CN102773026A - Surface modification method for polytetrafluoroethylene separation membrane - Google Patents
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Abstract
The invention relates to a surface modification method for a polytetrafluoroethylene separation membrane. The method comprises the following steps of: activating the surface of the PTFE (polytetrafluoroethylene) membrane by virtue of a plasma technology, and then continuously depositing thin oxide layers on the surfaces of pore channels of the separation membrane by virtue of an atomic layer deposition technology to realize precise adjustment and control on pore diameter and surface properties of the separation membrane. According to the method, the plasma technology is used for pretreating, and then the atomic layer deposition is carried out, so that the growth mechanism of a deposition layer on the surface of the PTFE membrane is changed, the island type growthof the deposition layer is changed to conformal growth, the deposition layer is uniform and smooth, and the hydrophily, the pure water flux, the separating property and the anti-pollution capacity of the separation membrane are all obviously improved.
Description
Technical field
The present invention relates to a kind of diffusion barrier modification technology, particularly a kind of method of polytetrafluorethyleseparation separation membrane surface modification.
Background technology
Polytetrafluoroethylene (PTFE) is very important a kind of engineering plastics owing to have the chemistry and the physical property of a series of excellences, in a lot of fields application is arranged all, also is a kind of important membrane material.Yet when handling aqueous phase separation, can produce two problems: the one, strong-hydrophobicity needs bigger driving force during separation, and energy consumption is big, and flux is little; The 2nd, be prone to produce absorption and pollute, make membrane flux diminish, the life-span shortens.
Both at home and abroad the researcher has done a large amount of research to the surface modification of PTFE film, injects modification, filling-modified etc. comprising high-energy radiation graft modification, plasma treatment modification, chemical treatment modification, high-temperature melting method, ion beam.These methods have pluses and minuses separately, are difficult to find a kind of method of excellent combination property.Though high-energy radiation graft modification method is easy and simple to handle, be easy to control, the PTFE substrate after the modification is damaged easily, and mechanical property obviously descends; Effect cannot not held time longly after the plasma processing method modification, and the degree of hydrophilic modifying is limited; The chemical solution facture need be carried out in strong acid or strong alkali environment, and treatment temperature is also higher, complex procedures not only, and operational danger is higher, also produces a large amount of waste liquids; High-temperature melting method needs higher operating temperature, and the PTFE film is prone to deform, and pore structure is destroyed easily.
(Atomic Layer Deposition ALD) is a kind of gas phase deposition technology to ald, and at the concurrent limited reactions of being conigenous of substrate surface absorption, it can accurately control the thickness of sedimentary deposit on inferior dust level level based on gaseous precursor.The rarely found all reports of the application of ALD on diffusion barrier, several work of minority all are to concentrate under higher temperature, to use the ALD technology that the small-bore inoranic membrane is carried out surface modification, are used for gas and separate.
This seminar patent applied for " a kind of method " to the polytetrafluorethyleseparation separation membrane surface modification, application number 201110318831.X.We utilize the method for ald, and direct depositing metal oxide layer on poly tetrafluoroethylene improves the hydrophily of polytetrafluorethyleseparation separation membrane, reaching the increase pure water flux, and adjustable aperture simultaneously, increase the rejection of p-poly-phenyl ethene.But because PTFE film surface lacks active group, like hydroxyl, carboxyl, amino etc., at first in the subsurface nucleation of substrate, growth is carried out the pattern of the rounded particle of sedimentary deposit, rough surface around nuclear to the gas phase presoma then.Under lower frequency of depositing, limited to the hydrophily change of film, influence the increase of pure water flux.
Therefore, change sedimentation mechanism, make sedimentary deposit even, smooth, under less cycle-index, hydrophily changes obviously, and the PTFE membrane structure is destroyed little surface modifying method, has very important significance.
Summary of the invention
The objective of the invention is in order to change the growth mechanism of atomic layer deposition lamination at the PTFE separation membrane surface; Make sedimentary deposit even, smooth; Change that PTFE diffusion barrier hydrophily is poor, flux is little, be prone to pollute and the modified technique complicated problems, and provide a kind of simply, the method for polytetrafluorethyleseparation separation membrane surface modification efficiently.
Technical scheme of the present invention is: the method for polytetrafluorethyleseparation separation membrane surface modification is characterized in that comprising following concrete steps:
A places plasm reaction cavity with polytetrafluorethyleseparation separation membrane, vacuumizes, and regulates power 10w ~ 300w, processing time 1～10min, and each handles positive and negative once;
B will place ald instrument reative cell through the polytetrafluorethyleseparation separation membrane after step a handles, and vacuumize and heat to make reaction chamber temperature reach 50 ~ 200 ℃, make film under design temperature, keep 1 ~ 5min;
C at first closes air outlet valve, and first kind of presoma 0.01～1s of pulse keeps a period of time 0 ~ 60s; Open air outlet valve then, pulse cleaning gas, cleaning 5 ~ 60s; Close air outlet valve again, second kind of presoma 0.01 ~ 1s of pulse keeps a period of time 0 ~ 60s; Open air outlet valve at last again, pulse cleaning gas, cleaning 5 ~ 60s;
D is according to concrete needs, and repeating step c makes the polytetrafluorethyleseparation separation membrane of modification.
First kind of presoma described in the preferred steps c is trimethyl aluminium, titanium tetrachloride or isopropyl titanate; Second kind of presoma described in the preferred steps c is water or ozone; Cleaning gas described in the preferred steps c is nitrogen or argon gas.The number of times of repeating step c described in the preferred steps d is 10 ~ 500 times.
Beneficial effect:
The present invention utilizes plasma technique earlier the PTFE separation membrane surface to be carried out activation, re-uses technique for atomic layer deposition at its surface deposition layer of metal oxide skin(coating), and the combination property of diffusion barrier is significantly improved after the modification.With deposition titanium oxide layer on poly tetrafluoroethylene is example, and hydrophilicity strengthens, and directly shows contact angle from about the 130 original degree, and minimum can change to below 20 degree; The pure water flux maximum reach before unmodified more than 2.5 times; Improved contamination resistance; Single rejection of silicon oxide microsphere of disperseing to average grain diameter 142nm significantly improves, and can improve more than 60% at most before unmodified relatively, and technology of the present invention simply is easy to produce in batches.
Advantage of the present invention:
(1) with plasma basement membrane is carried out pre-treatment and activation, introduce active group, make the growth mechanism of metal oxide layer grown by island type growth becoming conformal, sedimentary deposit evenly, smoothly;
(2) on various basement membranes, all can deposit inorganic layer, and the thickness of sedimentary deposit can regulate on the level of atom level, thereby realize the aperture of diffusion barrier and continuous, the accurate adjusting of surface nature;
(3) easy production in batch, and the film character after the modification keeps permanent.
Description of drawings
Fig. 1 is SEM (SEM) photo before and after the modification of PTFE film among the embodiment 1, and figure a is the picture of the former film of PTFE; Figure b is the picture after the plasma treatment; Figure c is the photo of 150 titanium oxide circulations of deposition.
Fig. 2 is embodiment 1 depositing Ti O
2After, composite membrane Static Water contact angle is along with the situation of change figure of frequency of depositing.
Fig. 3 is embodiment 1 depositing Ti O
2After, the composite membrane pure water flux with to the single situation of change figure that disperses the silicon oxide microsphere rejection along with frequency of depositing of 142nm; Wherein ● the expression pure water flux, ■ representes rejection.
The specific embodiment
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: deionized water, nitrogen, trimethyl aluminium (TMA analyzes pure), silicon oxide microsphere (PS, self-control, average diameter 142nm); PTFE microporous barrier (Germany, Sartorius, average pore size 0.2 μ m, diameter 25mm); Plasma appearance (HPD-280, Nanjing Su Man Electronics Co., Ltd.); ALD deposits appearance (Cambridge NanoTech company, Savannah S100); X-ray photoelectron spectroscopic analysis (XPS, Thermo ESCALAB 250) field emission scanning electron microscope (FESEM, Hitachi S4800); Laser particle analyzer (U.S. Microtrac company, NPA152-31A; Contact angle measurement (Europe, the east of a river, Ningbo City hundred million detecting instrument companies, Dropmeter A-100); Total organic carbon analyzer (TOC, Japan, Shimadzu TOC-VCPH); Flux determinator (Amicon8010 of Millipore company type).
Embodiment 1: at first the PTFE diffusion barrier is put into plasma chamber, vacuumize, the adjusting plasma power is 22W, and positive and negative was respectively handled 5 minutes.Adopting isopropyl titanate (TIP) respectively is first kind of presoma, deionized water (H
2O) be second kind of presoma, high pure nitrogen (N
2) as carrier gas and cleaning gas.Two kinds of presoma burst lengths are respectively 0.2s, 0.015s, presoma open-assembly time 5s, cleaning time 20s.Reacting by heating room temperature to 150 ℃ makes film under the reative cell design temperature, keep 2min, and the preparation cycle-index is respectively 20,50,100,150,200,250,300 times modified membrane.
Table 1 is before and after the PTFE film plasma treatment, the composition of surface-element.(XPS records)
Can be found out that by table 1 the PTFE film is after plasma treatment, oxygen 1.06 (at.%) and nitrogen 0.31 (at.%) have been introduced in the surface.Because the introducing amount is less, the side has proved that plasma treatment maybe be less to the change of the chemistry of film and physical property.
SEM (SEM) photo in the present embodiment before and after the modification of PTFE film is as shown in Figure 1, and figure a is the picture of the former film of PTFE; Figure b is the picture after the plasma treatment; Figure c is the photo of 150 titanium oxide circulations of deposition.Can find out by Fig. 1 b, the PTFE film after plasma treatment pattern and former film (Fig. 1 a) does not have an obviously difference.After Fig. 1 c was 150 titanium oxide of deposition, the surface topography of film can find out that sedimentary deposit is deposited on the film surface uniform and smoothly, meets the conformal growth mechanism.
Present embodiment depositing Ti O
2After, composite membrane Static Water contact angle is along with the situation of change figure of frequency of depositing is as shown in Figure 2; Assay method: film is placed on the sample stage, and every film is got 10 positions, records data and averages.Can find out only 50 circulation times by Fig. 2, contact angle is reduced to 74.2 ± 4 ° from 131 ± 3 °; When deposition proceeded to 150 times, contact angle was 28 ± 5 °; Being increased to once more 250 times of frequency of depositing, 20 ± 5 ° of contact angles.
Present embodiment depositing Ti O
2After, the composite membrane pure water flux with to the single silicon oxide microsphere rejection of disperseing of 142nm along with the situation of change of frequency of depositing is as shown in Figure 3; (certain rotating speed stirs down, uses 16.17KPa pressure, and to composite membrane precompressed half an hour, per then 10 minutes meter one secondary data are counted 3 groups to average, and use the Millipore Amicon8010 of company type to measure the pure water flux of film.Under certain rotating speed, use 8KPa pressure, record the rejection data.) can see that by Fig. 3 the pure water flux of membrane increases along with the increase of cycle-index, reach the effect that effect changes greater than the film hydrophily because fenestra diminishes after the maximum, pure water flux diminishes gradually.The pure water flux maximum reach before unmodified more than 2.5 times.Rejection to silicon oxide microsphere increases along with the increase of frequency of depositing, and through 300 depositions, rejection is increased to 55.1% by original 16%.
With 150 times be example, contrast former film, when having realized that flux increases by 154%, rejection has also increased by 17% simultaneously, the combination property of film is improved.
Embodiment 2: at first the PTFE diffusion barrier is put into plasma chamber, vacuumize, the adjusting plasma power is 10W, and positive and negative was respectively handled 10 minutes.Adopt first kind of presoma of trimethyl aluminium (TMA) respectively, deionized water (H
2O) be second kind of presoma, argon gas (Ar) is as carrier gas and cleaning gas.Two kinds of presoma burst lengths are respectively 0.015s, 0.5s, and presoma open-assembly time is respectively 10s, 50s, and the cleaning time is respectively 30s, 60s.Reacting by heating room temperature to 70 ℃ makes film under the reative cell design temperature, keep 5min, and the preparation cycle-index is respectively 20,50,80,100 times modified membrane.
Film in the present embodiment after the surface modification, through the scanning electron microscope observation analysis, membrane aperture reduces along with the increase of frequency of depositing, and hydrophilic angle changes to 70 ± 4 °, 35 ± 5 °, 15 ± 6 °, 14 ± 6 ° by original 131 ° respectively.Pure water flux increases by 28%, 70%, 130%, 125% respectively, and the rejection of silicon oxide microsphere has been increased by 3%, 5%, 11%, 16% respectively.
Embodiment 3: at first the PTFE diffusion barrier is put into plasma chamber, vacuumize, the adjusting plasma power is 300W, and positive and negative was respectively handled 1 minute.Adopt titanium tetrachloride (TiCl respectively
4) be first kind of presoma, ozone (O
3) be second kind of presoma, argon gas (Ar) is as carrier gas and cleaning gas.Two kinds of presoma burst lengths are respectively 0.015s, 1s, and presoma open-assembly time is 0s, and the cleaning time is respectively 10s, 5s.Reacting by heating room temperature to 200 ℃ makes film under the reative cell design temperature, keep 1min, the modified membrane that the preparation cycle-index is 500 times.
Static Water contact angle through characterizing modified membrane is 28 ± 5 °, and pure water flux increases by 19%, to the rejection increase by 64% of silicon oxide microsphere.
Embodiment 4: at first the PTFE diffusion barrier is put into plasma chamber, vacuumize, the adjusting plasma power is 15W, and positive and negative was respectively handled 7 minutes.Adopting trimethyl aluminium (TMA) respectively is first kind of presoma, deionized water (H
2O) be second kind of presoma, high pure nitrogen (N
2) as carrier gas and cleaning gas.Two kinds of presoma burst lengths are respectively 1s, 0.01s, and presoma open-assembly time is respectively 55s, 8s, and the cleaning time is respectively 60s, 40s.Reacting by heating room temperature to 55 ℃ makes film under the reative cell design temperature, keep 1min, the modified membrane that the preparation cycle-index is 400 times.
Static Water contact angle through characterizing modified membrane is 34 ± 5 °, and pure water flux increases by 26%, to the rejection increase by 53% of silicon oxide microsphere.
Claims (5)
1. the method for polytetrafluorethyleseparation separation membrane surface modification, its concrete steps are following:
A places plasm reaction cavity with polytetrafluorethyleseparation separation membrane, vacuumizes, and regulates power 10w ~ 300w, processing time 1 ~ 10min, and each handles positive and negative once;
B will place ald instrument reative cell through the polytetrafluorethyleseparation separation membrane after step a handles, and vacuumize and heat to make reaction chamber temperature reach 50 ~ 200 ℃, make film under design temperature, keep 1 ~ 5min;
C at first closes air outlet valve, and first kind of presoma 0.01～1s of pulse keeps a period of time 0 ~ 60s; Open air outlet valve then, pulse cleaning gas, cleaning 5 ~ 60s; Close air outlet valve again, second kind of presoma 0.01 ~ 1s of pulse keeps a period of time 0 ~ 60s; Open air outlet valve at last again, pulse cleaning gas, cleaning 5 ~ 60s;
D is according to concrete needs, and repeating step c makes the polytetrafluorethyleseparation separation membrane of modification.
2. method according to claim 1 is characterized in that first kind of presoma described in the step c is trimethyl aluminium, titanium tetrachloride or isopropyl titanate.
3. method according to claim 1 is characterized in that second kind of presoma described in the step c is water or ozone.
4. method according to claim 1 is characterized in that the cleaning gas described in the step c is nitrogen or argon gas.
5. method according to claim 1, the number of times that it is characterized in that the repeating step c described in the steps d is 10 ~ 500 times.
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| CN104325803A (en) * | 2013-07-22 | 2015-02-04 | 财团法人工业技术研究院 | Screen printing film and surface modification method thereof |
| CN104524985A (en) * | 2014-12-11 | 2015-04-22 | 南京工业大学 | Method for hydrophobic and oleophobic modification of surface of separation membrane |
| CN106391317A (en) * | 2015-07-07 | 2017-02-15 | I3薄膜有限公司 | Metal coated polymembrane and method for electrofiltration and electro sorption by means of a metal coated polymembrane |
| CN108258155A (en) * | 2018-01-16 | 2018-07-06 | 福州大学 | A kind of method of the carrier transport of regulation and control and balance full-inorganic QLED |
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| GB2585038A (en) * | 2019-06-25 | 2020-12-30 | Inst Jozef Stefan | Method |
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| CN104325803A (en) * | 2013-07-22 | 2015-02-04 | 财团法人工业技术研究院 | Screen printing film and surface modification method thereof |
| CN104524985A (en) * | 2014-12-11 | 2015-04-22 | 南京工业大学 | Method for hydrophobic and oleophobic modification of surface of separation membrane |
| CN104524985B (en) * | 2014-12-11 | 2017-02-08 | 江苏久朗高科技股份有限公司 | Method for hydrophobic and oleophobic modification of surface of separation membrane |
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| CN110038445B (en) * | 2019-04-08 | 2022-09-16 | 同济大学 | Hydrophilic modification method for hydrophobic membrane |
| CN110038445A (en) * | 2019-04-08 | 2019-07-23 | 同济大学 | A kind of hydrophobic membrane hydrophilic modification method |
| CN113993555A (en) * | 2019-05-15 | 2022-01-28 | 首尔大学校产学协力团 | Method for manufacturing ePTFE artificial vascular grafts with improved hemocompatibility by selective plasma etching |
| GB2585038A (en) * | 2019-06-25 | 2020-12-30 | Inst Jozef Stefan | Method |
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