Stir 4～6 hours under temperature conditions, obtain bronzing homogeneous system, cooling, obtain red-brownish coloured particles and sink
Form sediment, complete to be coated with for the first time outside granule；3) by after above-mentioned red-brownish coloured particles precipitation cleaning-drying, take
1.0～1.5g, add 10～25mL distilled water, prepare homogeneous colloids solution；Take six water Gadolinium trinitrates
0.200～0.310g and carbamide 0.200～0.300g be dissolved in 20～25mL distilled water, prepare C mixed liquor；
4) by step 3) the homogeneous colloids solution prepared and the mixing of C mixed liquor, prepare solution D, add 40～80ml
Distilled water, stirs 4～6 hours at a temperature of 80～95 DEG C, obtains red homogeneous system, cooling, obtains
Red granules precipitates, and completes second time cladding outside granule；5) take the red granules after above-mentioned cladding to carry out
Core etching, goes the red granules precipitation of bottom；6) after the red granules of bottom being precipitated cleaning-drying
The Gd of the i.e. available required preparation of the dried powder hydrogen reducing obtained2O3Parcel Fe3O4Magnetic fluorescence
Nano-hollow ball.But, owing to chemical etching method is relatively big to the dependency dissolving environment, subsequent treatment is adopted
Remove template with highly basic NaOH etching kernel, not only increase technological process, and be easily destroyed target
Nanostructured in material, additionally, system can be caused by impurity introduced in mould material course of dissolution
Impact.
Summary of the invention
For solving the technical problem of above-mentioned existence, meeting the clinical and needs of medical research, the present invention provides
The preparation method of a kind of magnetic fluorescent composite material based on ferroso-ferric oxide hollow ball, uses polyphenyl second
Alkene pearl is that template is prepared for based on Fe3O4The magnetic fluorescent composite material of hollow ball, has high specific surface
The characteristics such as the long-pending cavity medicine carrying little good dispersion of particle density, can effectively overcome and solve above-mentioned
Problems of the prior art, thus strengthen it before medicine transmission storage with the application in release field
Scape.
The preparation method of a kind of magnetic fluorescent composite material based on ferroso-ferric oxide hollow ball, including following
Step:
1) ferric chloride, carbamide, polystyrene bead, poly N-vinyl pyrrolidone and water are mixed,
Prepare A mixed liquor, A mixed liquor be aged under 90～110 DEG C of temperature conditionss 20～24h, cool down afterwards,
Obtain red-brownish coloured particles precipitation；
2) red-brownish coloured particles precipitation is dispersed in water, centrifugal, separate, wash and obtain granule precipitate；
3) granule precipitate is vacuum dried under the conditions of temperature 70 C～80 DEG C 10～12h, obtains hydrogen-oxygen
Change granule (PS@Fe (OH) of ferrum cladding polystyrene bead3)；
4) take yittrium oxide, europium oxide is dissolved in nitric acid, ultrasonic 10～30min until mixed liquor is completely dissolved,
Add ammonia and remove the nitric acid of excess, regulate pH to 2～3, prepare B mixed liquor；
5) by B mixed liquor, water, carbamide mix and blend until forming settled solution, hydrated ferric oxide. is added
The granule of cladding polystyrene bead, ultrasonic disperse, prepare C mixed liquor；
6) C mixed liquor being heated to 90～110 DEG C, stirring maintains 3h～4h, cooling, is centrifuged afterwards,
Remove the supernatant, then granule is precipitated ultrasonic disperse in water, washing, obtain product；
7) product vacuum is dried, obtains being coated with the magnetic fluorescence granular precursor of polystyrene bead
(PS@Fe(OH)3@(Y,Eu)(OH)CO3·H2O)；
8) by the magnetic fluorescence granular precursor of cladding polystyrene bead under argon atmosphere,
450～500 DEG C of heat treatments 2～3h, remove PS pearl by thermal decomposition, it is thus achieved that hollow ball Fe3O4@
(Y,Eu)(OH)CO3·H2O particle, the most further at 700～800 DEG C of heat treatments 1～3h, it is thus achieved that hollow
Magnetic fluorescent nanometer particle (the Hollow sphere Fe of ball3O4@Y2O3:Eu3+), i.e. based on four oxidations three
The magnetic fluorescent composite material of ferrum hollow ball.
Step 1) in, in A mixed liquor, the concentration of ferric chloride is 1.0～2.0mmol/L, carbamide
Concentration is 0.2～0.3mol/L, and the concentration of polystyrene bead is 0.1～0.2g/L, poly N-vinyl pyrrolidine
The mass percent of ketone is 0.2%～0.4%；
20～24h it are aged so that iron salt homogeneously precipitates in polystyrene bead under 90～110 DEG C of temperature conditionss
Surface, cooling, obtain red-brownish coloured particles precipitation.
Step 2) in, described centrifugal condition is: at 6000～10000 revs/min centrifugal 5～20min.
Step 4) in, described nitric acid uses dust technology, and the mass percent of dust technology is 20%～40%；
Step 5) in, the time of described mix and blend is 20～30min；
Step 6) in, described centrifugal condition is: employing centrifuge speed 6000～8000 revs/min,
8～10min, i.e. at 6000～8000 revs/min centrifugal 8～10min.
Step 7) in, described vacuum drying condition is: vacuum under the conditions of temperature 70 C～80 DEG C
It is dried 10h～12h.
Step 8) in, described heat treatment is carried out in tube furnace.
Compared with prior art, the invention have the benefit that
One, through twice cladding on the surface of polystyrene bead, obtain corresponding presoma, then lead to
Overheating Treatment technique, final acquisition magnetic fluorescent composite material based on ferroso-ferric oxide hollow ball, this system
Preparation Method technique high, operation safety simple, repeatable；
Two, the composite obtained has good fluorescence property, compared to Gadolinia. parcel four oxidation
Three-iron magnetic fluorescence nano hollow ball particle, by rare earth ion Eu3+Doping, preparation based on four oxygen
The fluorescence property changing three-iron hollow ball magnetic fluorescent particles gets a promotion.
Three, obtained hollow ball compound particle good dispersion, specific surface area is high, and cavity medicine carrying is good；
Four, the target-oriented drug of magnetic material, fluorescent material markup can be realized simultaneously and possess medicine
Thing transmission, storage and release function, will be greatly expanded biomedical application prospect and using value.
Five, in the present invention, proposition is a kind of using polystyrene bead as template, is synthesized by homogeneous precipitation process
The hollow ball Fe of particle size uniformity3O4@Y2O3:Eu3+Nanoparticle, it is thus achieved that magnetic fluorescence hollow ball
Particle has the advantages such as high specific surface area cavity medicine carrying good dispersion, by magnetic behavior and glimmering
While optical property rolls into one, there is again medicine transmission storage and release function, lead in biomedicine
Territory has preferable potential application foreground and is worth.
Accompanying drawing explanation
Fig. 1 is the hollow ball Fe prepared in embodiment 13O4@Y2O3:Eu3+Nanoparticle X-ray is spread out
Penetrate figure；
Fig. 2 is polystyrene bead granule (PS@Fe (OH) of hydrated ferric oxide. cladding in embodiment 13)
SEM schemes, and in Fig. 2, (a) and (b) is the polystyrene bead granule of hydrated ferric oxide. cladding under different multiplying
(PS@Fe(OH)3) SEM figure；
Fig. 3 is the hollow ball Fe of preparation in 254nm burst of ultraviolel embodiment 13O4@Y2O3:Eu3+Receive
The fluorescence emission spectrogram of rice corpuscles；
Fig. 4 is embodiment 1 hollow bulbus cordis Fe3O4@Y2O3:Eu3+The magnetic hysteresis of nanoparticle returns line chart.
Detailed description of the invention
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Embodiment 1
1) by ferric chloride, carbamide, polystyrene bead (diameter: 600nm), poly N-vinyl pyrroles
Alkanone and water mixing, prepared A mixed liquor, ferric chloride 1.50mM (mmol/L) in A mixed liquor,
Carbamide 0.24mol/L in A mixed liquor, in A mixed liquor, the concentration of polystyrene bead is 0.2g/L, A mixing
In liquid, the mass percent of poly N-vinyl pyrrolidone is 0.3wt%；
2) above-mentioned A mixed liquor is moved in reactor (capacity: 50mL), 100 DEG C of temperature conditionss
Lower ageing 24h so that iron salt homogeneously precipitates in the surface of polystyrene bead, cooling, obtain bronzing
Grain precipitation；
3) by step 2) in preparation red-brownish coloured particles precipitation dispersion in deionized water, use centrifuge
Rotating speed 8000 revs/min, 10min, remove the supernatant, the granule after being processed, then will process
After granule ultrasonic disperse in deionized water, obtain granule precipitate；
4) step 3) in triplicate, acquisition granule precipitate is placed in vacuum drying oven, in temperature
Under the conditions of 75 DEG C, it is dried 12h, obtains polystyrene bead granule (PS@Fe (OH) of hydrated ferric oxide. cladding3)；
5) take 0.95mmol yittrium oxide, 0.05mmol europium oxide, be dissolved in dust technology (wt30%), super
Sound 30min, until mixed liquor is completely dissolved, adds ammonia and removes the nitric acid of excess, and solution ph regulates
2.5, prepare B mixed liquor；
6) by B mixed liquor, deionized water (60mL), carbamide (6.0g) mix and blend 30min is straight
To forming settled solution, add PS@Fe (OH) of 2mg3(the i.e. polystyrene bead of hydrated ferric oxide. cladding
Granule) ultrasonic disperse, prepare C mixed liquor；
7) C mixed liquor is heated to 90 DEG C, is stirred vigorously maintenance 4h, cooling, uses centrifuge speed
8000 revs/min, 10min, remove the supernatant, then granule is precipitated ultrasonic disperse in deionized water,
Wash three times, obtain product；
8) product is placed in vacuum drying oven, under the conditions of temperature 75 DEG C, is dried 12h, is coated with
Magnetic fluorescence granular precursor (PS@Fe (OH) of polystyrene bead3@(Y,Eu)(OH)CO3·H2O)；
9) the magnetic fluorescence granular precursor of cladding polystyrene bead is placed in tube furnace, argon atmosphere
Under, heat treatment 500 DEG C, 3h, remove PS pearl by thermal decomposition, it is thus achieved that hollow ball
Fe3O4@(Y,Eu)(OH)CO3·H2O particle, then further heat treatment 800 DEG C, 2h, it is thus achieved that hollow
Magnetic fluorescent nanometer particle (the Hollow sphere Fe of ball3O4@Y2O3:Eu3+), heat treatment process in
Temperature tube furnace is carried out.
Fig. 1 is the hollow ball Fe prepared in embodiment 13O4@Y2O3:Eu3+Nanoparticle X-ray is spread out
Penetrate figure, the standard card Fe as it is shown in figure 1, thing is consistent3O4:PDF#75-1610,Y2O3:PDF#88-1040。
Fig. 2 is polystyrene bead granule (PS@Fe (OH) of hydrated ferric oxide. cladding in embodiment 13)
SEM schemes, and in Fig. 2, (a) and (b) is the polystyrene bead granule of hydrated ferric oxide. cladding under different multiplying
(PS@Fe(OH)3) SEM figure.Figure shows: the polystyrene bead granule of hydrated ferric oxide. cladding
(PS@Fe(OH)3) there is good spherical morphology, good dispersion, uniform particle sizes.
Fig. 3 is the hollow ball Fe of preparation in 254nm burst of ultraviolel embodiment 13O4@Y2O3:Eu3+Receive
The fluorescence emission spectrogram of rice corpuscles.Figure shows: there is at 612nm good Eu3+Transmitting
Peak, can be used in fluorescence display.
Fig. 4 is embodiment 1 hollow bulbus cordis Fe3O4@Y2O3:Eu3+The magnetic hysteresis of nanoparticle returns line chart,
The saturation magnetization of magnetic fluorescent nanometer particle based on ferroso-ferric oxide hollow ball has as seen from the figure
Magnetic behavior.
In a word, the present invention proposes a kind of using polystyrene bead as template, closed by homogeneous precipitation process
Become the hollow ball Fe of particle size uniformity3O4@Y2O3:Eu3+Nanoparticle, it is thus achieved that magnetic fluorescence hollow
Spherolite has the advantages such as high specific surface area cavity medicine carrying good dispersion, by magnetic behavior and
While fluorescence property rolls into one, there is again medicine transmission storage and release function, in biomedicine
Field has preferable potential application foreground and is worth.
Embodiment 2
1) by ferric chloride, carbamide, polystyrene bead (diameter: 600nm), poly N-vinyl pyrroles
Alkanone and water mixing, prepared A mixed liquor, ferric chloride 1.00mM (mmol/L) in A mixed liquor,
Carbamide 0.2mol/L in A mixed liquor, in A mixed liquor, the concentration of polystyrene bead is 0.1g/L, A mixing
In liquid, the mass percent of poly N-vinyl pyrrolidone is 0.2wt%；
2) above-mentioned A mixed liquor is moved in reactor (capacity: 50mL), 100 DEG C of temperature conditionss
Lower ageing 24h so that iron salt homogeneously precipitates in the surface of polystyrene bead, cooling, obtain bronzing
Grain precipitation；
3) by step 2) in preparation red-brownish coloured particles precipitation dispersion in deionized water, use centrifuge
Rotating speed 7000 revs/min, 15min, remove the supernatant, the granule after being processed, then will process
After granule ultrasonic disperse in deionized water, obtain granule precipitate；
4) step 3) in triplicate, acquisition granule precipitate is placed in vacuum drying oven, in temperature
Under the conditions of 80 DEG C, it is dried 10h, obtains polystyrene bead granule (PS@Fe (OH) of hydrated ferric oxide. cladding3)；
5) take 0.95mmol yittrium oxide, 0.05mmol europium oxide, be dissolved in dust technology (wt30%), super
Sound 20min, until mixed liquor is completely dissolved, adds ammonia and removes the nitric acid of excess, and solution ph regulates
3, prepare B mixed liquor；
6) by B mixed liquor, deionized water (60mL), carbamide (6.0g) mix and blend 20min is straight
To forming settled solution, add PS@Fe (OH) of 2mg3(the i.e. polystyrene bead of hydrated ferric oxide. cladding
Granule) ultrasonic disperse, prepare C mixed liquor；
7) C mixed liquor is heated to 100 DEG C, is stirred vigorously maintenance 3.5h, cooling, uses centrifuge
Rotating speed 9000 revs/min, 8min, remove the supernatant, then granule is precipitated ultrasonic disperse at deionization
In water, wash three times, obtain product；
8) product is placed in vacuum drying oven, under the conditions of temperature 70 C, is dried 12h, is coated with
Magnetic fluorescence granular precursor (PS@Fe (OH) of polystyrene bead3@(Y,Eu)(OH)CO3·H2O)；
9) the magnetic fluorescence granular precursor of cladding polystyrene bead is placed in tube furnace, argon atmosphere
Under, heat treatment 450 DEG C, 3h, remove PS pearl by thermal decomposition, it is thus achieved that hollow ball
Fe3O4@(Y,Eu)(OH)CO3·H2O particle, then further heat treatment 750 DEG C, 2h, it is thus achieved that hollow
Magnetic fluorescent nanometer particle (the Hollow sphere Fe of ball3O4@Y2O3:Eu3+), heat treatment process in
Temperature tube furnace is carried out.
Embodiment 3
1) by ferric chloride, carbamide, polystyrene bead (diameter: 600nm), poly N-vinyl pyrroles
Alkanone and water mixing, prepared A mixed liquor, ferric chloride 2.00mM (mmol/L) in A mixed liquor,
Carbamide 0.3mol/L in A mixed liquor, in A mixed liquor, the concentration of polystyrene bead is 0.2g/L, A mixing
In liquid, the mass percent of poly N-vinyl pyrrolidone is 0.4wt%；
2) above-mentioned A mixed liquor is moved in reactor (capacity: 50mL), 110 DEG C of temperature conditionss
Lower ageing 20h so that iron salt homogeneously precipitates in the surface of polystyrene bead, cooling, obtain bronzing
Grain precipitation；
3) by step 2) in preparation red-brownish coloured particles precipitation dispersion in deionized water, use centrifuge
Rotating speed 9000 revs/min, 8min, remove the supernatant, the granule after being processed, after then processing
Granule ultrasonic disperse in deionized water, obtain granule precipitate；
4) step 3) in triplicate, acquisition granule precipitate is placed in vacuum drying oven, in temperature
Under the conditions of 70 DEG C, it is dried 12h, obtains polystyrene bead granule (PS@Fe (OH) of hydrated ferric oxide. cladding3)；
5) take 0.95mmol yittrium oxide, 0.05mmol europium oxide, be dissolved in dust technology (wt30%), super
Sound 20min, until mixed liquor is completely dissolved, adds ammonia and removes the nitric acid of excess, and solution ph regulates
3, prepare B mixed liquor；
6) by B mixed liquor, deionized water (60mL), carbamide (6.0g) mix and blend 20min is straight
To forming settled solution, add PS@Fe (OH) of 2mg3(the i.e. polystyrene bead of hydrated ferric oxide. cladding
Granule) ultrasonic disperse, prepare C mixed liquor；
7) C mixed liquor is heated to 110 DEG C, is stirred vigorously maintenance 3h, cooling, uses centrifugal basket
Speed 7000 revs/min, 15min, remove the supernatant, then granule is precipitated ultrasonic disperse at deionization
In water, wash three times, obtain product；
8) product is placed in vacuum drying oven, under the conditions of temperature 80 DEG C, is dried 10h, is coated with
Magnetic fluorescence granular precursor (PS@Fe (OH) of polystyrene bead3@(Y,Eu)(OH)CO3·H2O)；
9) the magnetic fluorescence granular precursor of cladding polystyrene bead is placed in tube furnace, argon atmosphere
Under, heat treatment 450 DEG C, 3h, remove PS pearl by thermal decomposition, it is thus achieved that hollow ball
Fe3O4@(Y,Eu)(OH)CO3·H2O particle, then further heat treatment 750 DEG C, 2h, it is thus achieved that hollow
Magnetic fluorescent nanometer particle (the Hollow sphere Fe of ball3O4@Y2O3:Eu3+), heat treatment process in
Temperature tube furnace is carried out.
Claims (8)
1. a preparation method for magnetic fluorescent composite material based on ferroso-ferric oxide hollow ball, it is special
Levy and be, comprise the following steps:
1) ferric chloride, carbamide, polystyrene bead, poly N-vinyl pyrrolidone and water are mixed,
Prepare A mixed liquor, A mixed liquor be aged under 90～110 DEG C of temperature conditionss 20～24h, cool down afterwards,
Obtain red-brownish coloured particles precipitation；
2) red-brownish coloured particles precipitation is dispersed in water, centrifugal, separate, wash and obtain granule precipitate；
3) granule precipitate is vacuum dried under the conditions of temperature 70 C～80 DEG C 10～12h, obtains hydrogen-oxygen
Change the granule of ferrum cladding polystyrene bead；
4) take yittrium oxide, europium oxide is dissolved in nitric acid, ultrasonic 10～30min until mixed liquor is completely dissolved,
Add ammonia and remove the nitric acid of excess, regulate pH to 2～3, prepare B mixed liquor；
5) by B mixed liquor, water, carbamide mix and blend until forming settled solution, hydrated ferric oxide. is added
The granule of cladding polystyrene bead, ultrasonic disperse, prepare C mixed liquor；
6) C mixed liquor being heated to 90～110 DEG C, stirring maintains 3h～4h, cooling, is centrifuged afterwards,
Remove the supernatant, then granule is precipitated ultrasonic disperse in water, washing, obtain product；
7) product vacuum is dried, obtains being coated with the magnetic fluorescence granular precursor of polystyrene bead；
8) by the magnetic fluorescence granular precursor of cladding polystyrene bead under argon atmosphere,
450～500 DEG C of heat treatments 2～3h, remove PS pearl by thermal decomposition, it is thus achieved that hollow ball particle, then enter
One step is at 700～800 DEG C of heat treatments 1～3h, it is thus achieved that magnetic fluorescence based on ferroso-ferric oxide hollow ball is multiple
Condensation material.
Magnetic fluorescent composite material based on ferroso-ferric oxide hollow ball the most according to claim 1
Preparation method, it is characterised in that step 1) in, in A mixed liquor, the concentration of ferric chloride is 1.0～2.0
Mmol/L, the concentration of carbamide is 0.2～0.3mol/L, and the concentration of polystyrene bead is 0.1～0.2g/L, poly-
The mass percent of NVP is 0.2%～0.4%.
Magnetic fluorescent composite material based on ferroso-ferric oxide hollow ball the most according to claim 1
Preparation method, it is characterised in that step 2) in, described centrifugal condition is: 6000～10000
Revs/min centrifugal 5～20min.
Magnetic fluorescent composite material based on ferroso-ferric oxide hollow ball the most according to claim 1
Preparation method, it is characterised in that step 4) in, described nitric acid uses dust technology, dust technology
Mass percent is 20%～40%.
Magnetic fluorescent composite material based on ferroso-ferric oxide hollow ball the most according to claim 1
Preparation method, it is characterised in that step 5) in, the time of described mix and blend is 20～30min.
Magnetic fluorescent composite material based on ferroso-ferric oxide hollow ball the most according to claim 1
Preparation method, it is characterised in that step 6) in, described centrifugal condition is: 6000～8000
Revs/min centrifugal 8～10min.
Magnetic fluorescent composite material based on ferroso-ferric oxide hollow ball the most according to claim 1
Preparation method, it is characterised in that step 7) in, described vacuum drying condition is: in temperature
10h～12h it is vacuum dried under the conditions of 70 DEG C～80 DEG C.
Magnetic fluorescent composite material based on ferroso-ferric oxide hollow ball the most according to claim 1
Preparation method, it is characterised in that step 8) in, described heat treatment is carried out in tube furnace.
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| CN111498911A (en) * | 2020-04-22 | 2020-08-07 | 常熟理工学院 | Purple Fe with monodisperse hollow structure3O4@SiO2Material and preparation method |
| CN113247958A (en) * | 2021-06-04 | 2021-08-13 | 国网河南省电力公司许昌供电公司 | Magnetic fluorescent nano composite material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102198385A (en) * | 2011-05-23 | 2011-09-28 | 同济大学 | Preparation method of magnetic fluorescence dual-function silicon oxide hollow microspheres |
| CN103215037A (en) * | 2013-03-29 | 2013-07-24 | 长春理工大学 | Method for synthesizing upconversion fluorescence hollow nanosphere based on sodium polyacrylate microsphere template synthesis |
| CN103923656A (en) * | 2013-01-14 | 2014-07-16 | 宁波大学 | Preparation method of gadolinium oxide-coated ferroferric oxide magnetic fluorescent nano hollow spheres |
| CN104562295A (en) * | 2014-12-29 | 2015-04-29 | 长春理工大学 | Erbium-doped yttrium oxysulfide up-conversion luminescent hollow nanofibers and preparation method thereof |
| CN104588027A (en) * | 2015-01-26 | 2015-05-06 | 太原理工大学 | Preparation method of multifunctional nano composite with yellow shell structure |
-
2016
- 2016-04-29 CN CN201610282135.0A patent/CN105950148A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102198385A (en) * | 2011-05-23 | 2011-09-28 | 同济大学 | Preparation method of magnetic fluorescence dual-function silicon oxide hollow microspheres |
| CN103923656A (en) * | 2013-01-14 | 2014-07-16 | 宁波大学 | Preparation method of gadolinium oxide-coated ferroferric oxide magnetic fluorescent nano hollow spheres |
| CN103215037A (en) * | 2013-03-29 | 2013-07-24 | 长春理工大学 | Method for synthesizing upconversion fluorescence hollow nanosphere based on sodium polyacrylate microsphere template synthesis |
| CN104562295A (en) * | 2014-12-29 | 2015-04-29 | 长春理工大学 | Erbium-doped yttrium oxysulfide up-conversion luminescent hollow nanofibers and preparation method thereof |
| CN104588027A (en) * | 2015-01-26 | 2015-05-06 | 太原理工大学 | Preparation method of multifunctional nano composite with yellow shell structure |
Non-Patent Citations (2)
| Title |
|---|
| LIZHU TONG等: "Magnetic and luminescent Fe3O4/Y2O3:Eu3+ composites with hollow spheres and mesoporous silica", 《DYES AND PIGMENTS》 * |
| 李旺: "磁性-荧光性复合纳米材料多功能空心球的制备与表征", 《宁波大学硕士学位论文》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108956828A (en) * | 2018-06-11 | 2018-12-07 | 安徽省佳逸环保科技有限公司 | A kind of method of trace halogenated biphenyl in quick detection water body |
| CN108956828B (en) * | 2018-06-11 | 2021-11-02 | 安徽省佳逸环保科技有限公司 | Method for rapidly detecting trace halogenated biphenyl in water body |
| CN108956982A (en) * | 2018-07-09 | 2018-12-07 | 广州华澳生物科技有限公司 | A kind of rheumatoid arthritis marker joint quantitative testing test paper and preparation method thereof |
| CN111498911A (en) * | 2020-04-22 | 2020-08-07 | 常熟理工学院 | Purple Fe with monodisperse hollow structure3O4@SiO2Material and preparation method |
| CN111498911B (en) * | 2020-04-22 | 2021-11-05 | 常熟理工学院 | Purple Fe with monodisperse hollow structure3O4@SiO2Material and preparation method |
| CN113247958A (en) * | 2021-06-04 | 2021-08-13 | 国网河南省电力公司许昌供电公司 | Magnetic fluorescent nano composite material and preparation method and application thereof |
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