CN104353368B - A kind of ordered micro-cellular structure ceramic membrane and preparation method thereof - Google Patents
A kind of ordered micro-cellular structure ceramic membrane and preparation method thereof Download PDFInfo
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- CN104353368B CN104353368B CN201410649089.4A CN201410649089A CN104353368B CN 104353368 B CN104353368 B CN 104353368B CN 201410649089 A CN201410649089 A CN 201410649089A CN 104353368 B CN104353368 B CN 104353368B
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Abstract
The invention discloses a kind of ceramic membrane with ordered micro-cellular structure and preparation method thereof.The present invention has the ceramic membrane of ordered micro-cellular structure, and, the spherical ordered arrangement architecture porous ceramics of hole shape rule homogeneous for aperture, the aperture of ceramic membrane is between 0.2 5 μm, and porosity is between 50 80%.The specific practice of the inventive method is first to prepare ordered arrangement organic high polymer microsphere template, then this template is impregnated with ceramic precursor, it is transferred in gasification furnace progressively be warming up to uniform temperature after having impregnated and carries out heat treatment, realize the removal of template and the crosslinking of precursor simultaneously, finally it is placed in high temperature sintering furnace and further heats up cracking, i.e. prepare ordered micro-cellular structure ceramic membrane.Utilize this ordered micro-cellular structure ceramic membrane pore-size distribution narrow, the feature that separation accuracy is high, can be used for the applications such as water process, air cleaning, it is achieved the precision of specific dimensions material is separated.
Description
Technical field
The invention belongs to ceramic separation film technical field, be specifically related to a kind of pottery with ordered micro-cellular structure
Film and preparation method thereof.
Background technology
Compared with organic membrane, inorganic ceramic film has good stability, can be high temperature resistant, corrosion-resistant, resistance to organic
Solvent, resistance to microbial attack；Mechanical strength is big, and pressure wearability is good；Vapor sterilization sterilization can be carried out,
The advantages such as cleaning and regeneration is convenient, can be used for gas separation, liquid isolation of purified and membrane reactor, at food
Industry, pharmacy all have extensively with the field such as petrochemical industry and environmental conservation with biological engineering, chemistry
Application.
The pore structure of ceramic membrane is the key affecting ceramic membrane application, and has the separating property of ceramic membrane
Material impact.Therefore, in order to regulate and control the pore size of ceramic membrane, shape and distribution, many both at home and abroad
Research worker has carried out substantial amounts of research work to this.Nijmeijer etc. (Am.Ceram.Soc.Bull.,
1998,77 (4): 95) centrifuging is utilized to prepare the Alpha-alumina ceramic-film tube of long 13cm, diameter 16mm,
Aperture in this membrane tube radially graded, is not easily formed fenestra in water treatment procedure and silts up, and
Pollutant under retaining rest on key-course surface, easily clean, interception capacity and flux after mechanical cleaning
Can nearly 100% recovery.South China Science & Engineering University Sui Xian grade (CN 00117221.2) uses melt film centrifuging process
Preparing gradient porous ceramics film, its fenestra aperture is by managing interior outwards distribution, inner surface apertures in continuous gradient
Footpath is minimum, and outer surface aperture is maximum, and fenestra aperture is 0.05-20 μm, and porosity is 30-80%.Zeng Yu
Equality (CN 200710048076.1) is sintered by ball milling mixing, flow casting molding, lyophilization, unsticking
Also preparing gradient porous ceramics film etc. technique, its fenestra aperture is 0.1-100 μm, and porosity is
20-90%, oriented linear porosity, hole has orientation open communication and aperture gradient variable in a thickness direction
Change.Nanjing University of Technology's Xu Nan equality (CN 200810023905.5) passes through sol-gel process at macropore
The supporting body surface in footpath prepares perfect sunken small-bore ceramic super-filtering film.(the CN such as Tan little Yao
200810249536.1) use inversion of phases-sintering process to prepare there is porous support layer, transition zone and effectively
The honeycomb type ceramic film of stratum disjunctum unsymmetric structure, it is big that this ceramic membrane has unit volume membrane area
(500-9000m2/m3), the feature such as intensity high (200-1200MPa), easy sealing.
Ceramic membrane separation accuracy in actual application is affected by maximum diameter of hole, due to above-mentioned porous
The ceramic membrane pore-size distribution that ceramic membrane preparation technology obtains is wider, hole shape heterogeneity, and it cannot be guaranteed that hole
Footpath size is completely the same, therefore limits the raising of ceramic membrane separation precision, it is impossible to realizes precision and filters.
Summary of the invention
It is an object of the invention to the deficiency overcoming above-mentioned prior art to exist, it is provided that one has orderly micropore
Ceramic membrane of structure and preparation method thereof.
The present invention has the ceramic membrane of ordered micro-cellular structure, it is characterized in that, described ceramic membrane be aperture homogeneous,
The spherical ordered arrangement architecture porous ceramics of hole shape rule, the aperture of ceramic membrane between 0.2-5 μm, hole
Gap rate is between 50-80%.
The present invention uses polymer pyrolysis-template, utilizes the ordered arrangement structure of template, in conjunction with pottery first
Driving body transformation technology and accurately control the microcellular structure parameter of ceramic membrane, final preparing has uniform pore diameter, row
Show the microporous membrane of sequence.Specific practice is first to prepare ordered arrangement organic high polymer microsphere template, so
Impregnate this template with ceramic precursor afterwards, be transferred to after having impregnated in gasification furnace progressively be warming up to a constant temperature
Degree carries out heat treatment, realizes the removal of template and the crosslinking of precursor simultaneously, is finally placed in high temperature sintering furnace
In further heat up cracking, i.e. prepare ordered micro-cellular structure ceramic membrane.
The preparation process of ordered micro-cellular structure ceramic membrane is as follows:
(1) preparation of template
It is that 1:10～1:30 adds in beaker in mass ratio by organic high polymer microsphere and deionized water, carries out
Ultrasonic disperse 1～2h, is then transferred in high speed centrifuge be centrifuged settling 0.5～1h, removes upper strata
Deionized water, takes out lower sediment thing and is placed in 80～120 DEG C dry 2～6h in baking oven, it is thus achieved that organic high score
Sub-microsphere template.
(2) infiltration of precursor
It is that 1:1～1:5 adds in beaker in mass ratio by ceramic precursor and organic solvent, is sufficiently stirred for molten
Ceramic setter liquid solution is prepared to obtain after solution；This ceramic precursor solution for vacuum impregnation steps (1) is obtained
Organic high polymer microsphere template, after having impregnated, carries out decompression and organic solvent is distilled off.
(3) removal of template and the crosslinking of precursor
The organic high polymer microsphere template penetrating into ceramic precursor step (2) obtained is placed into gasification furnace
In, progressively it is warming up to 200～400 DEG C, is incubated 1～4h so that organic high polymer microsphere template is gasified
Eliminate, complete the crosslinking of ceramic precursor simultaneously, have been formed with sequence uniform cell structure the most in the material.
(4) ceramic of precursor
The product that step (3) obtains is transferred in high temperature sintering furnace, is warming up to 1000～1300 DEG C, protect
Temperature 1～2h carries out Pintsch process, makes ceramic precursor be fully converted to inorganic ceramic, the most prepared after cooling
Ordered micro-cellular structure ceramic membrane.
Described organic high polymer microsphere is polystyrene microsphere, polrvinyl chloride microsphere, polyethylene microsphere or poly-
Acryl microbeads.
Described ceramic precursor is polysiloxanes, Polycarbosilane, polymethyl silicane or polysilazane.
Described organic solvent is toluene, dimethylbenzene, oxolane or normal hexane.
The inventive method can accurately control ceramic membrane microcellular structure (include hole shape, aperture size,
Hole arrangement architecture), thus improve ceramic membrane separation precision, it is achieved the precision of specific dimensions material is separated.
Ordered micro-cellular structure ceramic membrane prepared by the present invention is the spherical ordered arrangement that aperture is homogeneous, hole shape is regular
Structural porous pottery.According to the diameter of the organic high polymer microsphere as template, the aperture of ceramic membrane
Caning be controlled between 0.2-5 μm, controlled porosity is between 50-80%.Utilize this ordered micro-cellular structure
Ceramic membrane pore-size distribution is narrow, the feature that separation accuracy is high, can be used for the application necks such as water process, air cleaning
Territory, it is achieved the precision of specific dimensions material is separated.
There is advantages that
Generally ceramic membrane mainly utilizes " screening " principle to separate solute, and film allows the component less than its aperture
By and retain bigger than its aperture or suitable with pore size component.Aperture due to conventional ceramic film
Wider distribution, hole shape is irregular, limits the raising of ceramic membrane separation precision, it is impossible to realizes precision and filters.
The ordered micro-cellular structure ceramic membrane that the present invention provides, by regulating the organic high polymer microsphere as template
Diameter and arrangement architecture, it is possible to accurately control the microcellular structure of ceramic membrane, thus improve ceramic membrane
Separation accuracy, can make particle diameter, variform component be separated, it is achieved to specific dimensions material
Precision separates, and has good application prospect at aspects such as water process, air cleanings.
Prepare additionally, current orderly micropore ceramics generally uses the inorganic matters such as silicon dioxide to do template, follow-up
Template remove technique more complicated.The present invention uses organic polymer to do template, the removal of template and pioneer
The crosslinking of body synchronously completes, and template is removed more complete, and technical process is simpler, low cost of manufacture, it is easy to
Realize large-scale production.
Accompanying drawing explanation
Fig. 1 is the SEM photograph of embodiment 1 ordered arrangement polystyrene microsphere template；
Fig. 2 is the SEM photograph 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
It is further discussed below the present invention below in conjunction with embodiment.Specific embodiment is not intended to the right of the present invention and wants
Ask.
Embodiment 1
(1) polystyrene microsphere and the deionized water of particle diameter 300nm are added burning for 1:15 in mass ratio
In Bei, carry out ultrasonic disperse 1h, be then transferred in high speed centrifuge be centrifuged settling 0.5h, take out
Lower sediment thing is placed in 100 DEG C of dry 4h in baking oven, it is thus achieved that polystyrene microsphere template.
(2) polymethyl silicane and toluene are added in beaker for 1:4 in mass ratio, are sufficiently stirred for dissolving,
The polystyrene microsphere template obtained by this polymethyl silicane solution for vacuum impregnation steps (1), dipping completes
After, carry out decompression and toluene is distilled off.
(3) product that step (2) obtains is placed in gasification furnace, is progressively warming up to 300 DEG C, insulation
2h so that polystyrene microsphere template is gasified elimination, completes the crosslinking of polymethyl silicane, then simultaneously
Being transferred in high temperature sintering furnace, be warming up to 1000 DEG C, insulation 1h carries out Pintsch process, the most prepared after cooling
Ordered micro-cellular structure ceramic membrane.
Ceramic membrane uniform pore diameter, hole shape that the present embodiment 1 prepares are regular, arrangement is orderly, and average pore size is
354nm, porosity is 70.3%.Fig. 1 is ordered into arranging the SEM photograph of polystyrene microsphere template；Figure
2 SEM photograph being ordered into microporous membrane；Fig. 3 is ordered into the pore size distribution curve of microporous membrane.
Embodiment 2
(1) polrvinyl chloride microsphere and the deionized water of particle diameter 500nm are added burning for 1:20 in mass ratio
In Bei, carry out ultrasonic disperse 1h, be then transferred in high speed centrifuge be centrifuged settling 1h, under taking-up
Layer precipitate is placed in 110 DEG C of dry 4h in baking oven, it is thus achieved that polrvinyl chloride microsphere template.
(2) Polycarbosilane and dimethylbenzene are added in beaker for 1:5 in mass ratio, are sufficiently stirred for dissolving,
The polrvinyl chloride microsphere template that this Polycarbosilane solution for vacuum impregnation steps (1) is obtained, after having impregnated,
Carry out decompression and dimethylbenzene is distilled off.
(3) product that step (2) obtains is placed in gasification furnace, is progressively warming up to 350 DEG C, insulation
1h so that polrvinyl chloride microsphere template is gasified elimination, completes the crosslinking of Polycarbosilane simultaneously, then turns
Moving in high temperature sintering furnace, be warming up to 1100 DEG C, insulation 1h carries out Pintsch process, and i.e. preparing after cooling has
Sequence microcellular structure ceramic membrane.
Ceramic membrane uniform pore diameter, hole shape that the present embodiment 2 prepares are regular, arrangement is orderly, and average pore size is
568nm, porosity is 65.2%.
Embodiment 3
(1) polyethylene microsphere and the deionized water of particle diameter 1 μm are added in beaker for 1:25 in mass ratio,
Carry out ultrasonic disperse 2h, be then transferred in high speed centrifuge be centrifuged settling 0.5h, take out lower floor and sink
Shallow lake thing is placed in 120 DEG C of dry 2h in baking oven, it is thus achieved that polyethylene microsphere template.
(2) polysiloxanes and oxolane are added in beaker for 1:3 in mass ratio, are sufficiently stirred for dissolving,
The polyethylene microsphere template that this polysiloxane solution vacuum impregnation step (1) is obtained, after having impregnated,
Carry out decompression and oxolane is distilled off.
(3) product that step (2) obtains is placed in gasification furnace, is progressively warming up to 380 DEG C, insulation
2h so that polyethylene microsphere template is gasified elimination, completes the crosslinking of polysiloxanes simultaneously, then shifts
To high temperature sintering furnace, being warming up to 1300 DEG C, insulation 1h carries out Pintsch process, i.e. prepares in order after cooling
Microcellular structure ceramic membrane.
Ceramic membrane uniform pore diameter, hole shape that the present embodiment 3 prepares are regular, arrangement is orderly, and average pore size is
1.1 μm, porosity is 61.6%.
Embodiment 4
(1) polypropylene microsphere and the deionized water of particle diameter 4 μm are added in beaker for 1:15 in mass ratio,
Carry out ultrasonic disperse 2h, be then transferred in high speed centrifuge be centrifuged settling 0.5h, take out lower floor and sink
Shallow lake thing is placed in 110 DEG C of dry 3h in baking oven, it is thus achieved that polypropylene microsphere template.
(2) polysilazane and toluene are added in beaker for 1:2 in mass ratio, be sufficiently stirred for dissolving, will
The polypropylene microsphere template that this polysilazane solution for vacuum impregnation steps (1) obtains, after having impregnated, enters
Row decompression is distilled off toluene.
(3) product that step (2) obtains is placed in gasification furnace, is progressively warming up to 320 DEG C, insulation
1h so that polypropylene microsphere template is gasified elimination, completes the crosslinking of polysilazane simultaneously, then shifts
To high temperature sintering furnace, being warming up to 1200 DEG C, insulation 1h carries out Pintsch process, i.e. prepares in order after cooling
Microcellular structure ceramic membrane.
Ceramic membrane uniform pore diameter, hole shape that the present embodiment 4 prepares are regular, arrangement is orderly, and average pore size is
4.2 μm, porosity is 54.8%.
Claims (4)
1. a preparation method for ordered micro-cellular structure ceramic membrane, is characterized in that, according to following step
Suddenly carry out:
(1) preparation of template
It is that 1:10～1:30 adds beaker in mass ratio by organic high polymer microsphere and deionized water
In, carry out ultrasonic disperse 1～2h, be then transferred in high speed centrifuge be centrifuged sedimentation
0.5～1h, remove upper strata deionized water, take out lower sediment thing and be placed in baking oven 80～120
DEG C be dried 2～6h, it is thus achieved that organic high polymer microsphere template；
(2) infiltration of precursor
It is that 1:1～1:5 adds in beaker in mass ratio by ceramic precursor and organic solvent, fills
Ceramic setter liquid solution is prepared to obtain after point stirring and dissolving；This ceramic precursor solution for vacuum is impregnated
The organic high polymer microsphere template that step (1) obtains, after having impregnated, carries out decompression distillation
Remove organic solvent；
(3) removal of template and the crosslinking of precursor
The organic high polymer microsphere template penetrating into ceramic precursor step (2) obtained is placed
In gasification furnace, progressively it is warming up to 200～400 DEG C, is incubated 1～4h so that organic polymer
Microsphere template is gasified elimination, completes the crosslinking of ceramic precursor, the most simultaneously
Form orderly uniform cell structure；
(4) ceramic of precursor
The product that step (3) obtains is transferred in high temperature sintering furnace, is warming up to 1000～1300
DEG C, insulation 1～2h carries out Pintsch process, makes ceramic precursor be fully converted to inorganic ceramic,
Ordered micro-cellular structure ceramic membrane is i.e. prepared after cooling.
The preparation method of ordered micro-cellular structure ceramic membrane the most according to claim 1, it is special
Levying and be, described step (1) organic high polymer microsphere is that polystyrene microsphere, polrvinyl chloride are micro-
Ball, polyethylene microsphere or polypropylene microsphere.
The preparation method of ordered micro-cellular structure ceramic membrane the most according to claim 1, its
Feature is, in described step (2), ceramic precursor is polysiloxanes, Polycarbosilane, poly-methyl
Silane or polysilazane.
The preparation method of ordered micro-cellular structure ceramic membrane the most according to claim 1, its
Feature is, in described step (2), organic solvent is toluene, dimethylbenzene, oxolane or just own
Alkane.
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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 |
| 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 |
| 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 |
| CN115513477B (en) * | 2022-11-11 | 2023-03-10 | 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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