CN102491777A - Method for continuously precisely adjusting bore diameter of ceramic film - Google Patents
Method for continuously precisely adjusting bore diameter of ceramic film Download PDFInfo
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- CN102491777A CN102491777A CN2011103773972A CN201110377397A CN102491777A CN 102491777 A CN102491777 A CN 102491777A CN 2011103773972 A CN2011103773972 A CN 2011103773972A CN 201110377397 A CN201110377397 A CN 201110377397A CN 102491777 A CN102491777 A CN 102491777A
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- film
- presoma
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Abstract
The invention relates to a method for continuously precisely adjusting bore diameter of a ceramic film, which realizes continuous adjustment of the bore diameter from micrometer to nanometer and precise change from micro-filtration film to nano-filtration film and compact film. The method is characterized in that oxide film layers are deposited on the surfaces of particles of a ceramic film separating layer continuously by utilizing the technology of atomic layer deposition (ALD) and changing effective size of gaps among the particles so that continuous precise adjustment of film holes is realized. The method mainly includes steps of (1) controlling a certain reaction temperature and deposing a film tube in a reaction chamber and keeping for a certain time; (2) inflating a metal source precursor, pulse cleaning air, an oxidation precursor and pulse cleaning air into the reaction chamber; and (3) precisely controlling the thickness of a deposition layer by adjusting circular times of deposition. The method is simple in processing and controllable in process height, overcomes the defect that ration relation for controlling parameters and microstructure of the film cannot be built during preparing utilizing the conventional film preparing method, and the bore diameter of the ceramic film can be adjusted continuously precisely.
Description
Technical field
The present invention relates to the ceramic membrane aperture and carry out the method that continuous precision is regulated, utilize technique for atomic layer deposition critically to regulate the separating layer duct size of ceramic membrane more precisely, belong to the ceramic foam field.
Background technology
The ceramic foam mould material because have that chemicalstability is good, physical strength is big, outstanding advantage such as but strong, the high temperature resistant high pressure back flushing of antimicrobial pollution capacity, regenerative power are strong, have broad application prospects in fields such as normal temperature and high temperature filtration device, support of the catalyst and inorganic reaction separators.The method for preparing at present ceramic membrane mainly contains solid particles sintering process, sol-gel method (Sol-Gel) and chemical Vapor deposition process (CVD).The particles sintering method is the modal preparation method of commercialization ceramic membrane; Can wait the ceramic membrane for preparing different apertures through particle and the suitable temperature of selecting different size; But this method makes film in drying or sintering process, tend to take place perhaps skin effect phenomenon of cracking, and is the ceramic membrane of preparation small-bore, needs to use repeatedly sintering formation transition layer of different size particle warp; Operation is comparatively complicated, and energy consumption is high.The Sol-Gel method is important a kind of film-forming method, but its preparation liquid infiltrates in the macropore of supporting body surface easily, therefore needs one deck or multilayer intermediate layer, thereby causes existing in the film use bigger resistance; Coarse and the macroporous structure of supporting body surface can make the rete of preparation produce defective simultaneously.And CVD method of regulating in membrane pore size owned by France generally is applicable to the film that adjustment aperture is bigger, easy obstruction duct for the film of small-bore, and also general depositing temperature is higher as more than 600 ℃.In addition, traditional film-forming method all is difficult to set up the quantitative relationship of controlled variable and film microstructure in the membrane prepare process, realizes the quantitative control of membrane prepare process.Therefore develop and simple the method for minute adjustment is carried out in the ceramic membrane aperture, realize obtaining the ceramic membrane in other apertures, expand its range of application, have very important significance from the ceramic membrane of known pore size size.
Summary of the invention
The objective of the invention is in order to overcome the weak point of prior art, and propose a kind of the ceramic membrane aperture is carried out the method that continuous precision regulates and need not to introduce transition layer.
Technical scheme of the present invention is: a kind of method that the continuous precision adjusting is carried out in the ceramic membrane aperture, and its concrete steps are following:
A places ald instrument reaction chamber with ceramic separation film, vacuumizes and reacting by heating chambers temp to 250～450 ℃, makes sample under design temperature, keep 5～30min, and the interior air pressure of reaction chamber is 0.01～10torr;
B at first closes air outlet valve, pulse metal source presoma, and the time is 0.01～1s, then keeps for some time 0～60s; Open air outlet valve then, pulse cleaning gas, cleaning 3～15s; Close air outlet valve again, pulse oxidizes presoma 0.01～1s keeps for some time 0～60s; Open air outlet valve at last again, pulse cleaning gas, cleaning 3～15s; The homo(io)thermism of two kinds of presomas is between 20～50 ℃;
C is according to concrete needs, repeating step b, the size in minute adjustment duct.
Source metal presoma described in the preferred steps b is trimethylaluminium or titanium isopropylate or titanium tetrachloride; Described oxidation presoma is a deionized water.Cleaning gas described in the preferred steps b is nitrogen or argon gas.
The number of times of repeating step b described in the preferred steps c is 10～2000 times; More preferably 100～2000 times.
Beneficial effect:
The present invention utilizes technique for atomic layer deposition, and successive sedimentation even compact sull in duct, ceramic membrane top layer carries out minute adjustment to the aperture of ceramic separation film, realized the aperture by micron order to nano level continuous adjusting.Through changing the sedimentary cycle index of ALD, the alumina layer of deposition different thickness on ceramic basement membrane.Scanning electronic microscope observation has confirmed the increase along with frequency of depositing, and membrane pore size progressively reduces until complete closed, and formation has the ultra-thin separating layer of graded pore structure; Tested the pure water flux of different frequency of depositing film pipes and to the rejection of bovine serum albumin (BSA); The result shows the increase along with frequency of depositing; The pure water flux of film diminishes gradually and the rejection of BSA is increased gradually, and the amplitude that rejection rises is apparently higher than the flux decline scope.Like 600 ALD cyclic deposition aluminum oxide of warp, membrane flux is by presedimentary 1700L (m
2Hbar)
-1Drop to 110L (m
2Hbar)
-1, the rejection of BSA then is increased to 98% by presedimentary 3%, realized basement membrane from the microfiltration membrane to the ultra-filtration membrane, nf membrane is so that the transformation of dense film.
(1) precision of aperture adjustment is high.ALD circulation each time, the thickness of the settled layer of generation also is that fenestra can reduce on the precision that is superior to 0.1 nanometer below 0.1 nanometer;
(2) the aperture adjustment process is evenly continuous.The deposit thickness that ALD produces on ceramic membrane can come even successive control through changing cycle index, obtains any aperture of aperture between basement membrane and dense film;
(3) simple to operation.Before the ald reaction, do not need basement membrane is carried out pre-treatment; And each step reaction is all carried out in cavity in the deposition process, can control automatically, does not need manual intervention, and does not need aftertreatment after the deposition end, can directly use;
(4) technology green non-pollution.ALD to the aperture adjustment process of ceramic membrane not with an organic solvent, unnecessary presoma or by product are recyclable, do not have " three wastes " discharging.
Description of drawings
Fig. 1 is the surperficial SEM figure of not sedimentary ceramic membrane basement membrane.
Fig. 2 has been deposited the surperficial SEM figure behind the alumina layer 100 times for the ceramic membrane basement membrane.
Fig. 3 has been deposited the surperficial SEM figure behind the alumina layer 600 times for the ceramic membrane basement membrane.
Fig. 4 has been deposited the surperficial SEM figure behind the titanium oxide layer 400 times for the ceramic membrane basement membrane.
Fig. 5 has been deposited the surperficial SEM figure behind the titanium oxide layer 2000 times for the ceramic membrane basement membrane.
The practical implementation method
Provide specific embodiment of the present invention below, but the present invention not merely is defined in these embodiment, these embodiment do not constitute the restriction to claim saturation range of the present invention.
Agents useful for same and instrument: the ceramic-film tube that uses in the experiment comes from Nanjing JiuSi High-Tech Co.,Ltd, and the film O.D.T. is 12.15mm, and internal diameter is 7.72mm, and internal surface is ZrO
2Rete, thickness are about 12 μ m, and mean pore size is 50nm, and supporter is Al
2O
3Depositing Al
2O
3Trimethylaluminium (TMA) presoma that layer uses is available from MO institute of Nanjing University, and purity is 99.99%; What the test rejection was used is the bovine serum albumin (BSA) available from GM Corporation, and its purity is greater than 97%.The ald appearance (ALD) that uses is purchased the company in Cambridge NanoTech, and its model is Savannah S100.(FESEM, Hitachi S4800) observe the microstructure of film by field emission scanning electron microscope;
Concrete steps of the present invention are: a places ald instrument reaction chamber with ceramic separation film, vacuumizes and the reacting by heating chamber, and sample is kept for some time under design temperature;
B at first closes air outlet valve, and pulse metal source presoma then keeps for some time; Open air outlet valve then, pulse cleaning gas, cleaning; Close air outlet valve again, the pulse oxidizes presoma keeps for some time; Open air outlet valve at last again, pulse cleaning gas, cleaning;
C is according to concrete needs, repeating step b, the size in minute adjustment duct.
Embodiment 1: adopt trimethylaluminium (TMA) respectively, deionized water (H
2O) be presoma, the homo(io)thermism of presoma is at 20 ℃, high pure nitrogen (N
2) as carrier gas and cleaning gas.Two kinds of presoma burst lengths all are 0.015s, and presoma keeps exposure duration to be 10s, equal 20s of cleaning time.Reacting by heating chambers temp to 250 ℃ lets the film pipe under the reaction chamber design temperature, keep 20min, and the air pressure in the reaction chamber is 0.01torr, and frequency of depositing is 100 times.What Fig. 1 and Fig. 2 provided is the surface scan electron micrograph of the film after ALD handles under ceramic membrane basement membrane and the above-mentioned condition.The pure water flux of this film and be respectively 1230L (m to the rejection of BSA
2Hbar)
-1With 15%
Embodiment 2: adopt trimethylaluminium (TMA) respectively, deionized water (H
2O) be presoma, the homo(io)thermism of presoma is at 30 ℃, high pure nitrogen (N
2) as carrier gas and cleaning gas.Two kinds of presoma burst lengths all are 0.1s, and presoma keeps equal 0s of exposure duration, and equal 6s of cleaning time, carrier gas flux are 20sccm.Reacting by heating chambers temp to 450 ℃ lets the film pipe under the reaction chamber design temperature, keep 5min, and the air pressure in the reaction chamber is 0.1torr, and frequency of depositing is 600 times.What Fig. 3 provided is the surface scan electron micrograph of this film.The pure water flux of this film is 110L (m
2Hbar)
-1, be 98% to the rejection of BSA.And undressed its pure water flux of ceramic membrane basement membrane and the rejection of BSA is respectively 1700L (m
2Hbar)
-1With 3%.
Embodiment 3: adopt titanium tetrachloride respectively, deionized water is a presoma, and the homo(io)thermism of presoma is at 40 ℃, and high pure nitrogen is as carrier gas and cleaning gas.Two kinds of presoma burst lengths all are 0.5s, presoma equal 30s of exposure duration, and equal 3s of cleaning time, carrier gas flux are 20sccm.Reacting by heating chambers temp to 300 ℃ lets the film pipe under the reaction chamber design temperature, keep 30min, and the air pressure in the reaction chamber is 5torr, and frequency of depositing is 400 times.What Fig. 4 provided is the surface scan electron micrograph of this film.The pure water flux of this film and be respectively 200L (m to the rejection of BSA
2Hbar)
-1With 65%.
Embodiment 4: adopt titanium isopropylate respectively, deionized water is a presoma, and the homo(io)thermism of presoma is at 50 ℃, and high pure nitrogen is as carrier gas and cleaning gas.Two kinds of presoma burst lengths all are 1s, presoma exposure duration 60s, and cleaning time 10s, carrier gas flux is 20sccm.Reacting by heating chambers temp to 350 ℃ lets the film pipe under the reaction chamber design temperature, keep 10min, and the air pressure in the reaction chamber is 10torr, and frequency of depositing is 2000 times.What Fig. 5 provided is the surface scan electron micrograph of this film.When measuring pure water flux, this film is under the pressure of 0.5MPa, and surpassing 5 hours does not all have penetrating fluid, can think the duct of this film by complete closed, and pure water flux is 0, is 100% to the rejection of BSA.
More ceramic basement membrane surface topography (Fig. 1) and the ceramic membrane that deposited through ALD can be found out the particle surface of handling back formation separating layer through ALD by smooth coating, the intermittence between the particle corresponding reduce (Fig. 2 to Fig. 5).And change ALD mode of deposition, coating degree and gap length adjustable.Along with the aggravation of the degree of coating, hole diminishes, even can be formed whole continuous film by complete adhesion between the particle.On macroscopic view, be presented as pure water flux to reduce gradually and the rejection raising.
Claims (4)
1. method to ceramic separation film duct minute adjustment, its concrete steps are following:
A places ald instrument reaction chamber with ceramic separation film, vacuumizes and reacting by heating chambers temp to 250～450 ℃, makes sample under design temperature, keep 5～30min, and the interior air pressure of reaction chamber is 0.01～10torr;
B at first closes air outlet valve, pulse metal source presoma, and the time is 0.01～1s, then keeps for some time 0～60s; Open air outlet valve then, pulse cleaning gas, cleaning 3～15s; Close air outlet valve again, pulse oxidizes presoma 0.01～1s keeps for some time 0～60s; Open air outlet valve at last again, pulse cleaning gas, cleaning 3～15s; The homo(io)thermism of two kinds of presomas is between 20～50 ℃;
C is according to concrete needs, repeating step b, the size in minute adjustment duct.
2. method according to claim 1 is characterized in that the source metal presoma described in the step b is trimethylaluminium or titanium isopropylate or titanium tetrachloride; Described oxidation presoma is a deionized water.
3. method according to claim 1 is characterized in that the cleaning gas described in the step b is nitrogen or argon gas.
4. method according to claim 1, the number of times that it is characterized in that the repeating step b described in the step c is 10～2000 times.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102728238A (en) * | 2012-07-06 | 2012-10-17 | 南京工业大学 | Method for modifying surface of polypropylene separation membrane |
| CN105771684A (en) * | 2016-05-04 | 2016-07-20 | 南京工业大学 | Novel ceramic nanofiltration membrane preparation method |
| CN110508155A (en) * | 2019-08-21 | 2019-11-29 | 南京大学 | A kind of preparation method of zinc-base inorganic-organic hybridization nanoporous seperation film |
| CN111111467A (en) * | 2020-01-06 | 2020-05-08 | 常州费曼生物科技有限公司 | Method for preparing precise liquid medicine filter membrane and precise liquid medicine filter membrane |
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| CN102021535A (en) * | 2010-12-21 | 2011-04-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing aluminum-doped zinc oxide transparent conducting films at low temperature |
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2011
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Patent Citations (5)
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| JP2005306625A (en) * | 2004-04-16 | 2005-11-04 | Denso Corp | Ceramic porous plate and method and apparatus for manufacturing the same |
| CN101688298A (en) * | 2007-05-02 | 2010-03-31 | 法国原子能委员会 | The method and apparatus of preparation multilayered coating on substrate |
| CN102202820A (en) * | 2008-08-25 | 2011-09-28 | 印可得株式会社 | Method for manufacturing metal flakes |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102728238A (en) * | 2012-07-06 | 2012-10-17 | 南京工业大学 | Method for modifying surface of polypropylene separation membrane |
| CN102728238B (en) * | 2012-07-06 | 2015-02-18 | 南京工业大学 | Method for modifying surface of polypropylene separation membrane |
| CN105771684A (en) * | 2016-05-04 | 2016-07-20 | 南京工业大学 | Novel ceramic nanofiltration membrane preparation method |
| CN105771684B (en) * | 2016-05-04 | 2018-07-20 | 南京工业大学 | A kind of preparation method of nanofiltration membrane |
| CN110508155A (en) * | 2019-08-21 | 2019-11-29 | 南京大学 | A kind of preparation method of zinc-base inorganic-organic hybridization nanoporous seperation film |
| CN111111467A (en) * | 2020-01-06 | 2020-05-08 | 常州费曼生物科技有限公司 | Method for preparing precise liquid medicine filter membrane and precise liquid medicine filter membrane |
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Application publication date: 20120613 |