CN103204695B - Method for preparing porous ceramic microballs by low-temperature coaxial electrostatic spraying - Google Patents
Method for preparing porous ceramic microballs by low-temperature coaxial electrostatic spraying Download PDFInfo
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- CN103204695B CN103204695B CN201310077024.2A CN201310077024A CN103204695B CN 103204695 B CN103204695 B CN 103204695B CN 201310077024 A CN201310077024 A CN 201310077024A CN 103204695 B CN103204695 B CN 103204695B
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Abstract
The invention discloses a method for preparing porous ceramic microballs by low-temperature coaxial electrostatic spraying. The method includes steps of firstly subjecting electric-spraying liquid to low-temperature coaxial electrostatic spraying to obtain spherical composite materials, freezing and drying the spherical composite materials and sintering to obtain porous ceramic microballs. The ceramic microballs prepared by the method are of porous structures, specific surface area is high, the porous structures are easy to control, adsorption, catalysis, separation and sensing performances of the ceramic microballs are improved beneficially, and the ceramic microballs have wide application prospect in the fields of biological medicine, filter materials, catalyst carriers, fuel cells and electronic components.
Description
Technical field
The invention belongs to technical field of material, relate to a kind of method that coaxial low temperature electrostatic spray prepares porous ceramics microballoon.
Background technology
Ceramic microsphere refers to the inorganic spherical non-metallic material of diameter at micron or nanoscale, because it has less size and larger surface energy, small-size effect, surface effects or interfacial effect etc. can be produced in use, thus show special performance in physics and chemistry properties.
Ceramic microsphere is when field application such as medicine controlled releasing, Bone Defect Repari filler, catalytic carrier and piezoelectrics, its porosity and specific surface area are the key factors affecting performance, surface due to porous ceramics microballoon has mesoporous or macroporous structure, higher porosity and specific surface area can be obtained relative to conventional ceramic microballoon, during carrier especially as catalyzed reaction and medicament slow release, there is higher adsorptive capacity and charge capacity, thus show excellent performance, so develop high porosity and specific surface area porous ceramics microballoon is most important.
Chinese patent " nano titanium dioxide porous microsphere " (application number: 02112734.4, publication number: 1443601, publication date: 2003-09-24), disclose a kind of nano titanium dioxide porous microsphere and manufacture method thereof, nano titanium dioxide powder mixes with nano titanium oxide colloid by the method, grind, obtain the mixed slurry of nano titanium oxide, then mist projection granulating is adopted, obtain nano titanium dioxide porous microsphere through thermal treatment, its vesicular structure mainly to be volatilized fast when drying by the solvent in colloidal tio 2 and stays.Chinese patent " a kind of preparation method of diatomite-based porous ceramic microspheres " (application number: 201110228418.4, publication number: 102391011A, publication date: 2012-03-28), disclose a kind of preparation method of diatomite-based porous ceramic microspheres, take diatomite as main raw material, prepare porous ceramics microballoon by spraying dry, its vesicular structure mainly when sintering diatomaceous gap to be formed.The specific surface area of porous ceramics microballoon prepared by above-mentioned two kinds of methods is less, mostly at 300m
2/ below g, simultaneously more difficult for the control ratio of porous ceramics microballoon pore structure (porosity and hole dimension), can not actual needs be met.
Summary of the invention
The object of this invention is to provide a kind of method that coaxial low temperature electrostatic spray prepares porous ceramics microballoon, solve the little and pore structure problem more rambunctious of the specific surface area of porous ceramics microballoon prepared by existing method.
The technical solution adopted in the present invention is, coaxial low temperature electrostatic spray prepares the method for porous ceramics microballoon, first EFI liquid is carried out coaxial low temperature electrostatic spray and obtain spherical matrix material, then spherical matrix material is sintered after lyophilize, namely obtain porous ceramics microballoon.
Feature of the present invention is also,
EFI liquid is made up of solvent and solute, and solute is made up of ceramic forerunner and polymkeric substance, adds polymkeric substance and ceramic forerunner successively in a solvent, obtains EFI liquid after mixing; The mass ratio of solvent and solute is 95 ~ 70:5 ~ 30, and the mass ratio of ceramic forerunner and polymkeric substance is 20 ~ 80:80 ~ 20.
EFI liquid enters low temperature cavity body in electrostatic atomiser after coaxial electrostatic spraying forms spherical drop, and then fall on the receiver, the temperature of low temperature cavity is-50 ~ 10 DEG C.
Lyophilize is carried out in vacuum environment, and low vacuum is in 6Pa, and the temperature of sintering is 300 DEG C ~ 1200 DEG C.
Solvent is any one in water, the trimethyl carbinol, amphene, water-trimethyl carbinol and the trimethyl carbinol-amphene.
Ceramic forerunner is any one in butyl (tetra) titanate, titanium isopropylate, tetraethoxy, three isopropoxy vanadium oxides, zinc acetate, zinc nitrate, zirconium nitrate, nickelous acetate, nitrate of baryta, iron nitrate, cerous nitrate, Yttrium trinitrate, indium nitrate and Silver Nitrate.
Polymkeric substance is any one in polyvinylpyrrolidone, polyacrylonitrile, polyvinyl butyral acetal, polyvinyl acetate, polymethylmethacrylate, polyvinyl alcohol, Mierocrystalline cellulose, nylon66 fiber, polystyrene and poly(lactic acid).
The invention has the beneficial effects as follows, ceramic microsphere prepared by the method that coaxial low temperature electrostatic spray of the present invention prepares porous ceramics microballoon has vesicular structure, specific surface area is high, and its pore structure is easy to control, contribute to the absorption of raising ceramic microsphere, catalysis, separation and sensing capabilities, have broad application prospects in biological medicine, filtering material, support of the catalyst, fuel cell and field of electrical components.
Accompanying drawing explanation
Fig. 1 is the structural representation that coaxial low temperature electrostatic spray of the present invention prepares electrostatic atomiser in the method for porous ceramics microballoon.
In figure, 1. inner tube micro pump; 2. outer tube micro pump, 3. saturated gas transfer lime, the 4. saturated gas of solvent, 5. Coaxial nozzle inner tube, 6. Coaxial nozzle outer tube, 7. receptor, 8. low temperature cavity.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Coaxial low temperature electrostatic spray of the present invention prepares the method for porous ceramics microballoon, first EFI liquid is carried out coaxial low temperature electrostatic spray and obtains spherical matrix material, then sintered after lyophilize by spherical matrix material, namely obtain porous ceramics microballoon.
Concrete steps are as follows:
Step 1, the preparation of EFI liquid
Add polymkeric substance and ceramic forerunner successively in a solvent, after mixing, obtain EFI liquid; The mass ratio of solvent and solute is 95 ~ 70:5 ~ 30, and the mass ratio of ceramic forerunner and polymkeric substance is 20 ~ 80:80 ~ 20;
Step 2, coaxial low temperature electrostatic spray
Coaxial low temperature electrostatic spray carries out in the electrostatic atomiser shown in Fig. 1, the structure of electrostatic atomiser is: comprise the Coaxial nozzle be connected with high-voltage DC power supply positive pole, Coaxial nozzle comprises Coaxial nozzle inner tube 5 and Coaxial nozzle outer tube 6, Coaxial nozzle inner tube 5 is communicated with inner tube micro pump 1, Coaxial nozzle outer tube 6 is communicated with outer tube micro pump 2, outer tube micro pump 2 is connected with saturated gas container by saturated gas transfer lime 3, immediately below Coaxial nozzle, 10 ~ 30cm place is provided with the receptor 7 be placed in low temperature cavity 8, receptor 7 ground connection, EFI liquid step 1 obtained pours inner tube micro pump 1 into, the saturated gas 4 of solvent is passed into outer tube micro pump 2 by saturated gas transfer lime 3, then under the voltage of 10 ~ 40kV, the temperature of low temperature controlling box is-50 ~ 10 DEG C, inner tube micro pump 1 is advanced with the speed of 0.5 ~ 2.5ml/h, outer tube micro pump 2 is advanced with the speed of 1 ~ 5ml/h, EFI liquid is ejected from Coaxial nozzle inner tube 5 by electrostatic spray, and spherical drop is formed under the effect of electrical forces, simultaneously by the encirclement of the saturated gas of solvent sprayed from Coaxial nozzle outer tube 6, the volatilization of solvent in spherical drop non-volatile or minute quantity quick freezing, drop on receptor 7 after finally entering low temperature cavity 8, obtain spherical matrix material,
Step 3, lyophilize, sintering
Spherical matrix material step 3 obtained carries out lyophilize under vacuum conditions, and low vacuum, in 6Pa, finally sinters, namely obtains porous ceramics microballoon at 300 ~ 1200 DEG C.
Wherein, solvent is any one in water, the trimethyl carbinol, amphene, water-trimethyl carbinol and the trimethyl carbinol-amphene.
Ceramic forerunner is any one in butyl (tetra) titanate, titanium isopropylate, tetraethoxy, three isopropoxy vanadium oxides, zinc acetate, zinc nitrate, zirconium nitrate, nickelous acetate, nitrate of baryta, iron nitrate, cerous nitrate, Yttrium trinitrate, indium nitrate and Silver Nitrate.
Polymkeric substance is any one in polyvinylpyrrolidone, polyacrylonitrile, polyvinyl butyral acetal, polyvinyl acetate, polymethylmethacrylate, polyvinyl alcohol, Mierocrystalline cellulose, nylon66 fiber, polystyrene and poly(lactic acid).
Ceramic microsphere prepared by the method that coaxial low temperature electrostatic spray of the present invention prepares porous ceramics microballoon has vesicular structure, specific surface area is high, and its pore structure is easy to control, contribute to the absorption of raising ceramic microsphere, catalysis, separation and sensing capabilities, have broad application prospects in biological medicine, filtering material, support of the catalyst, fuel cell and field of electrical components.
Embodiment 1
Step 1, adds 4.0g polyvinyl acetate and 1.0g Butyl Phthalate successively, obtains EFI liquid after mixing in the 95g trimethyl carbinol;
Step 2, EFI liquid step 1 obtained pours inner tube micro pump 1 into, the saturated gas of the trimethyl carbinol is passed into outer tube micro pump 2 by saturated gas transfer lime 3, then under the voltage of 20kV, the temperature of low temperature controlling box is 10 DEG C, distance between Coaxial nozzle outer tube 6 and collector 7 is 30cm, collector ground connection, inner tube micro pump 1 is advanced with the speed of 2.5ml/h, outer tube micro pump 2 is advanced with the speed of 5ml/h, EFI liquid is ejected from Coaxial nozzle inner tube 5 by electrostatic spray, and spherical drop is formed under the effect of electrical forces, simultaneously by the encirclement of the saturated gas of the trimethyl carbinol sprayed from Coaxial nozzle outer tube 6, the volatilization of solvent in spherical drop non-volatile or minute quantity quick freezing, drop on receptor 7 after finally entering low temperature cavity 8, obtain spherical matrix material,
Step 3, spherical matrix material step 3 obtained carries out lyophilize under vacuum conditions, and vacuum tightness is 5.5Pa, finally sinters at 550 DEG C, namely obtains titanium dioxide porous ceramic microballoon.
Embodiment 2
Step 1, adds 6.0g polyvinyl alcohol and 24.0g zinc acetate successively, obtains EFI liquid after mixing in 70g water;
Step 2, EFI liquid step 1 obtained pours inner tube micro pump 1 into, water saturation gas is passed into outer tube micro pump 2 by saturated gas transfer lime 3, then under the voltage of 40kV, the temperature of low temperature controlling box is-50 DEG C, distance between Coaxial nozzle outer tube 6 and collector 7 is 10cm, collector ground connection, inner tube micro pump 1 is advanced with the speed of 0.5ml/h, outer tube micro pump 2 is advanced with the speed of 1ml/h, EFI liquid is ejected from Coaxial nozzle inner tube 5 by electrostatic spray, and spherical drop is formed under the effect of electrical forces, simultaneously by the encirclement of water saturation gas sprayed from Coaxial nozzle outer tube 6, the volatilization of solvent in spherical drop non-volatile or minute quantity quick freezing, drop on receptor 7 after finally entering low temperature cavity 8, obtain spherical matrix material,
Step 3, spherical matrix material step 3 obtained carries out lyophilize under vacuum conditions, and vacuum tightness is 5Pa, finally sinters at 300 DEG C, namely obtains zinc oxide porous ceramic microsphere.
Embodiment 3
Step 1, adds 6.0g polystyrene and 14.0g tetraethoxy successively, obtains EFI liquid after mixing in 80g amphene;
Step 2, EFI liquid step 1 obtained pours inner tube micro pump 1 into, the saturated gas of amphene is passed into outer tube micro pump 2 by saturated gas transfer lime 3, then under the voltage of 10kV, the temperature of low temperature controlling box is 0 DEG C, distance between Coaxial nozzle outer tube 6 and collector 7 is 20cm, collector ground connection, inner tube micro pump 1 is advanced with the speed of 1ml/h, outer tube micro pump 2 is advanced with the speed of 3ml/h, EFI liquid is ejected from Coaxial nozzle inner tube 5 by electrostatic spray, and spherical drop is formed under the effect of electrical forces, simultaneously by the encirclement of the saturated gas of amphene sprayed from Coaxial nozzle outer tube 6, the volatilization of solvent in spherical drop non-volatile or minute quantity quick freezing, drop on receptor 7 after finally entering low temperature cavity 8, obtain spherical matrix material,
Step 3, spherical matrix material step 3 obtained carries out lyophilize under vacuum conditions, and vacuum tightness is 5.8Pa, finally sinters at 1200 DEG C, namely obtains porous silica ceramic microsphere.
Embodiment 4
Step 1, adds 7.0g polyvinylpyrrolidone and 3.0g tri-isopropoxy vanadium oxide successively, obtains EFI liquid after mixing in 90g water-trimethyl carbinol;
Step 2, EFI liquid step 1 obtained pours inner tube micro pump 1 into, the saturated gas of water-trimethyl carbinol is passed into outer tube micro pump 2 by saturated gas transfer lime 3, then under the voltage of 30kV, the temperature of low temperature controlling box is-30 DEG C, distance between Coaxial nozzle outer tube 6 and collector 7 is 25cm, collector ground connection, inner tube micro pump 1 is advanced with the speed of 2.0ml/h, outer tube micro pump 2 is advanced with the speed of 4ml/h, EFI liquid is ejected from Coaxial nozzle inner tube 5 by electrostatic spray, and spherical drop is formed under the effect of electrical forces, simultaneously by the encirclement of the saturated gas of water-trimethyl carbinol sprayed from Coaxial nozzle outer tube 6, the volatilization of solvent in spherical drop non-volatile or minute quantity quick freezing, drop on receptor 7 after finally entering low temperature cavity 8, obtain spherical matrix material,
Step 3, spherical matrix material step 3 obtained carries out lyophilize under vacuum conditions, and vacuum tightness is 5Pa, finally sinters at 500 DEG C, namely obtains Vanadium Pentoxide in FLAKES porous ceramics microballoon.
In the present embodiment, solvent is water-trimethyl carbinol, also can be water, the trimethyl carbinol, amphene, with any one in the trimethyl carbinol-amphene, in the present embodiment, ceramic forerunner is three isopropoxy vanadium oxides, also can be butyl (tetra) titanate, titanium isopropylate, tetraethoxy, , zinc acetate, zinc nitrate, zirconium nitrate, nickelous acetate, nitrate of baryta, iron nitrate, cerous nitrate, Yttrium trinitrate, any one in indium nitrate and Silver Nitrate, in the present embodiment, polymkeric substance is polyvinylpyrrolidone, also can be polyacrylonitrile, polyvinyl butyral acetal, polyvinyl acetate, polymethylmethacrylate, polyvinyl alcohol, Mierocrystalline cellulose, nylon66 fiber, any one in polystyrene and poly(lactic acid).
The diameter of the porous ceramics microballoon that table 1 embodiment 1-4 makes and specific surface area
| Embodiment | Composition | Diameter (nm) | Specific surface area (m 2/g） |
| 1 | TiO 2 | 20-100 | 583.7 |
| 2 | ZnO | 80-300 | 394.6 |
| 3 | SiO2 | 50-150 | 468.1 |
| 4 | V 2O 5 | 300-600 | 230.4 |
The diameter of the porous ceramics microballoon that table 1 is made for embodiment 1-4 and specific surface area, as can be seen from Table 1, porous ceramics microballoon prepared by embodiment 1-4 has vesicular structure, and the porous ceramics microballoon prepared than prior art has higher specific surface area.
Claims (6)
1. coaxial low temperature electrostatic spray prepares the method for porous ceramics microballoon, it is characterized in that, first EFI liquid is carried out coaxial low temperature electrostatic spray and obtains spherical matrix material, then sintered after lyophilize by spherical matrix material, namely obtain porous ceramics microballoon;
The detailed process of coaxial electrostatic spraying is: EFI liquid is poured into inner tube micro pump (1), the saturated gas (4) of solvent is passed into outer tube micro pump (2) by saturated gas transfer lime (3), then under the voltage of 10 ~ 40kV, the temperature of low temperature controlling box is-50 ~ 10 DEG C, inner tube micro pump (1) is advanced with the speed of 0.5 ~ 2.5ml/h, outer tube micro pump (2) is advanced with the speed of 1 ~ 5ml/h, EFI liquid is ejected from Coaxial nozzle inner tube (5) by electrostatic spray, and spherical drop is formed under the effect of electrical forces, simultaneously by the encirclement of the saturated gas of solvent sprayed from Coaxial nozzle outer tube (6), the volatilization of solvent in spherical drop non-volatile or minute quantity quick freezing, drop on receptor (7) after finally entering low temperature cavity (8), obtain spherical matrix material.
2. coaxial low temperature electrostatic spray according to claim 1 prepares the method for porous ceramics microballoon, it is characterized in that, described EFI liquid is made up of solvent and solute, described solute is made up of ceramic forerunner and polymkeric substance, add polymkeric substance and ceramic forerunner successively in a solvent, after mixing, obtain EFI liquid; The mass ratio of described solvent and described solute is 95 ~ 70:5 ~ 30, and the mass ratio of described ceramic forerunner and described polymkeric substance is 20 ~ 80:80 ~ 20.
3. coaxial low temperature electrostatic spray according to claim 1 and 2 prepares the method for porous ceramics microballoon, it is characterized in that, described lyophilize is carried out in vacuum environment, and low vacuum is in 6Pa, and the temperature of sintering is 300 DEG C ~ 1200 DEG C.
4. coaxial low temperature electrostatic spray according to claim 3 prepares the method for porous ceramics microballoon, it is characterized in that, described solvent is any one in water, the trimethyl carbinol, amphene, water-trimethyl carbinol and the trimethyl carbinol-amphene.
5. coaxial low temperature electrostatic spray according to claim 4 prepares the method for porous ceramics microballoon, it is characterized in that, described ceramic forerunner is any one in butyl (tetra) titanate, titanium isopropylate, tetraethoxy, three isopropoxy vanadium oxides, zinc acetate, zinc nitrate, zirconium nitrate, nickelous acetate, nitrate of baryta, iron nitrate, cerous nitrate, Yttrium trinitrate, indium nitrate and Silver Nitrate.
6. coaxial low temperature electrostatic spray according to claim 5 prepares the method for porous ceramics microballoon, it is characterized in that, described polymkeric substance is any one in polyvinylpyrrolidone, polyacrylonitrile, polyvinyl butyral acetal, polyvinyl acetate, polymethylmethacrylate, polyvinyl alcohol, Mierocrystalline cellulose, nylon66 fiber, polystyrene and poly(lactic acid).
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| CN103408319B (en) * | 2013-07-26 | 2015-01-14 | 中南大学 | Method for preparing porous ceramic microspheres with different pore structures and spraying and freezing device |
| CN104529504B (en) * | 2014-12-16 | 2017-01-04 | 广州中国科学院先进技术研究所 | A kind of method preparing micrometer level porous ceramic microsphere and EFI solution and device |
| CN105999292B (en) * | 2016-05-06 | 2019-01-22 | 中南大学 | A kind of preparation method of porous, hollow ceramic microballoon |
| CN106757414A (en) * | 2016-11-30 | 2017-05-31 | 上海理工大学 | A kind of solvent circulation coaxial high pressure electrostatic spraying method and device |
| CN108247814B (en) * | 2018-01-08 | 2021-03-02 | 广东新秀新材料股份有限公司 | Manufacturing method of ceramic rear cover and manufacturing module of ceramic rear cover |
| WO2022120712A1 (en) * | 2020-12-10 | 2022-06-16 | 中国科学院深圳先进技术研究院 | Size-controllable aerogel ball and preparation method and application thereof |
| CN115044093B (en) * | 2022-06-24 | 2023-08-04 | 厦门安踏体育用品有限公司 | Porous moisture-permeable membrane and preparation method and application thereof |
| CN116041075A (en) * | 2023-04-03 | 2023-05-02 | 华南理工大学 | Hollow ceramic microsphere and preparation method and application thereof |
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