CN104353368A - Ceramic film with ordered microporous structure and preparation method of ceramic film - Google Patents
Ceramic film with ordered microporous structure and preparation method of ceramic film Download PDFInfo
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- CN104353368A CN104353368A CN201410649089.4A CN201410649089A CN104353368A CN 104353368 A CN104353368 A CN 104353368A CN 201410649089 A CN201410649089 A CN 201410649089A CN 104353368 A CN104353368 A CN 104353368A
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Abstract
The invention discloses a ceramic film with an ordered microporous structure and a preparation method of the ceramic film. The ceramic film with the ordered microporous structure is spherical ordered arrangement structure multiporous ceramic with uniform apertures and regular hole shapes, wherein the aperture of the ceramic film is 0.2-5 microns, and the porosity is 50-80 percent. The preparation method comprises the specific steps of preparing an ordered arrangement organic macromolecular microsphere template, soaking a template by a ceramic precursor, transferring the template which is soaked into a gasification furnace, gradually heating the gasification furnace to certain temperature for thermal treatment, simultaneously carrying out removal of the template and crosslinking of the precursor, and finally arranging the precursor into a high-temperature sintering furnace for further heating cracking to obtain the ceramic film with the ordered microporous structure. By the use of the characteristics that the ceramic film with the ordered microporous structure is narrow in aperture distribution and high in separation precision, the ceramic film can be applied to the field of water treatment, air purification and the like, and precision separation of materials with specific sizes is realized.
Description
Technical field
The invention belongs to ceramic separation film technical field, be specifically related to a kind of ceramic membrane with ordered micro-cellular structure and preparation method thereof.
Background technology
Compared with organic film, inorganic ceramic membrane has good stability, energy high temperature resistant, corrosion-resistant, organic solvent-resistant, resistance to microbial attack; Mechanical strength is large, and withstand voltage wearability is good; Can carry out moise-heat sterilization sterilization, the advantages such as cleaning and regeneration is convenient, can be used for gas separaion, fluid separation applications purification and membrane reactor, are all widely used in food industry, pharmacy and bioengineering, chemistry and the field such as petrochemical industry and environmental protection.
The pore structure of ceramic membrane is the key affecting ceramic membrane application, and has material impact to the separating property of ceramic membrane.Therefore, in order to regulate and control the pore size of ceramic membrane, shape and distribution, domestic and international many researchers are to this has been a large amount of research work.(the Am.Ceram.Soc.Bull. such as Nijmeijer, 1998,77 (4): 95) centrifugal process is utilized to prepare long 13cm, the Alpha-alumina ceramic-film tube of diameter 16mm, aperture radially graded in this film pipe, not easily forms fenestra and silt up, and the pollutant under retaining rests on key-course surface in water treatment procedure, easy cleaning, after mechanical cleaning, interception capacity and flux can nearly 100% recoveries.South China Science & Engineering University Sui Xian grade (CN 00117221.2) adopts melt film centrifuging process to prepare gradient porous ceramics film, its fenestra aperture is by managing the interior outwards distribution in continuous gradient, inner surface aperture is minimum, outer surface aperture is maximum, fenestra aperture is 0.05-20 μm, and porosity is 30-80%.Once space equality (CN 200710048076.1) also prepared gradient porous ceramics film by techniques such as ball milling mixing, flow casting molding, freeze drying, unsticking sintering, its fenestra aperture is 0.1-100 μm, porosity is 20-90%, oriented linear porosity, hole has directed open communication and aperture graded in a thickness direction.Nanjing University of Technology Xu Nan equality (CN 200810023905.5) prepares perfect sunken small-bore ceramic super-filtering film by sol-gel process in wide-aperture supporting body surface.Tan little Yao etc. (CN200810249536.1) adopt inversion of phases-sintering process to obtain to have the honeycomb type ceramic film of porous support layer, transition zone and effective separating layer unsymmetric structure, and this ceramic membrane has the large (500-9000m of unit volume membrane area
2/ m
3), the feature such as intensity high (200-1200MPa), easily sealing.
The separation accuracy of ceramic membrane in actual application affects by maximum diameter of hole, the ceramic membrane pore-size distribution obtained due to above-mentioned porous ceramic film preparation technology is wider, hole shape heterogeneity, and can not ensure that pore size is completely the same, because which limit the raising of ceramic membrane separation precision, precision can not be realized and filter.
Summary of the invention
The object of the invention is the deficiency overcoming the existence of above-mentioned prior art, a kind of ceramic membrane with ordered micro-cellular structure and preparation method thereof is provided.
The present invention has the ceramic membrane of ordered micro-cellular structure, it is characterized in that, described ceramic membrane is the spherical ordered arrangement architecture porous ceramics that aperture is homogeneous, hole shape is regular, and the aperture of ceramic membrane is between 0.2-5 μm, and porosity is between 50-80%.
The present invention adopts polymer pyrolysis-template, utilizes the ordered arrangement structure of template, accurately controls the microcellular structure parameter of ceramic membrane in conjunction with ceramic precursor transformation technology, final obtained has uniform pore diameter, arranges orderly microporous membrane.Specific practice first prepares ordered arrangement organic high polymer microsphere template, then this template is flooded with ceramic precursor, be transferred to after having flooded in gasification furnace and be progressively warming up to uniform temperature and heat-treat, realize the removal of template and the crosslinked of precursor simultaneously, finally be placed in high temperature sintering furnace to heat up further cracking, i.e. obtained ordered micro-cellular structure ceramic membrane.
The preparation process of ordered micro-cellular structure ceramic membrane is as follows:
(1) preparation of template
Organic high polymer microsphere and deionized water are added in beaker for 1:10 ~ 1:30 in mass ratio, carry out ultrasonic disperse 1 ~ 2h, then be transferred in supercentrifuge and carry out centrifugal sedimentation 0.5 ~ 1h, remove upper strata deionized water, take out lower sediment thing and be placed in baking oven 80 ~ 120 DEG C of drying 2 ~ 6h, obtain organic high polymer microsphere template.
(2) infiltration of precursor
Ceramic precursor and organic solvent are added in beaker for 1:1 ~ 1:5 in mass ratio, after abundant stirring and dissolving, prepares to obtain ceramic setter liquid solution; By the organic high polymer microsphere template that this ceramic precursor solution for vacuum impregnation steps (1) obtains, after having flooded, carry out decompression distillation removing organic solvent.
(3) removal of template and the crosslinked of precursor
The organic high polymer microsphere template of infiltration ceramic precursor step (2) obtained is placed in gasification furnace, progressively be warming up to 200 ~ 400 DEG C, insulation 1 ~ 4h, organic high polymer microsphere template is made to be vaporized elimination, complete the crosslinked of ceramic precursor simultaneously, now form orderly uniform cell structure in the material.
(4) ceramic of precursor
Transfer in high temperature sintering furnace by the product that step (3) obtains, be warming up to 1000 ~ 1300 DEG C, insulation 1 ~ 2h carries out Pintsch process, makes ceramic precursor be converted into inorganic ceramic completely, namely obtains ordered micro-cellular structure ceramic membrane after cooling.
Described organic high polymer microsphere is polystyrene microsphere, polyvinyl chloride microballoon, polyethylene microballoon or polypropylene microballoon.
Described ceramic precursor is polysiloxanes, Polycarbosilane, polymethyl silicane or polysilazane.
Described organic solvent is toluene, dimethylbenzene, oxolane or n-hexane.
The inventive method accurately can control the microcellular structure (comprising hole shape, aperture size, hole arrangement architecture) of ceramic membrane, thus improves ceramic membrane separation precision, realizes being separated the precision of specific dimensions material.
Ordered micro-cellular structure ceramic membrane prepared by the present invention is the spherical ordered arrangement architecture porous ceramics that aperture is homogeneous, hole shape is regular.According to the diameter of the organic high polymer microsphere as template, the aperture of ceramic membrane can be controlled between 0.2-5 μm, and controlled porosity is between 50-80%.Utilize this ordered micro-cellular structure ceramic membrane pore-size distribution narrow, the feature that separation accuracy is high, can be used for the application such as water treatment, purification of air, realizes being separated the precision of specific dimensions material.
The present invention has following beneficial effect:
Usual ceramic membrane mainly utilizes " screening " principle to be separated solute, and film allows the component less than its aperture pass through and retain the component larger or suitable with pore size than its aperture.Because the pore-size distribution of conventional ceramic film is wider, hole shape is irregular, limits the raising of ceramic membrane separation precision, can not realize precision and filter.
Ordered micro-cellular structure ceramic membrane provided by the invention, by regulating as the diameter of the organic high polymer microsphere of template and arrangement architecture, accurately can control the microcellular structure of ceramic membrane, thus improve ceramic membrane separation precision, particle diameter can be made, variform component is separated, realize being separated the precision of specific dimensions material, there is good application prospect in water treatment, purification of air etc.
In addition, current orderly micropore ceramics uses the inorganic matters such as silica to do Template preparation usually, and it is more complicated that follow-up template removes technique.The present invention adopts organic polymer to do template, and the removal of template and the crosslinked of precursor synchronously complete, and template is removed more complete, and technical process is simpler, and low cost of manufacture, is easy to realize large-scale production.
Accompanying drawing explanation
Fig. 1 is the SEM photo of embodiment 1 ordered arrangement polystyrene microsphere template;
Fig. 2 is the SEM photo of the orderly microporous membrane of embodiment 1;
Fig. 3 is the pore size distribution curve of the orderly microporous membrane of embodiment 1.
Detailed description of the invention
The present invention is described further below in conjunction with embodiment.Specific embodiment does not limit claim of the present invention.
Embodiment 1
(1) by the polystyrene microsphere of particle diameter 300nm and deionized water in mass ratio for 1:15 adds in beaker, carry out ultrasonic disperse 1h, then be transferred in supercentrifuge and carry out centrifugal sedimentation 0.5h, take out lower sediment thing and be placed in baking oven 100 DEG C of dry 4h, obtain polystyrene microsphere template.
(2) by polymethyl silicane and toluene in mass ratio for 1:4 adds in beaker, abundant stirring and dissolving, by the polystyrene microsphere template that this polymethyl silicane solution for vacuum impregnation steps (1) obtains, after having flooded, carry out decompression distillation removing toluene.
(3) product that step (2) obtains is placed in gasification furnace, progressively be warming up to 300 DEG C, insulation 2h, polystyrene microsphere template is made to be vaporized elimination, complete the crosslinked of polymethyl silicane simultaneously, be then transferred in high temperature sintering furnace, be warming up to 1000 DEG C, insulation 1h carries out Pintsch process, namely obtains ordered micro-cellular structure ceramic membrane after cooling.
In order, average pore size is 354nm, and porosity is 70.3% for the ceramic membrane uniform pore diameter that the present embodiment 1 obtains, hole shape rule, arrangement.Fig. 1 is the SEM photo of ordered arrangement polystyrene microsphere template; Fig. 2 is the SEM photo of orderly microporous membrane; Fig. 3 is the pore size distribution curve of orderly microporous membrane.
Embodiment 2
(1) by the polyvinyl chloride microballoon of particle diameter 500nm and deionized water in mass ratio for 1:20 adds in beaker, carry out ultrasonic disperse 1h, then be transferred in supercentrifuge and carry out centrifugal sedimentation 1h, take out lower sediment thing and be placed in baking oven 110 DEG C of dry 4h, obtain polyvinyl chloride microsphere template.
(2) by Polycarbosilane and dimethylbenzene in mass ratio for 1:5 adds in beaker, abundant stirring and dissolving, by the polyvinyl chloride microsphere template that this Polycarbosilane solution for vacuum impregnation steps (1) obtains, after having flooded, carry out decompression distillation except removal xylene.
(3) product that step (2) obtains is placed in gasification furnace, progressively be warming up to 350 DEG C, insulation 1h, polyvinyl chloride microsphere template is made to be vaporized elimination, complete the crosslinked of Polycarbosilane simultaneously, be then transferred in high temperature sintering furnace, be warming up to 1100 DEG C, insulation 1h carries out Pintsch process, namely obtains ordered micro-cellular structure ceramic membrane after cooling.
In order, average pore size is 568nm, and porosity is 65.2% for the ceramic membrane uniform pore diameter that the present embodiment 2 obtains, hole shape rule, arrangement.
Embodiment 3
(1) by the polyethylene microballoon of particle diameter 1 μm and deionized water in mass ratio for 1:25 adds in beaker, carry out ultrasonic disperse 2h, then be transferred in supercentrifuge and carry out centrifugal sedimentation 0.5h, take out lower sediment thing and be placed in baking oven 120 DEG C of dry 2h, obtain polyethylene microsphere template.
(2) by polysiloxanes and oxolane in mass ratio for 1:3 adds in beaker, abundant stirring and dissolving, by the polyethylene microsphere template that this polysiloxane solution vacuum impregnation step (1) obtains, after having flooded, carry out decompression distillation removing oxolane.
(3) product that step (2) obtains is placed in gasification furnace, progressively be warming up to 380 DEG C, insulation 2h, polyethylene microsphere template is made to be vaporized elimination, complete the crosslinked of polysiloxanes simultaneously, be then transferred in high temperature sintering furnace, be warming up to 1300 DEG C, insulation 1h carries out Pintsch process, namely obtains ordered micro-cellular structure ceramic membrane after cooling.
In order, average pore size is 1.1 μm, and porosity is 61.6% for the ceramic membrane uniform pore diameter that the present embodiment 3 obtains, hole shape rule, arrangement.
Embodiment 4
(1) by the polypropylene microballoon of particle diameter 4 μm and deionized water in mass ratio for 1:15 adds in beaker, carry out ultrasonic disperse 2h, then be transferred in supercentrifuge and carry out centrifugal sedimentation 0.5h, take out lower sediment thing and be placed in baking oven 110 DEG C of dry 3h, obtain polypropylene microsphere template.
(2) by polysilazane and toluene in mass ratio for 1:2 adds in beaker, abundant stirring and dissolving, by the polypropylene microsphere template that this polysilazane solution for vacuum impregnation steps (1) obtains, after having flooded, carries out decompression distillation removing toluene.
(3) product that step (2) obtains is placed in gasification furnace, progressively be warming up to 320 DEG C, insulation 1h, polypropylene microsphere template is made to be vaporized elimination, complete the crosslinked of polysilazane simultaneously, be then transferred in high temperature sintering furnace, be warming up to 1200 DEG C, insulation 1h carries out Pintsch process, namely obtains ordered micro-cellular structure ceramic membrane after cooling.
In order, average pore size is 4.2 μm, and porosity is 54.8% for the ceramic membrane uniform pore diameter that the present embodiment 4 obtains, hole shape rule, arrangement.
Claims (5)
1. have a ceramic membrane for ordered micro-cellular structure, it is characterized in that, described ceramic membrane is the spherical ordered arrangement architecture porous ceramics that aperture is homogeneous, hole shape is regular, and the aperture of ceramic membrane is between 0.2-5 μm, and porosity is between 50-80%.
2. a preparation method for ordered micro-cellular structure ceramic membrane, is characterized in that, carries out in accordance with the following steps:
(1) preparation of template
Organic high polymer microsphere and deionized water are added in beaker for 1:10 ~ 1:30 in mass ratio, carry out ultrasonic disperse 1 ~ 2h, then be transferred in supercentrifuge and carry out centrifugal sedimentation 0.5 ~ 1h, remove upper strata deionized water, take out lower sediment thing and be placed in baking oven 80 ~ 120 DEG C of drying 2 ~ 6h, obtain organic high polymer microsphere template;
(2) infiltration of precursor
Ceramic precursor and organic solvent are added in beaker for 1:1 ~ 1:5 in mass ratio, after abundant stirring and dissolving, prepares to obtain ceramic setter liquid solution; By the organic high polymer microsphere template that this ceramic precursor solution for vacuum impregnation steps (1) obtains, after having flooded, carry out decompression distillation removing organic solvent;
(3) removal of template and the crosslinked of precursor
The organic high polymer microsphere template of infiltration ceramic precursor step (2) obtained is placed in gasification furnace, progressively be warming up to 200 ~ 400 DEG C, insulation 1 ~ 4h, organic high polymer microsphere template is made to be vaporized elimination, complete the crosslinked of ceramic precursor simultaneously, now form orderly uniform cell structure in the material;
(4) ceramic of precursor
Transfer in high temperature sintering furnace by the product that step (3) obtains, be warming up to 1000 ~ 1300 DEG C, insulation 1 ~ 2h carries out Pintsch process, makes ceramic precursor be converted into inorganic ceramic completely, namely obtains ordered micro-cellular structure ceramic membrane after cooling.
3. the preparation method of ordered micro-cellular structure ceramic membrane according to claim 2, is characterized in that, described step (1) organic high polymer microsphere is polystyrene microsphere, polyvinyl chloride microballoon, polyethylene microballoon or polypropylene microballoon.
4. the preparation method of ordered micro-cellular structure ceramic membrane according to claim 2, is characterized in that, in described step (2), ceramic precursor is polysiloxanes, Polycarbosilane, polymethyl silicane or polysilazane.
5. the preparation method of ordered micro-cellular structure ceramic membrane according to claim 2, is characterized in that, in described step (2), organic solvent is toluene, dimethylbenzene, oxolane or n-hexane.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106495734A (en) * | 2016-10-20 | 2017-03-15 | 合肥创想能源环境科技有限公司 | A kind of micropore finely tunes ceramic film preparation method |
| CN107082641A (en) * | 2017-05-24 | 2017-08-22 | 广西碧清源环保科技有限公司 | A kind of ceramic membrane materials component |
| CN109289540A (en) * | 2018-09-21 | 2019-02-01 | 武汉纺织大学 | Has micropore-nano pore structure nanofiber porous membrane and preparation method thereof |
| CN109351205A (en) * | 2018-09-19 | 2019-02-19 | 广州中国科学院先进技术研究所 | A kind of silicon-oxygen-carbon ceramic hollow-fibre membrane and preparation method thereof |
| CN115513477A (en) * | 2022-11-11 | 2022-12-23 | 国家电投集团氢能科技发展有限公司 | Microporous layer slurry of proton exchange membrane fuel cell, gas diffusion layer and preparation method of microporous layer slurry |
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| US6716275B1 (en) * | 2001-12-11 | 2004-04-06 | Sandia Corporation | Gas impermeable glaze for sealing a porous ceramic surface |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106495734A (en) * | 2016-10-20 | 2017-03-15 | 合肥创想能源环境科技有限公司 | A kind of micropore finely tunes ceramic film preparation method |
| CN107082641A (en) * | 2017-05-24 | 2017-08-22 | 广西碧清源环保科技有限公司 | A kind of ceramic membrane materials component |
| CN107082641B (en) * | 2017-05-24 | 2023-04-25 | 广西碧清源环保科技有限公司 | Ceramic membrane material assembly |
| CN109351205A (en) * | 2018-09-19 | 2019-02-19 | 广州中国科学院先进技术研究所 | A kind of silicon-oxygen-carbon ceramic hollow-fibre membrane and preparation method thereof |
| CN109289540A (en) * | 2018-09-21 | 2019-02-01 | 武汉纺织大学 | Has micropore-nano pore structure nanofiber porous membrane and preparation method thereof |
| CN109289540B (en) * | 2018-09-21 | 2021-04-23 | 武汉纺织大学 | Nanofiber porous filter membrane with micropore-nanopore structure and preparation method thereof |
| CN115513477A (en) * | 2022-11-11 | 2022-12-23 | 国家电投集团氢能科技发展有限公司 | Microporous layer slurry of proton exchange membrane fuel cell, gas diffusion layer and preparation method of microporous layer slurry |
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