CN104624189A - Magnetic titanium dioxide compound hollow microsphere and preparation method thereof - Google Patents
Magnetic titanium dioxide compound hollow microsphere and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a magnetic titanium dioxide compound hollow microsphere. According to the invention, nanometer magnetic materials are uniformly dispersed in titanium dioxide to form the spherical shell of the magnetic titanium dioxide compound hollow microsphere, wherein the thickness of the spherical shell accounts for 4-10% of the diameter of the sphere body and the adding amount of the magnetic materials accounts for 2-20wt% of the total quantity of the nanometer titanium dioxide and the magnetic materials. The invention also provides a preparation method of the magnetic titanium dioxide compound hollow microsphere. The method starts from raw materials and utilizes mixed crystal effect to directly regulate and control photocatalytic performances of a product. The method is simple and flexible in process, convenient to operate, rapid in speed, high in efficiency and easy to industrially produce on large scale. The product prepared according to the method has good photocatalytic performances and magnetism, so that recycling of the product after service is facilitated.
Description
Technical field
The invention belongs to the technical field of catalysis material, specifically relate to a kind of magnetic titanium dioxide composite hollow microballoon and preparation method thereof.
Background technology
Tellurian total Water is 1.386 × 10
18cubic meter, fresh water only accounts for 2.8%.In limited freshwater resources, polar glacier accounts for 75%, but this part freshwater resources is difficult to be utilized, and the another threat of directly being wasted and polluting of the utilized fresh water of not enough earth total Water 1%.Along with people are to the raising of quality of life and healthy attention degree, a lot of sewage disposal technology, drink water purifying technology are developed in succession.
From 1967, since Teng Dao finds photochemical catalyzing, photocatalysis technology can utilize sustainable clean solar energy as light source to drive light-catalyzed reaction because of it, and have important application prospect at the energy and environmental area, it causes the extensive concern of researcher.Wherein, titanium dioxide (TiO
2) be the photochemical catalyst that investigation and application is maximum, be commonly called as " titanium dioxide ", there is stable chemical property, Strong oxdiative ability, high-durability, and nontoxic cheapness.
Along with going deep into of research, light-catalyzed reaction mechanism is revealed more and more in detail, and corresponding light catalysis technique is also constantly developed improvement.But in actual application, pellet type catalyst, especially nano-scale particle catalyst, easily occur reunite and weaken its catalytic performance.In addition, pellet type catalyst is difficult to after being on active service in liquid phase environment recycle, thus limits the application of fine catalyst.
Current solution has: 1) by TiO
2in powder load to matrix or preparation TiO
2coating/thin film.Technics comparing is simple, easy to operate, TiO
2can be securely fixed on matrix, thus solve recycling problem.But TiO can be reduced largely so simultaneously
2the specific area of product, and then weaken photocatalysis performance.2) composite technology is utilized, by magnetic material and TiO
2carry out powder-product and carry out compound, make the powder of final preparation have certain magnetic, can be recycled by externally-applied magnetic field.
The Chinese patent literature being CN101816937A as publication number discloses a kind of magnetic loading type nano-photocatalyst TiO
2/ Fe
3o
4preparation method, by coprecipitation, with ferrous sulfate, ferric sulfate, ammoniacal liquor for primary raw material, prepare dispersed nanometer Fe preferably
3o
4particle, then use sol-gel process at Fe
3o
4surface coating one deck there is the TiO of photocatalytic
2, form the TiO of nucleocapsid structure
2/ Fe
3o
4composite.But be although that magnet carried photocatalyst prepared by carrier easily reclaims with magnetic particle, because its density is large, free settling not easily suspends, makes photochemical catalyst be subject to illumination poor effect, thus affect catalytic effect.Relative to solid powder, hollow ball powder has low-density, Large ratio surface sum some special physics, optical properties.
As the publication number Chinese patent literature that is CN102302933A discloses the preparation method of a kind of magnetic oxide tiny balloon/titanium dioxide composite photocatalyst, carry out as follows: 1) magnetic metal oxide tiny balloon preparation, metal cation salt is joined in organic polar solvent and dissolves completely, then solid alkali metal salt and surfactant is added, the mixed solution of composition reacts at 160-200 DEG C, obtains magnetic metal oxide tiny balloon; 2) with this tiny balloon for matrix, add titanium source, through hydrolysis, then through vacuum drying or high-temperature calcination, obtain magnetic oxide tiny balloon/titanium dioxide composite nanostructure material.Although this preparation method has prepared magnetic oxide tiny balloon/titanium dioxide composite nanostructure material, need multistep operation, preparation process more complicated, and production efficiency is lower.
Magnetic oxide tiny balloon/titanium dioxide composite photocatalyst prepared by this application, the magnetic oxide hollow ball prepared with centre is carrier, magnetic carrying of titanium dioxide photocatalyst is prepared by hydrolysis, though photochemical catalyst band can be made to be magnetic, but Hollow sphere particles preparation technology inconvenience regulation and control, in photochemical catalyst, magnetic oxide ratio is high, on the one hand the photocatalysis performance of meeting Units of Limitation quality photochemical catalyst, and another aspect catalyst under arms process excessively easily attracts each other and reunites.In addition, it is wayward that titanium dioxide technical process is prepared in hydrolysis, and the appearance and size of composite photo-catalyst (geometric properties) is difficult to be guaranteed.The titanium dioxide crystal degree obtained is poor, though can regulate and control crystal formation component by high-temperature calcination, adds the complexity of technique.
Summary of the invention
The invention provides a kind of magnetic titanium dioxide composite hollow microballoon and preparation method thereof.The method, from raw material, utilizes Mixed crystal effect, directly regulates and controls the photocatalysis performance of product and magnetic, technique simple and flexible, easy to operate, rapidly and efficiently, is easy to large-scale industrial production.The product prepared has good photocatalysis performance, and possesses magnetic, is convenient to be recycled after product is on active service.
A kind of magnetic titanium dioxide composite hollow microballoon, the spherical shell forming magnetic titanium dioxide composite hollow microballoon is dispersed in titanium dioxide by nano magnetic material, shell thickness accounts for 4 ~ 10% of sphere diameter, and the addition of magnetic material is 2 ~ 20wt.% of nano titanium oxide and magnetic material gross mass.
The preparation method of described magnetic titanium dioxide composite hollow microballoon, comprises the steps:
(1) deionized water and absolute ethyl alcohol are mixed to get presoma solvent, surfactant, binding agent are mixed with described presoma solvent, add nano titanium oxide and nano magnetic material again, be uniformly dispersed and obtain presoma suspension after stirring;
(2) step (1) gained presoma suspension obtains described magnetic titanium dioxide composite hollow microballoon through plasma spray technology.
As preferably, in step (1), the volume ratio of described deionized water and absolute ethyl alcohol is 0.5 ~ 4.More preferably 1 ~ 3.
As preferably, in step (1), in described presoma suspension, the concentration of nano titanium oxide is 25 ~ 75g/L, and further preferably, in described presoma suspension, the concentration of nano titanium oxide is 40 ~ 60g/L.
As preferably, in step (1), described nano magnetic material includes but are not limited to the ferrites such as magnetic ferroferric oxide, magnetic di-iron trioxide, barium ferrite.
As preferably, in step (1), the quality of described nano magnetic material accounts for 2 ~ 20wt.% of nano titanium oxide and nano magnetic material gross mass.Further preferably, the quality of nano magnetic material accounts for 5 ~ 20wt.% of nano titanium oxide and nano magnetic material gross mass.By controlling the mass ratio of nano magnetic material, the magnetic size of final products can be regulated.
As preferably, described nano titanium oxide is the mixture of anatase-type nanometer titanium dioxide and rutile type nano titanic oxide, the mass percent of anatase-type nanometer titanium dioxide is 70 ~ 95%, and the particle size of described nano titanium oxide is 5 ~ 30nm.Further preferably, the mass percent of anatase-type nanometer titanium dioxide is 75 ~ 85%.With the nano titanium oxide of this composition for raw material, by adding magnetic material, the more excellent product of catalytic performance can be obtained through follow-up plasma spray technology.
Described surfactant includes but are not limited to polyethylene glycol, dodecylbenzene sodium sulfonate, softex kw etc.Described binding agent includes but are not limited to PVP and polyvinyl alcohol etc.Add binding agent, make suspension more stable on the one hand, in the several months can not there is sedimentation in nano particle, and can impel the formation of micron ball in thermal spray process on the other hand, structure does not occur loose or caves in.
As preferably, in step (1), the quality of described surfactant accounts for 5 ~ 10wt.% of nano titanium oxide and nano magnetic material gross mass, and the quality of binding agent accounts for 10 ~ 50wt.% of nano titanium oxide and nano magnetic material gross mass.When both additions are less, stability of suspension is poor, nano particle free settling, and bond effect is poor, and final powder is difficult to form spherical structure; When adding more, suspension viscosity is comparatively large, and be not beneficial to feeding, the powder-product obtained is yielding, balling-up poor effect.Further preferably, described surfactant is polyethylene glycol, and described binding agent is PVP.
As preferably, in step (2), described presoma suspension is sent in thermal spraying flame stream by drawing-in device, obtains described magnetic titanium dioxide composite hollow microballoon; Described drawing-in device comprises peristaltic pump needle-based drawing-in device or drive nozzle atomization drawing-in device.
As preferably, described drawing-in device is peristaltic pump needle-based drawing-in device, and feed rate is 30 ~ 100mL/min.
As preferably, in step (2), described plasma spray technology is flame spray technique, plasma spraying technology or HVAF technology.
Further preferably, described plasma spray technology is plasma spraying technology, and technical parameter is: main atmospheric pressure: 0.4 ~ 0.7Mpa; Secondary atmospheric pressure: 0.2 ~ 0.5Mpa; Spraying current: 400 ~ 600A; Spray voltage: 40 ~ 60V.Described nano titanium oxide is the mixture of anatase-type nanometer titanium dioxide and rutile type nano titanic oxide, and the mass percent of anatase-type nanometer titanium dioxide is 70 ~ 95%, and the particle size of described nano titanium oxide is 5 ~ 30nm.
Preferred again, described feed rate is 35 ~ 80mL/min;
The technical parameter of plasma spraying technology is: main atmospheric pressure: 0.5Mpa; Secondary atmospheric pressure: 0.3Mpa; Spraying current: 400 ~ 500A; Spray voltage: 50 ~ 60V;
Nano titanium oxide is the mixture of anatase-type nanometer titanium dioxide and rutile type nano titanic oxide, and the mass percent of anatase-type nanometer titanium dioxide is 80%.
The present invention directly with the nano titanium oxide of specific crystal formation for raw material, and by accuracy controlling to reaction condition, retain the structure of raw material to greatest extent, utilize Mixed crystal effect, from raw material, directly the photocatalysis performance of product and magnetic size are regulated and controled.The nano titanium oxide of the special composition of above-mentioned preferred plasma spray technology parameter and employing adapts, and the product prepared has more excellent catalytic performance.
The present invention utilizes suspension plasma spray technology, and presoma, through atomization, evaporation, ablation, solidification, forms magnetic titanium dioxide composite hollow microballoon.Effectively realize the compound of magnetic material and titanium dioxide, the product of preparation has certain magnetic, is conducive to product recycling in actual applications.The characteristic parameter such as pattern, phase content of final powder is effectively controlled by the parameter such as mass ratio, spray power controlling nano particle and PVP in suspension.
In order to characterize the performance of the magnetic titanium dioxide composite hollow microballoon prepared, can utilize X-ray diffractometer (XRD), SEM (SEM) and photocatalysis sterilization experimental facilities, be below concrete performance test methods.
Crystal structure detects: after powder product sample preparation, utilize X-ray diffractometer to detect its crystal structure.
Microstructure is observed: take a morsel powder product sample, adheres on sample stage with conducting resinl, after spray Pt, utilizes its heterogeneous microstructure of scanning electronic microscope observation.
Photocatalysis is tested: take Escherichia coli as subjects, carry out photocatalysis performance test to powder product.
In sum, the present invention by liquid-phase thermal spray technology, suspension is sent in thermal spraying flame stream, evaporates, ablation, solidification, obtain magnetic titanium dioxide composite hollow microballoon, achieve the compound of nano titanium oxide and magnetic material quickly and efficiently.
Compared with traditional titanium dioxide optical catalyst and technology of preparing, tool of the present invention has the following advantages:
(1) the magnetic titanium dioxide composite hollow microballoon prepared by, inner hollow, Stability Analysis of Structures, specific area is large, has excellent photocatalysis performance, has certain magnetic simultaneously, be convenient to externally-applied magnetic field and carry out being recycled of powder.
(2) adopt liquid-phase thermal spray technology, can effectively reduce being heated of nano particle, thus reduce phase in version, tiny anatase-phase nano titanium dioxide particle is more preserved.Be conducive to the photocatalysis performance improving obtained powder.
(3) the liquid-phase thermal spray technology adopted, technique is flexible, simple and easy to control, rapidly and efficiently, is convenient to industrialization large-scale production.
Therefore, the preparation method of magnetic titanium dioxide composite hollow microballoon provided by the invention, have technique simple and easy to control, with low cost, rapidly and efficiently, be convenient to the advantages such as industrially scalable production.Prepared magnetic titanium dioxide composite hollow microballoon has uniform composition, photocatalysis performance excellence, is with the advantages such as being convenient to recycling that is magnetic, and has broad application prospects in the environmental sanitation such as sewage disposal, drink water purifying field.
Accompanying drawing explanation
The XRD collection of illustrative plates of magnetic titanium dioxide composite hollow microballoon prepared by embodiment 1 ~ 5 is provided respectively in Fig. 1;
Fig. 2 is the microstructure morphology figure of magnetic titanium dioxide composite hollow microballoon prepared by embodiment 2:
(a) overall pattern; (b) single Hollow sphere particles pattern; C spherical shell pattern that () is broken; (d) spherical shell section high power pattern;
Fig. 3 is the M-H magnetization curve of the magnetic titanium dioxide composite hollow microballoon prepared respectively in embodiment 2,4 and 5;
Fig. 4 is the photo-catalyst design sketch of magnetic titanium dioxide composite hollow microballoon prepared by embodiment 2.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is described in further detail, it is pointed out that the following stated embodiment is intended to be convenient to the understanding of the present invention, and any restriction effect is not play to it.
Embodiment 1
In this example, weigh a certain amount of polyethylene glycol and PVP joins in the absolute ethyl alcohol and deionized water mixed solvent that volume ratio is 1:1, after fully dissolving, nano titanium oxide and Nanometer Magnetite particle is added, mechanical agitation ultrasonic disperse 60min in solution.Subsequently, the presoma suspension of preparation is sent in plasma spraying flame stream by peristaltic pump needle-based drawing-in device, utilizes rustless steel container to collect, obtain magnetic titanium dioxide composite hollow microballoon, in Powdered.The concrete technology parameter preparing this composite powder is as follows:
(1) nano titanium oxide used is P25, and its addition is 40g/L;
(2) mass ratio of added titanium dioxide, tri-iron tetroxide, PVP, polyethylene glycol is 19:1:8:2;
(3) peristaltic pump feed rate is 65mL/min;
(4) plasma spraying voltage is 50V, and electric current is 400A, and the pressure of main gas and time gas is respectively 0.5Mpa and 0.3Mpa.
Embodiment 2
In this example, weigh a certain amount of polyethylene glycol and PVP joins in the absolute ethyl alcohol and deionized water mixed solvent that volume ratio is 1:2, after abundant solvent, nano titanium oxide and Nanometer Magnetite particle is added, mechanical agitation ultrasonic disperse 60min in solution.Subsequently, the presoma suspension of preparation is sent in plasma flame flow by peristaltic pump needle-based drawing-in device, utilizes rustless steel container to collect, obtain magnetic titanium dioxide composite hollow microballoon, in Powdered.Design parameter prepared by this composite powder is as follows:
(1) nano titanium oxide used is P25, and its addition is 50g/L;
(2) mass ratio of added titanium dioxide, tri-iron tetroxide, PVP, polyethylene glycol is 19:1:10:1;
(3) peristaltic pump feed rate is 50mL/min;
(4) plasma spraying voltage is 50V, and electric current is 500A, and the pressure of main gas and time gas is respectively 0.5Mpa and 0.3Mpa.
Embodiment 3
In this example, weigh a certain amount of polyethylene glycol and PVP joins in the absolute ethyl alcohol and deionized water mixed solvent that volume ratio is 1:3, after abundant solvent, nano titanium oxide and Nanometer Magnetite particle is added, mechanical agitation ultrasonic disperse 60min in solution.Subsequently, the presoma suspension of preparation is sent in plasma flame flow by peristaltic pump needle-based drawing-in device, utilizes rustless steel container to collect, obtain magnetic titanium dioxide composite hollow microballoon, in Powdered.Design parameter prepared by this composite powder is as follows:
(1) nano titanium oxide used is P25, and its addition is 60g/L;
(2) mass ratio of added titanium dioxide, tri-iron tetroxide, PVP, polyethylene glycol is 19:1:6:3;
(3) peristaltic pump feed rate is 35mL/min;
(4) plasma spraying voltage is 60V, and electric current is 500A, and the pressure of main gas and time gas is respectively 0.5Mpa and 0.3Mpa.
Embodiment 4
In this example, take polyethylene glycol and PVP joins in the absolute ethyl alcohol and deionized water mixed solvent that volume ratio is 1:1, after abundant solvent, in solution, add nano titanium oxide and Nanometer Magnetite particle, mechanical agitation ultrasonic disperse 60min.Subsequently, the presoma suspension of preparation is sent in plasma flame flow by peristaltic pump needle-based drawing-in device, utilizes rustless steel container to collect, obtain magnetic titanium dioxide composite hollow microballoon, in Powdered.Design parameter prepared by this composite powder is as follows:
(1) nano titanium oxide used is P25, and its addition is 40g/L;
(2) mass ratio of added titanium dioxide, tri-iron tetroxide, PVP, polyethylene glycol is 9:1:3:1;
(3) peristaltic pump feed rate is 80mL/min;
(4) plasma spraying voltage is 50V, and electric current is 500A, and the pressure of main gas and time gas is respectively 0.5Mpa and 0.3Mpa.
Embodiment 5
In this example, take polyethylene glycol and PVP joins in the absolute ethyl alcohol and deionized water mixed solvent that volume ratio is 1:1, after abundant solvent, in solution, add nano titanium oxide and Nanometer Magnetite particle, mechanical agitation ultrasonic disperse 60min.Subsequently, the presoma suspension of preparation is sent in plasma flame flow by peristaltic pump needle-based drawing-in device, utilizes rustless steel container to collect, obtain magnetic titanium dioxide composite hollow microballoon, in Powdered.Design parameter prepared by this composite powder is as follows:
(1) nano titanium oxide used is P25, and its addition is 40g/L;
(2) mass ratio of added titanium dioxide, tri-iron tetroxide, PVP, polyethylene glycol is 8:2:4:1;
(3) peristaltic pump feed rate is 70mL/min;
(4) plasma spraying voltage is 50V, and electric current is 500A, and the pressure of main gas and time gas is respectively 0.5Mpa and 0.3Mpa.
Embodiment 6
In this example, take polyethylene glycol and PVP joins in the absolute ethyl alcohol and deionized water mixed solvent that volume ratio is 1:1, after abundant solvent, in solution, add nano titanium oxide and Nanometer Magnetite particle, mechanical agitation ultrasonic disperse 60min.Subsequently, the presoma suspension of preparation is sent in plasma flame flow by peristaltic pump needle-based drawing-in device, utilizes rustless steel container to collect, obtain magnetic titanium dioxide composite hollow microballoon, in Powdered.Design parameter prepared by this composite powder is as follows:
(1) nano titanium oxide used is P25, and its addition is 40g/L;
(2) mass ratio of added titanium dioxide, tri-iron tetroxide, PVP, polyethylene glycol is 8:2:1:1;
(3) peristaltic pump feed rate is 60mL/min;
(4) plasma spraying voltage is 50V, and electric current is 500A, and the pressure of main gas and time gas is respectively 0.5Mpa and 0.3Mpa.
Embodiment 7
Test method, with embodiment 2, replaces Nanometer Magnetite with nano-magnetic di-iron trioxide, same obtained corresponding magnetic titanium dioxide hollow microsphere.
Embodiment 8
Test method, with embodiment 2, replaces Nanometer Magnetite with nano barium ferrite, same obtained corresponding magnetic titanium dioxide hollow microsphere.
The product prepared above each embodiment carries out material phase analysis, microscopic appearance is observed, magnetic size is tested and photo-catalyst performance test, and test result is as follows:
Material phase analysis:
Embodiment 1,2,3 is compared, and the product prepared after spraying is mainly containing Anatase, Rutile Type and magnetic iron ore phase.Compared with initial feed, the ratio of Anatase and Rutile Type reduces to some extent, and magnetic iron ore has no crystal transfer mutually.Along with the increase of spray power, more anatase phase titanium dioxide changes to Rutile Type, and the ratio of Anatase and Rutile Type reduces gradually, as shown in Fig. 1 (a).Can be drawn by Scherrer formulae discovery, in powder there is not significant change in the size of nano particle.
Embodiment 2,4,5 is compared, and the product prepared after spraying is mainly containing Anatase, Rutile Type and magnetic iron ore phase.Compared with initial feed, the ratio of Anatase and Rutile Type is substantially constant, and magnetic iron ore has no crystal transfer mutually.Along with the increase of nano ferriferrous oxide granule addition, in XRD spectra, the peak of magnetic iron ore phase increases by force, as shown in Fig. 1 (b).Can be drawn by Scherrer formulae discovery, in powder there is not significant change in the size of nano particle.
Microscopic appearance:
In embodiment 6, the balling ratio of powder reduces, and percentage of damage is higher.This is mainly because the addition of PVP decreases 3/4 relative to other groups.PVP not only increases the stability of suspension, and as binding agent, can promote the balling ratio of powder, less percentage of damage.
Embodiment 1 ~ 5, embodiment 8, embodiment 9, the spherical in shape or elliposoidal of powder, particle diameter 20 ~ 60 μm, balling ratio is high, as shown in Fig. 2 (a), (b).Can obviously be found out by indivedual broken particle (Fig. 2 (c)), powder inner hollow, shell thickness 1 ~ 4 μm, spherical shell is made up of nano particle, compared with initial nanometer powder, nanoparticle size size has no significant change, consistent with XRD analysis result, larger-size ferroferric oxide nano granules is evenly dispersed among titania nanoparticles, as shown in Fig. 2 (d).
Magnetic size is tested:
The product of comparative example 2,4,5, as shown in Figure 3, along with the increase of superparamag-netic iron oxide addition, powder magnetic increase, direct proportionality.
Photocatalysis performance is tested
Select embodiment 2 to carry out photo-catalyst test, the photocatalysis performance of gained powder is excellent, shown in Fig. 4.After photocatalysis, powder can be recycled by externally-applied magnetic field.
Above-described embodiment has been described in detail technical scheme of the present invention and beneficial effect; be understood that and the foregoing is only specific embodiments of the invention; be not limited to the present invention; all make in spirit of the present invention any amendment, supplement and equivalent to replace, all should be included within protection scope of the present invention.
Claims (10)
1. a magnetic titanium dioxide composite hollow microballoon, it is characterized in that, the spherical shell forming magnetic titanium dioxide composite hollow microballoon is dispersed in titanium dioxide by nano magnetic material, shell thickness accounts for 4 ~ 10% of sphere diameter, and the addition of magnetic material is 2 ~ 20wt.% of nano titanium oxide and magnetic material gross mass.
2. a preparation method for magnetic titanium dioxide composite hollow microballoon according to claim 1, is characterized in that, comprise the steps:
(1) deionized water and absolute ethyl alcohol are mixed to get presoma solvent, surfactant, binding agent are mixed with described presoma solvent, add nano titanium oxide and nano magnetic material again, be uniformly dispersed and obtain presoma suspension after stirring;
(2) step (1) gained presoma suspension obtains described magnetic titanium dioxide composite hollow microballoon through plasma spray technology.
3. the preparation method of magnetic titanium dioxide composite hollow microballoon according to claim 2, is characterized in that, in step (1), the volume ratio of described deionized water and absolute ethyl alcohol is 0.5 ~ 4.
4. the preparation method of magnetic titanium dioxide composite hollow microballoon according to claim 2, it is characterized in that, in step (1), described nano magnetic material be magnetic ferroferric oxide, magnetic oxide, ferritic one or more, in presoma suspension, the concentration of nano titanium oxide is 25 ~ 75g/L, and the quality of nano magnetic material accounts for 2 ~ 20wt.% of nano titanium oxide and nano magnetic material gross mass.
5. the preparation method of magnetic titanium dioxide composite hollow microballoon according to claim 4, it is characterized in that, described nano titanium oxide is the mixture of anatase-type nanometer titanium dioxide and rutile type nano titanic oxide, and the mass percent of anatase-type nanometer titanium dioxide is 70 ~ 95%.
6. the preparation method of magnetic titanium dioxide composite hollow microballoon according to claim 4, it is characterized in that, in step (1), the quality of described surfactant accounts for 5 ~ 10wt.% of nano titanium oxide and nano magnetic material gross mass, and the quality of binding agent accounts for 10 ~ 50wt.% of nano titanium oxide and nano magnetic material gross mass.
7. the preparation method of magnetic titanium dioxide composite hollow microballoon according to claim 2, it is characterized in that, in step (2), described presoma suspension is sent in thermal spraying flame stream by drawing-in device, obtains described magnetic titanium dioxide composite hollow microballoon;
Described drawing-in device comprises peristaltic pump needle-based drawing-in device or drive nozzle atomization drawing-in device.
8. the preparation method of magnetic titanium dioxide composite hollow microballoon according to claim 7, is characterized in that, described drawing-in device is peristaltic pump needle-based drawing-in device, and feed rate is 30 ~ 100mL/min.
9. the preparation method of magnetic titanium dioxide composite hollow microballoon according to claim 7, is characterized in that, in step (2), described plasma spray technology is flame spray technique, plasma spraying technology or HVAF technology.
10. the preparation method of the magnetic titanium dioxide composite hollow microballoon according to claim 5 or 9, is characterized in that, described plasma spray technology is plasma spraying technology, and technical parameter is: main atmospheric pressure: 0.4 ~ 0.7Mpa; Secondary atmospheric pressure: 0.2 ~ 0.5Mpa; Spraying current: 400 ~ 600A; Spray voltage: 40 ~ 60V.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110218099A (en) * | 2019-07-20 | 2019-09-10 | 兰州理工大学 | A kind of method that nickel fibers high-temperature slag prepares magnetic hollow ceramic microsphere |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1772363A (en) * | 2004-11-11 | 2006-05-17 | 中国科学院化学研究所 | Template process of preparing hollow ball and composite hollow ball |
| CN101428220A (en) * | 2008-12-26 | 2009-05-13 | 北京化工大学 | Magnetic titanium dioxide hollow ball and preparation method thereof |
| WO2009064964A2 (en) * | 2007-11-15 | 2009-05-22 | The University Of California | Switchable nano-vehicle delivery systems, and methods for making and using them |
| CN102302933A (en) * | 2011-06-23 | 2012-01-04 | 常州大学 | Method for preparing magnetic oxide hollow microsphere/titanium dioxide composite photocatalyst |
| CN102373397A (en) * | 2011-10-21 | 2012-03-14 | 中国科学院宁波材料技术与工程研究所 | Micro-nanometer structure TiO2 coating with high hardness and high adhesion force as well as preparation method thereof |
| CN103086700A (en) * | 2013-02-26 | 2013-05-08 | 江苏立达高科特种材料有限公司 | Preparation method of nano oxide ceramic hollow sphere used for thermal spraying |
| CN103949259A (en) * | 2014-05-05 | 2014-07-30 | 浙江师范大学 | Preparation and application of novel wastewater treatment agent, ZnFe2O4/TiO2 compound |
-
2015
- 2015-01-12 CN CN201510014384.7A patent/CN104624189B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1772363A (en) * | 2004-11-11 | 2006-05-17 | 中国科学院化学研究所 | Template process of preparing hollow ball and composite hollow ball |
| WO2009064964A2 (en) * | 2007-11-15 | 2009-05-22 | The University Of California | Switchable nano-vehicle delivery systems, and methods for making and using them |
| CN101428220A (en) * | 2008-12-26 | 2009-05-13 | 北京化工大学 | Magnetic titanium dioxide hollow ball and preparation method thereof |
| CN102302933A (en) * | 2011-06-23 | 2012-01-04 | 常州大学 | Method for preparing magnetic oxide hollow microsphere/titanium dioxide composite photocatalyst |
| CN102373397A (en) * | 2011-10-21 | 2012-03-14 | 中国科学院宁波材料技术与工程研究所 | Micro-nanometer structure TiO2 coating with high hardness and high adhesion force as well as preparation method thereof |
| CN103086700A (en) * | 2013-02-26 | 2013-05-08 | 江苏立达高科特种材料有限公司 | Preparation method of nano oxide ceramic hollow sphere used for thermal spraying |
| CN103949259A (en) * | 2014-05-05 | 2014-07-30 | 浙江师范大学 | Preparation and application of novel wastewater treatment agent, ZnFe2O4/TiO2 compound |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110218099A (en) * | 2019-07-20 | 2019-09-10 | 兰州理工大学 | A kind of method that nickel fibers high-temperature slag prepares magnetic hollow ceramic microsphere |
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