CN103157412A - Preparation method of electromagnetic composite hollow microspheres - Google Patents
Preparation method of electromagnetic composite hollow microspheres Download PDFInfo
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- CN103157412A CN103157412A CN2013100973251A CN201310097325A CN103157412A CN 103157412 A CN103157412 A CN 103157412A CN 2013100973251 A CN2013100973251 A CN 2013100973251A CN 201310097325 A CN201310097325 A CN 201310097325A CN 103157412 A CN103157412 A CN 103157412A
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Abstract
The invention provides a preparation method of electromagnetic composite hollow microspheres, relates to a preparation method of a composite hollow material and aims to solve the problems of poor conductivity, high density and high falling possibility of magnetic particles of the existing composite hollow material. The preparation method comprises the following steps: 1, preparing polystyrene microspheres; 2, dispersing the polystyrene microspheres in concentrated sulfuric acid, and sulfonating; 3, preparing a magnetic Fe3O4 nano particle suspension; 4, adding the sulfonic-group-containing SPS microspheres and the Fe3O4 nano particle suspension into a water solution; 5, adding ethanol and ammonia water, and dropwisely adding ethyl orthosilicate; 6, adding into a PVP-containing ethanol solution, and stirring; and 7, mixing an aniline solution with the PVP modified magnetic microspheres, dropwisely adding ammonium persulfate, drying, adding N,N-dimethylformamide, and soaking. For the prepared hollow microspheres, the conductivity is 0.01-1.0 S/cm, the density is low, and the magnetic particles are less prone to fall; and the hollow microspheres are mainly used in the fields of light-weight electromagnetic materials, photonic crystals, wave-absorbing materials and the like.
Description
Technical field
The present invention relates to a kind of composite hollow material preparation method.
Background technology
Tiny balloon all has potential application prospect in fields such as catalysis, drug delivery, artificial cell, light filler, insulating materials, advanced low-k materials and photonic crystals, has caused extensive concern.
At present, the method for preparation from nanoscale to micron-sized tiny balloon is a lot, and existing preparation method mainly comprises emulsion method, spray drying process, template and without template etc.Template nucleocapsid template particularly wherein, cause scholar's broad research interest, the committed step of this structure of nucleocapsid template synthesis relates to the shell that coats or react the another kind of material of formation at a kind of particle surface, its composition is adjustable, can be metal and oxide, polymer, inorganic matter and organic/inorganic composite.By introduce functional mass on shell, can change surface charge, the surface reaction characteristic of compound particle and strengthen the stable and dispersed of particle, give simultaneously the functional of compound particle.The surface deposition reaction is two kinds of main method of preparation nucleocapsid and tiny balloon structure composite particle with successively alternately adsorbing.The method of having reported is based on all that on template, functional group induces conducting polymer compound, carry out again the compound of magnetic ferroferric oxide, but because the composite material conductive network that forms is intercepted by outer field tri-iron tetroxide, and the alkaline environment that uses in the tri-iron tetroxide deposition process has also caused the dedoping of polyaniline, and then causes the product conductance of gained low.
Summary of the invention
The present invention seeks to for solve existing composite hollow material poorly conductive, density is large and the caducous problem of magnetic-particle, and provides a kind of preparation method of electromagnetism compound hollow microballoon.
The preparation method of electromagnetism compound hollow microballoon of the present invention follows these steps to realize:
One, with the AIBN(azodiisobutyronitrile of 0.4～0.8g), the mass concentration of 63～127g is 95% ethanol, the distilled water of 3.3～6.7g and the PVP(PVP of 1.0～2.0g) add in reactor, the St(styrene that adds 13.3～26.7g after stirring), be uniformly dispersed, it is 70～75 ℃ in reaction temperature, speed of agitator is 90～110r/min, react 10～14h under the condition of nitrogen protection, obtain the PS(polystyrene) microballoon;
Two, with the PS(polystyrene that obtains in step 1) to be scattered in mass concentration be in 98% sulfuric acid to microballoon, at 35～50 ℃ of lower sulfonation 1～4h, then wash 2～4 times with ethanol, then be washed to centrifugal rear supernatant liquor pH=6, obtain the surface after freeze drying and have sulfonic SPS microballoon;
Three, FeCl
36H
2O and FeCl
24H
2O is dissolved in distilled water, adds the pH=11 of the NaOH solution regulation system of 2mol/L, the temperature of 60～80 ℃, is washed till filtrate pH=7 with distilled water after reacting 1～3.0h under the condition of nitrogen protection, then is distributed in the aqueous solution, is configured to magnetic Fe
3O
4Nano granule suspension;
Four, in mass ratio for (4～6): 1 surface that step 2 is obtained has the magnetic Fe that sulfonic SPS microballoon and step 3 obtain
3O
4It is that in 3～5 hydrochloric acid solution, stirring reaction 20～40min obtains surface recombination Fe that nano granule suspension joins pH
3O
4The SPS microballoon;
Five, to surface recombination Fe
3O
4The SPS microballoon in add absolute ethyl alcohol, then to add ammoniacal liquor regulation system pH be 9～10, drips the ethyl orthosilicate of 0.3～1.0mL under mechanical agitation, obtains SiO
2The magnetic microsphere that coats;
Six, the SiO that step 5 is obtained
2The magnetic microsphere that coats joins and contains the PVP(polyvinylpyrrolidone) ethanolic solution in, stir after 5～6h standing 5～6h again, filter the magnetic microsphere that post-drying obtains the PVP modification;
seven, be that 50～60:1 mixes to get aniline solution with water and aniline by volume, add hydrochloric acid to regulate pH=1.5 in aniline solution, be that 20～25:1 mixes to get ammonium persulfate solution with water and ammonium persulfate in mass ratio, ammonium persulfate solution adds hydrochloric acid to regulate pH=1.5, the aniline solution of pH=1.5 and the magnetic microsphere of PVP modification are mixed, and then splash into the ammonium persulfate solution of pH=1.5, reacted under 0～5 ℃ 12～24 hours, get the electromagnetism complex microsphere after washing drying, add again N, dinethylformamide soaked the electromagnetism complex microsphere 2～10 hours, obtain the electromagnetism compound hollow microballoon.
The electromagnetism compound hollow microballoon that obtains by preparation method of the present invention is take magnetic ferroferric oxide as internal layer, and electrically conductive polyaniline is outer field composite hollow material.Magnetic-particle difficult drop-off on the electromagnetism compound hollow microballoon utilizes sulfonic acid group to Fe
3O
4Adsorptivity guarantees that magnetic-particle can be attached to microsphere surface, is being attached with Fe again simultaneously
3O
4The microsphere surface of particle synthesizes one deck SiO
2Clad can protect the internal magnetization particle not dissolve under the acid condition of aniline polymerization like this, again the hollow material after synthetic is increased one deck and prevents the overcoat that magnetic-particle comes off, then at SiO
2The outer polymerization one deck polyaniline again of layer, i.e. conductive layer, so direct contact external environment be conductive layer, protected magnetic-particle, prevented coming off of magnetic-particle.The saturated magnetization rate of the electromagnetism compound hollow microballoon that obtains is 1～8emu/g, and conductance is 0.01～1.0S/cm, and density is 0.85～1.00g/cm
3
Description of drawings
Fig. 1 is the PS(polystyrene that in embodiment one, step 1 obtains) stereoscan photograph of microballoon;
Fig. 2 is the stereoscan photograph that surface that in embodiment one, step 2 obtains has sulfonic SPS microballoon;
Fig. 3 is Fe in step 3 in embodiment one
3O
4XRD figure;
Fig. 4 is surface recombination Fe in step 4 in embodiment one
3O
4SPS microballoon stereoscan photograph;
Fig. 5 is the scanning electron microscope (SEM) photograph of the electromagnetism compound hollow microballoon that obtains of embodiment one.
The specific embodiment
The specific embodiment one: the preparation method of the square electromagnetism compound hollow microballoon of this enforcement follows these steps to implement:
One, with the AIBN(azodiisobutyronitrile of 0.4～0.8g), the mass concentration of 63～127g is 95% ethanol, the distilled water of 3.3～6.7g and the PVP(PVP of 1.0～2.0g) add in reactor, the St(styrene that adds 13.3～26.7g after stirring), be uniformly dispersed, it is 70～75 ℃ in reaction temperature, speed of agitator is 90～110r/min, react 10～14h under the condition of nitrogen protection, obtain the PS(polystyrene) microballoon;
Two, with the PS(polystyrene that obtains in step 1) to be scattered in mass concentration be in 98% sulfuric acid to microballoon, at 35～50 ℃ of lower sulfonation 1～4h, then wash 2～4 times with ethanol, then be washed to centrifugal rear supernatant liquor pH=6, obtain the surface after freeze drying and have sulfonic SPS microballoon;
Three, FeCl
36H
2O and FeCl
24H
2O is dissolved in distilled water, adds the pH=11 of the NaOH solution regulation system of 2mol/L, the temperature of 60～80 ℃, is washed till filtrate pH=7 with distilled water after reacting 1～3.0h under the condition of nitrogen protection, then is distributed in the aqueous solution, is configured to magnetic Fe
3O
4Nano granule suspension;
Four, in mass ratio for (4～6): 1 surface that step 2 is obtained has the magnetic Fe that sulfonic SPS microballoon and step 3 obtain
3O
4It is that in 3～5 hydrochloric acid solution, stirring reaction 20～40min obtains surface recombination Fe that nano granule suspension joins pH
3O
4The SPS microballoon;
Five, to surface recombination Fe
3O
4The SPS microballoon in add absolute ethyl alcohol, then to add ammoniacal liquor regulation system pH be 9～10, drips the ethyl orthosilicate of 0.3～1.0mL under mechanical agitation, obtains SiO
2The magnetic microsphere that coats;
Six, the SiO that step 5 is obtained
2The magnetic microsphere that coats joins and contains the PVP(polyvinylpyrrolidone) ethanolic solution in, stir after 5～6h standing 5～6h again, filter the magnetic microsphere that post-drying obtains the PVP modification;
seven, be that 50～60:1 mixes to get aniline solution with water and aniline by volume, add hydrochloric acid to regulate pH=1.5 in aniline solution, be that 20～25:1 mixes to get ammonium persulfate solution with water and ammonium persulfate in mass ratio, ammonium persulfate solution adds hydrochloric acid to regulate pH=1.5, the aniline solution of pH=1.5 and the magnetic microsphere of PVP modification are mixed, and then splash into the ammonium persulfate solution of pH=1.5, reacted under 0～5 ℃ 12～24 hours, get the electromagnetism complex microsphere after washing drying, add again N, dinethylformamide soaked the electromagnetism complex microsphere 2～10 hours, obtain the electromagnetism compound hollow microballoon.
Polystyrene microsphere is processed in the present embodiment sulfonation, utilizes electrostatic absorption principle magnetic ferroferric oxide in the absorption of sulfonated polystyrene microsphere surface, more compound one deck SiO
2, further adopting the PVP(polyvinylpyrrolidone) and effects on surface is with SiO
2Microballoon carry out the active absorption that is beneficial to polyaniline of processing.By changing the PVP(polyvinylpyrrolidone) processing time, control the content of microsphere surface composite conducting polyaniline, adopt at last the DMF dissolving to remove polystyrene moulding, obtaining internal layer is that magnetosphere, skin are the hollow material of conductive layer.This electromagnetism compound hollow microballoon has guaranteed the continuity of conducting medium, has improved the conductance of magnetic material, has reduced the density of composite hollow material.
The specific embodiment two: what present embodiment was different from the specific embodiment one is the PS(polystyrene of step 2 2g) to be scattered in the 40ml mass concentration be in 98% sulfuric acid to microballoon.Other step and parameter are identical with the specific embodiment one.
The specific embodiment three: what present embodiment was different from the specific embodiment one or two is that step 3 is that 1.5:1 is FeCl in molar ratio
36H
2O and FeCl
24H
2O is dissolved in distilled water.Other step and parameter are identical with the specific embodiment one or two.
The specific embodiment four: that present embodiment is different from one of specific embodiment one to three is the surface recombination Fe of step 5 1～2g
3O
4The SPS microballoon in add the absolute ethyl alcohol of 30～70ml.Other step and parameter are identical with one of specific embodiment one to three.
The specific embodiment five: what present embodiment was different from one of specific embodiment one to four is that step 5 drips the ethyl orthosilicate of 0.3～1.0mL under mechanical agitation, and the speed that drips ethyl orthosilicate is to drip 0.05～0.1mL ethyl orthosilicate every 1h.Other step and parameter are identical with one of specific embodiment one to four.
The specific embodiment six: what present embodiment was different from one of specific embodiment one to four is that step 5 drips the ethyl orthosilicate of 0.6～0.8mL under mechanical agitation, and the speed that drips ethyl orthosilicate is to drip 0.06～0.08mL ethyl orthosilicate every 1h.Other step and parameter are identical with one of specific embodiment one to four.
The specific embodiment seven: that present embodiment is different from one of specific embodiment one to six is the SiO that step 6 obtains 0.5～1.0g step 5
2The magnetic microsphere that coats joins and contains 2.5～5.0gPVP(polyvinylpyrrolidone) 100～200ml ethanolic solution in.Other step and parameter are identical with one of specific embodiment one to six.
The specific embodiment eight: what present embodiment was different from one of specific embodiment one to seven is to add hydrochloric acid adjusting pH=1.5 and ammonium persulfate solution to add hydrochloric acid to regulate pH=1.5 in the step 7 aniline solution, and wherein the concentration of hydrochloric acid is 2mol/L.Other step and parameter are identical with one of specific embodiment one to seven.
Embodiment one: the preparation method of the present embodiment electromagnetism compound hollow microballoon follows these steps to implement:
One, with the AIBN(azodiisobutyronitrile of 0.6g), the mass concentration of 95g is 95% ethanol, the distilled water of 5g and the PVP(PVP of 1.5g) add in reactor, the St(styrene that adds 20g after stirring), be uniformly dispersed, it is 75 ℃ in reaction temperature, speed of agitator is 100r/min, react 12h under the condition of nitrogen protection, obtain the PS(polystyrene) microballoon;
Two, with the PS(polystyrene that obtains in step 1) to be scattered in mass concentration be in 98% 40ml sulfuric acid to microballoon, at 40 ℃ of lower sulfonation 4h, then wash 3 times with ethanol, then be washed to centrifugal rear supernatant liquor pH=6, obtain the surface after freeze drying and have sulfonic SPS microballoon;
Three, be that 1.5:1 is FeCl in molar ratio
36H
2O and FeCl
24H
2O is dissolved in distilled water, adds the pH=11 of the NaOH solution regulation system of 2mol/L, the temperature of 80 ℃, is washed till filtrate pH=7 with distilled water after reaction 1h under the condition of nitrogen protection, then is distributed in the aqueous solution, is configured to magnetic Fe
3O
4Nano granule suspension;
Four, the surface that for 5:1, step 2 is obtained in mass ratio has the magnetic Fe that sulfonic SPS microballoon and step 3 obtain
3O
4Nano granule suspension joins in the hydrochloric acid solution of pH=4, and stirring reaction 30min obtains surface recombination Fe
3O
4The SPS microballoon;
Five, to surface recombination Fe
3O
4The SPS microballoon in add absolute ethyl alcohol, then to add ammoniacal liquor regulation system pH be 10, drips the ethyl orthosilicate of 0.7mL under mechanical agitation, obtains SiO
2The magnetic microsphere that coats;
Six, the 0.5g SiO that step 5 is obtained
2The magnetic microsphere that coats joins and contains 2.5g PVP(polyvinylpyrrolidone) the 100ml ethanolic solution in, stir after 6h standing 5h again, filter the magnetic microsphere that post-drying obtains the PVP modification;
seven, for 54.17:1, water and aniline are mixed to get aniline solution by volume, add hydrochloric acid to regulate pH=1.5 in aniline solution, for 22.1:1, water and ammonium persulfate are mixed to get ammonium persulfate solution in mass ratio, ammonium persulfate solution adds hydrochloric acid to regulate pH=1.5, the aniline solution of pH=1.5 and the magnetic microsphere of PVP modification are mixed, and then splash into the ammonium persulfate solution of pH=1.5, reaction is 12 hours under 5 ℃, get the electromagnetism complex microsphere after washing drying, add again N, dinethylformamide soaked the electromagnetism complex microsphere 3 hours, obtain the electromagnetism compound hollow microballoon.
Wherein step 5 drips the ethyl orthosilicate of 0.7mL under mechanical agitation, and the speed that drips ethyl orthosilicate is to drip the 0.07mL ethyl orthosilicate every 1h.
The PS(polystyrene that the present embodiment step 1 obtains) stereoscan photograph of microballoon as shown in Figure 1, demonstrates the PS microsphere features smooth surface by Fig. 1, the basic globulate of particle, and size distribution is more even.
The stereoscan photograph that the surface that the present embodiment step 2 obtains has a sulfonic SPS microballoon demonstrates the surface by Fig. 2 and has the basic globulate of sulfonic SPS microsphere particle as shown in Figure 2, and significant change does not occur surface texture.
Fe in the present embodiment step 3
3O
4XRD figure as shown in Figure 3, demonstrate Fe by Fig. 3
3O
4Has good crystalline texture.
The present embodiment step 4 obtains surface recombination Fe
3O
4SPS microballoon scanning electron microscope (SEM) photograph as shown in Figure 4, demonstrate particle balling preparation shape by Fig. 4, even particle size distribution is compared its rough surface with the SPS microsphere particle and is obviously increased, and shows that the SPS surface successfully is compounded with Fe
3O
4Particle.
The scanning electron microscope (SEM) photograph of the electromagnetism compound hollow microballoon that the present embodiment obtains as shown in Figure 5, find out that by this figure the electromagnetism composite hollow material that obtains is spherical structure, demonstrate electromagnetism composite hollow material and contain pore space structure (arrow indication) from the sample that breaks on a small quantity, show that sample is hollow material.
The saturated magnetization rate of the electromagnetism compound hollow microballoon that the present embodiment obtains is 6emu/g, and conductance is 0.8S/cm, and density is 0.92g/cm
3
Claims (8)
1. the preparation method of an electromagnetism compound hollow microballoon is characterized in that the preparation method of electromagnetism compound hollow microballoon follows these steps to realize:
One, the mass concentration with AIBN, the 63～127g of 0.4～0.8g is that 95% ethanol, the distilled water of 3.3～6.7g and the PVP of 1.0～2.0g add in reactor, the St that adds 13.3～26.7g after stirring, be uniformly dispersed, it is 70～75 ℃ in reaction temperature, speed of agitator is 90～110r/min, react 10～14h under the condition of nitrogen protection, obtain the PS microballoon;
Two, the PS microballoon that obtains in step 1 being scattered in mass concentration is in 98% sulfuric acid, at 35～50 ℃ of lower sulfonation 1～4h, then wash 2～4 times with ethanol, then be washed to centrifugal rear supernatant liquor pH=6, obtain the surface after freeze drying and have sulfonic SPS microballoon;
Three, FeCl
36H
2O and FeCl
24H
2O is dissolved in distilled water, adds the pH=11 of the NaOH solution regulation system of 2mol/L, the temperature of 60～80 ℃, is washed till filtrate pH=7 with distilled water after reacting 1～3.0h under the condition of nitrogen protection, then is distributed in the aqueous solution, is configured to magnetic Fe
3O
4Nano granule suspension;
Four, in mass ratio for (4～6): 1 surface that step 2 is obtained has the magnetic Fe that sulfonic SPS microballoon and step 3 obtain
3O
4It is that in 3～5 hydrochloric acid solution, stirring reaction 20～40min obtains surface recombination Fe that nano granule suspension joins pH
3O
4The SPS microballoon;
Five, to surface recombination Fe
3O
4The SPS microballoon in add absolute ethyl alcohol, then to add ammoniacal liquor regulation system pH be 9～10, drips the ethyl orthosilicate of 0.3～1.0mL under mechanical agitation, obtains SiO
2The magnetic microsphere that coats;
Six, the SiO that step 5 is obtained
2The magnetic microsphere that coats joins in the ethanolic solution that contains PVP, stirs after 5～6h standing 5～6h again, filters the magnetic microsphere that post-drying obtains the PVP modification;
seven, be that 50～60:1 mixes to get aniline solution with water and aniline by volume, add hydrochloric acid to regulate pH=1.5 in aniline solution, be that 20～25:1 mixes to get ammonium persulfate solution with water and ammonium persulfate in mass ratio, ammonium persulfate solution adds hydrochloric acid to regulate pH=1.5, the aniline solution of pH=1.5 and the magnetic microsphere of PVP modification are mixed, and then splash into the ammonium persulfate solution of pH=1.5, reacted under 0～5 ℃ 12～24 hours, get the electromagnetism complex microsphere after washing drying, add again N, dinethylformamide soaked the electromagnetism complex microsphere 2～10 hours, obtain the electromagnetism compound hollow microballoon.
2. the preparation method of a kind of electromagnetism compound hollow microballoon according to claim 1, it is in 98% sulfuric acid that the PS microballoon that it is characterized in that step 2 2g is scattered in the 40ml mass concentration.
3. the preparation method of a kind of electromagnetism compound hollow microballoon according to claim 1, is characterized in that step 3 is that 1.5:1 is FeCl in molar ratio
36H
2O and FeCl
24H
2O is dissolved in distilled water.
4. the preparation method of a kind of electromagnetism compound hollow microballoon according to claim 1 is characterized in that the surface recombination Fe of step 5 1～2g
3O
4The SPS microballoon in add the ethanol of 30～70ml.
5. the preparation method of a kind of electromagnetism compound hollow microballoon according to claim 1, it is characterized in that step 5 drips the ethyl orthosilicate of 0.3～1.0mL under mechanical agitation, the speed that drips ethyl orthosilicate is to drip 0.05～0.1mL ethyl orthosilicate every 1h.
6. the preparation method of a kind of electromagnetism compound hollow microballoon according to claim 5, it is characterized in that step 5 drips the ethyl orthosilicate of 0.6～0.8mL under mechanical agitation, the speed that drips ethyl orthosilicate is to drip 0.06～0.08mL ethyl orthosilicate every 1h.
7. the preparation method of a kind of electromagnetism compound hollow microballoon according to claim 1 is characterized in that the magnetic microsphere that SiO2 that step 6 obtains 0.5～1.0g step 5 coats joins in the 100～200ml ethanolic solution that contains 2.5～5.0gPVP.
8. the preparation method of a kind of electromagnetism compound hollow microballoon according to claim 1, is characterized in that adding in the step 7 aniline solution hydrochloric acid adjusting pH=1.5 and ammonium persulfate solution to add hydrochloric acid to regulate pH=1.5, and wherein the concentration of hydrochloric acid is 2mol/L.
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| CN103611479A (en) * | 2013-12-04 | 2014-03-05 | 江南大学 | Preparation method of Fe3O4/SiO2/PANI (Polyaniline) nano particle with core-shell structure |
| CN103657614A (en) * | 2013-12-26 | 2014-03-26 | 南京大学 | Polystyrene based magnetic nano ferroferric oxide arsenic removal composite and preparation method thereof |
| CN104746346A (en) * | 2015-04-20 | 2015-07-01 | 湖州哲豪丝绸有限公司 | Method for preparing novel flexible conductive fabric by using micro-sphere self-assembly technology |
| CN106749791A (en) * | 2016-12-07 | 2017-05-31 | 河海大学 | A kind of low-density polystyrene microballoon and preparation method thereof |
| CN108531130A (en) * | 2018-03-03 | 2018-09-14 | 王艺霖 | A kind of preparation method of tiny balloon absorbing material |
| CN108609649A (en) * | 2018-05-22 | 2018-10-02 | 河北工业大学 | A kind of preparation method of sea urchin shape magnetic hollow microsphere |
| CN110586026A (en) * | 2019-10-09 | 2019-12-20 | 东南大学 | Adsorbent for removing heavy metal arsenic and preparation method and application 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 |
| CN112246196A (en) * | 2020-09-18 | 2021-01-22 | 四川迈克生物新材料技术有限公司 | Preparation method of functionalized magnetic microsphere, magnetic microsphere and application |
| CN113603983A (en) * | 2021-08-19 | 2021-11-05 | 安徽瑞琦塑胶科技有限公司 | Wave-absorbing plastic master batch and preparation method thereof |
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| CN103611479B (en) * | 2013-12-04 | 2016-04-13 | 江南大学 | A kind of Fe with nucleocapsid structure 3o 4/ SiO 2the preparation method of/PANI nano particle |
| CN103611479A (en) * | 2013-12-04 | 2014-03-05 | 江南大学 | Preparation method of Fe3O4/SiO2/PANI (Polyaniline) nano particle with core-shell structure |
| CN103657614A (en) * | 2013-12-26 | 2014-03-26 | 南京大学 | Polystyrene based magnetic nano ferroferric oxide arsenic removal composite and preparation method thereof |
| CN104746346A (en) * | 2015-04-20 | 2015-07-01 | 湖州哲豪丝绸有限公司 | Method for preparing novel flexible conductive fabric by using micro-sphere self-assembly technology |
| CN106749791B (en) * | 2016-12-07 | 2018-10-23 | 河海大学 | A kind of low-density polystyrene microballoon and preparation method thereof |
| CN106749791A (en) * | 2016-12-07 | 2017-05-31 | 河海大学 | A kind of low-density polystyrene microballoon and preparation method thereof |
| CN108531130A (en) * | 2018-03-03 | 2018-09-14 | 王艺霖 | A kind of preparation method of tiny balloon absorbing material |
| CN108609649A (en) * | 2018-05-22 | 2018-10-02 | 河北工业大学 | A kind of preparation method of sea urchin shape magnetic hollow microsphere |
| CN110586026A (en) * | 2019-10-09 | 2019-12-20 | 东南大学 | Adsorbent for removing heavy metal arsenic and preparation method and application 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 |
| CN112246196A (en) * | 2020-09-18 | 2021-01-22 | 四川迈克生物新材料技术有限公司 | Preparation method of functionalized magnetic microsphere, magnetic microsphere and application |
| CN113603983A (en) * | 2021-08-19 | 2021-11-05 | 安徽瑞琦塑胶科技有限公司 | Wave-absorbing plastic master batch and preparation method thereof |
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Application publication date: 20130619 |