CN103272482A - Intermittent plasma modification method for porous separation membrane - Google Patents
Intermittent plasma modification method for porous separation membrane Download PDFInfo
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Abstract
The invention provides an intermittent plasma modification method for preparing a porous separation membrane. The intermittent plasma modification method comprises the following steps of: fixing a conventional ultrafiltration membrane or microfiltration membrane into a room temperature plasma chamber in which an electrode plate is arranged; introducing a gas into the chamber under a condition with a certain vacuum degree; and treating the surface of a base membrane at room temperature in an intermittent glow discharge manner to obtain a hydrophilic or hydrophobic porous separation membrane final product. Compared with the conventional continuous and impulse type room temperature plasma modification methods, the modification method provided by the invention is simple in process and strong in controllability, does not need special equipment, and can significantly enhance the hydrophilicity or hydrophobicity of the surface of the porous separation membrane; and the prepared hydrophilic porous separation membrane can be widely applied to processes such as ultrafiltration, microfiltration and dialysis, the prepared hydrophobic porous separation membrane can be widely applied to processes such as membrane distillation, membrane absorption, membrane extraction, vapor permeation and oily feed liquid clarification, and the prepared porous separation membrane can also be used as a base membrane used for preparing a composite membrane.
Description
Technical field
The present invention relates to a kind of method of modifying of porous diffusion barrier, particularly a kind of method that adopts the modified porous separation membrane surface of batch (-type) plasma mode.
Background technology
Membrane separation technique has obtained the develop rapidly that attracts people's attention in recent years as a kind of novel, fluid separation element operating technology efficiently, has been widely used in each department of national economy.Comprised world's diffusion barrier market scale of membrane product, device and correlation engineering in 2009 about 45,000,000,000 dollars, wherein membrane product is about 8,000,000,000 dollars.Domestic, separation membrane product market was about 6,000,000,000 yuans in 2009, added correlation engineering, and market scale reaches 25,000,000,000 yuans.
Different because of separate object and separation principle, separation membrane surface often is required to present higher hydrophily or hydrophobicity.For example, be the ultrafiltration, microfiltration process of driving force with the pressure differential and be the dialysis procedure of driving force with the concentration difference that used porous diffusion barrier surface need present high-hydrophilic to reduce the film pollution level in the separation process, improves film separation process efficient; Be the film still-process of driving force with the temperature difference and be that the process need faces such as membrane extraction, film absorption, steam infiltration of driving force present high hydrophobicity with the concentration difference, to increase the wetting ability of the anti-feed liquid of diffusion barrier, guarantee the long-term stability operation of process; In addition, when filtering clarification oiliness feed liquid, often wish that also separation membrane surface has the hydrophobicity of height, separate resistance in order to reduce.Therefore, hydrophilic, hydrophobic property and its process efficiency of separation membrane surface are closely related.
Though membrane separation technique is used widely, in order further to improve film separating process efficient, hydrophilic, hydrophobic character how to improve the film surface better is one of academia and industrial quarters problem of showing great attention to all the time.The hydrophilic, hydrophobic property in film surface also is subjected to the influence of membrane superficial tissue pattern simultaneously on the one hand from the chemical composition of membrane material itself, and the film surface chemistry is formed the function of surface that provides the foundation in the middle of both.It is generally acknowledged that when the film surface is hydrophily (water contact angle is less than 90 degree), the more big then hydrophily of surface roughness is more strong, in like manner, when the film surface is hydrophobicity (water contact angle is greater than 90 degree), the more big then hydrophobicity of surface roughness is more strong.
As a kind of effective surface modifying method, the room-temperature plasma modification technology has obtained studying widely and using in membrane surface modification.According to the difference of air inlet kind, the room-temperature plasma processing procedure can give separation membrane surface different hydrophilic, hydrophobic characteristics.Usually, select for use the gas that can make the film surface produce hydroxyl, carboxyl, amino isopolarity group to carry out the room-temperature plasma modification, can increase the hydrophily on film surface; And select fluoro-gas for use, contain phenyl ring gas, long chain alkane gas etc. can make the film surface produce the gas of low-surface-energy non-polar group, then can improve the hydrophobicity on film surface.For example, adopt the microporous polypropylene membrane of ammonia room-temperature plasma technical finesse surface hydrophobicity, prolongation along with the processing time, the water contact angle on microporous polypropylene membrane surface can be reduced to 53.7 degree (processing time 8min) gradually by 128.2 degree, the film surface hydrophilicity significantly increases, and makes the bovine serum albumin(BSA) adsorbance of microporous polypropylene membrane by 180 initial μ g/cm
2Be reduced to 120 μ g/cm gradually
2(processing time 8min) effectively improved the pollution capacity of anti-protein adsorption the [Chemical Engineering Journal, 145 (2008): 218-224] of hydrophobic microporous polypropylene membrane.And for example, adopt carbon tetrafluoride normal-temperature plasma technology modified poly (ether-sulfone) ultrafiltration membrane capable, by regulating key parameters such as power, processing time, the water contact angle on poly (ether sulfone) film surface can be increased to about 125 degree by 62 degree, the poly (ether-sulfone) ultrafiltration membrane successful transformation of script surface hydrophilicity is become can be used for the surface hydrophobicity perforated membrane [Journal of Membrane Sciences, 407-408 (2012): 164-175] of film distillation desalination.
Usually, surface modification at perforated membrane, existing room-temperature plasma processing procedure is generally under continuous mode, regulate film surface chemistry composition or structure and morphology by changing key parameters such as gaseous species, sample and electrode distance, chamber vacuum, power, processing time, obtain the required hydrophilic, hydrophobic property in film surface.Though big quantity research report all confirms, above-mentioned continous way room-temperature plasma modification technology is chemical composition and the structure and morphology on modified membrane surface effectively, but also there is following deficiency: along with the prolongation in processing time, the hydrophilic, hydrophobic property in film surface tends to reach stationary value, and it is then little to the hydrophilic, hydrophobic property influence of film surface to continue to increase the processing time.Be example [Journal of Membrane Sciences with above-mentioned carbon tetrafluoride plasma modification poly (ether-sulfone) ultrafiltration membrane, 407-408 (2012): 164-175], when the processing time increases to 5min by 0min, film surface water contact angle is significantly improved to 113 degree by 62 degree, but continue to prolong the processing time to 40min, film surface water contact angle only slowly is increased to 125 degree by 113 degree; If think further to change film surface water contact angle, can predict needs to handle the longer time, can bring thus that processing cost increases, equipment heating is difficult to control and the film surface pore structure is tending towards serial problem such as densified.
In the existing room-temperature plasma modification technology, the method that adopts pulsed plasma is arranged also.This method is carried out the sample surfaces processing by the millimicrosecond pulse (the glow switch time is controlled at millisecond or microsecond range scale) that modes such as hollow cathode pipe produce plasma.For example, adopt the pulsed plasma deposition process can prepare super-hydrophobic Nano microsphere [Chem.Mater., 14 (2002): 4566-4571], can make polymer can keep the function [Chem.Mater., 8 (1996): 37-42] of acid anhydrides better when adopting pulsed plasma technology polymerizable maleimide acid anhydrides.But so far, Shang Weiyou adopts the report of the modified porous diffusion barrier of pulsed room-temperature plasma technology, and the enforcement of this technology needs comparatively complex apparatus condition.
Summary of the invention
At existing continous way room-temperature plasma modification technology can not the hydrophilic, hydrophobic property in wider regulation and control porous diffusion barrier surface deficiency, and the deficiency of existing pulsed room-temperature plasma modification technology dependence complex device condition, the invention provides a kind of simple porous diffusion barrier batch (-type) plasma modification method.Perforated membrane method of modifying process provided by the invention is simple, controllability strong and need not special installation, can significantly strengthen hydrophily or the hydrophobicity on porous diffusion barrier surface; Adopt the made hydrophilic porous diffusion barrier of the present invention can be widely used in processes such as ultrafiltration, micro-filtration, dialysis, made hydrophobic porous diffusion barrier can be widely used in processes such as film distillation, film absorption, membrane extraction, steam infiltration, oiliness feed clarification, and made porous diffusion barrier also can be used as the preparation that basement membrane is used for composite membrane.
Batch (-type) plasma modification method at porous diffusion barrier provided by the invention comprises the steps, porous diffusion barrier is fixed in the room-temperature plasma chamber that battery lead plate is housed, under certain vacuum degree condition, gas is introduced chamber, adopt glow discharge at intermittence mode to handle the porous diffusion barrier surface under the room temperature and obtain final modified porous diffusion barrier product; Described glow discharge at intermittence mode is: open glow switch 1s～10min when arriving specified requirements, close glow switch 1s～10min(intermittent phase afterwards), and then unlatching glow switch 1s～10min, repeatable operation like this, but total processing time is no more than 120min, and preferable total processing time is 10～30min.
Described specified requirements is that vacuum can guarantee that room-temperature plasma glow discharge normally takes place in the chamber, and meanwhile, gas enters the flow of chamber and generally controls at 0.01～200L/min.
The scientific basis that the present invention proposes batch (-type) room temperature plasma method of modifying is: continuous glow discharge time is split, by indoor nucleation process and the germination process of compression glow discharge time regulation and control plasma chamber, control gas ionization degree or level of graft polymerization, and reduce the degree of secondary reaction as far as possible; By the batch process that increases, finish the supply of gas (or monomer); By regulating chemical composition and the structure and morphology of discharge time and intermittent time comprehensive regulation separation membrane surface, change the hydrophilic, hydrophobic characteristic in film surface to a greater degree with this.
Described porous diffusion barrier is conventional ultrafiltration film or the micro-filtration membrane of loose structure for surface and section, and the distance between itself and battery lead plate is 1～10cm.In addition, the present invention can change glow discharge power with reference to passing through in the prior art, and porous diffusion barrier sample and chamber are taked necessary pretreated mode optimization process.For example, the general preferable range of glow discharge power is 10～450W; Adopt pure water to wash repeatedly 3～10 times or mode that ultrasonic wave cleans 5～15min is cleaned in advance to the porous diffusion barrier sample earlier, remove impurity such as protection liquid in membrane surface and the fenestra or dust; The organic solvent of available heat cleans plasma chamber, or adopts the mode that inert gas is fed chamber and open glow discharge to clean plasma cavity.
The present invention can also carry out preliminary treatment to the porous diffusion barrier sample according to the mode of available technology adopting inert gas room-temperature plasma glow discharge, and purpose is cleaning film surface, produces avtive spot or regulate the membrane superficial tissue pattern in advance by corrasion at face; Also this kind preprocessing process can be combined with above-mentioned batch (-type) room-temperature plasma modifying process, form the batch (-type) room-temperature plasma modifying process that comprises " inert gas preliminary treatment, function gas (gas of the present invention) glow discharge, intermittent phase ".
Described milipore filter and micro-filtration membrane are milipore filter or the micro-filtration membrane that macromolecular materials such as polyether sulfone, polysulfones, Kynoar, polyacrylonitrile, polyvinyl chloride, polyvinyl alcohol, Pioloform, polyvinyl acetal, cellulose acetate, shitosan, polyamide, polyimides, PPSU, polybenzimidazoles ketone, polybenzimidazoles, PAEK, polyether-ether-ketone are made, or are milipore filter or micro-filtration membrane that inorganic material such as pottery, metal, metal oxide, cellular glass, zeolite are made; Form membrane can be plain film formula, doughnut formula or tubular type.
Described gas is oxygen, air, nitrogen, water vapour, ammonia, the steam of carboxy-containing acid group's acrylic monomer is (as acrylic acid, methacrylic acid etc.), the steam (as maleic anhydride etc.) that contains the anhydrides monomer of anhydride group, the steam of the amide-type monomer of amido-containing group is (as acrylamide, N,N-DMAA etc.), the steam of the acrylic ester monomer of hydroxyl and ester group group is (as hydroxypropyl acrylate, hydroxy-ethyl acrylate etc.), contain the steam of vinylpyridine class monomer of pyridine ring (as the 3-vinylpyridine, 4-vinylpridine etc.) or above-mentioned gas compound.When adopting above-mentioned gas, can form hydroxyl, amino or carboxyl isopolarity group on the porous diffusion barrier surface, thereby improved the hydrophily on film surface, the hydrophilic porous diffusion barrier product of preparation can be used for the basement membrane that ultrafiltration, micro-filtration, dialysis procedure or conduct prepare composite membrane.It is basement membrane that composite membrane herein refers to modified porous diffusion barrier, in NF membrane, reverse osmosis membrane, gas-permeable membrane, the infiltration evaporation preferential water permeable membrane of basement membrane by the preparation of methods such as coating, curtain coating, interfacial polymerization.
Described gas is the compound of the steam (as perfluoro butyl ethyl propylene acid esters, perfluoro capryl ethyl propylene acid esters, perfluoro butyl ethyl-methyl acrylate, perfluoro capryl ethyl-methyl acrylate etc.) of steam (as perfluorobutyl ethylene, perfluor decyl ethylene etc.), acrylate containing fluorine or the fluorine-containing methacrylate class monomer of fluoro-gas (as carbon tetrafluoride, perfluoroethane, octafluorocyclobutane etc.), fluorine-containing vinyl monomer, cinnamic steam or above-mentioned gas.When adopting above-mentioned gas, can form the non-polar group of low-surface-energy on the porous diffusion barrier surface, thereby improve the hydrophobicity on film surface, the hydrophobic porous diffusion barrier product of preparation can be used for the basement membrane that film distillation, film absorption, membrane extraction, steam infiltration, oiliness feed clarification or conduct prepare composite membrane.It is basement membrane that composite membrane herein refers to modified porous diffusion barrier, at basement membrane by the preferential saturating organic matter film of the infiltration evaporation of methods such as coating, curtain coating, interfacial polymerization preparations.
Described vacuum is for guaranteeing the required vacuum of the normal generation of room-temperature plasma glow discharge.The preferable range of absolute pressure value is 10～2000Pa in the plasma chamber of the present invention.
The flow that described gas enters chamber is 0.01～200L/min.
After plasma treatment finished, the present invention can carry out cooling processing to diffusion barrier sample or plasma cavity according to the mode that leaves standstill in the prior art usually, and the cooling processing time is generally 3～10min, during close air inlet but keep described vacuum condition.After membrane sample to be separated is cooled to room temperature, can also carry out post processing to it according to prior art, for example use the pure water rinsing sample 3～5 times, or adopt the mode of conventional extracting or immersion to remove the unnecessary component in striping surface in case of necessity.
Among the present invention, but above-mentioned condition any combination, and prepared hydrophilic porous diffusion barrier can be used for the basement membrane of composite membranes such as ultrafiltration, micro-filtration, dialysis procedure or conduct preparation NF membrane, reverse osmosis membrane, gas-permeable membrane, the preferential water permeable membrane of infiltration evaporation; Prepared hydrophobic porous diffusion barrier can be used for the basement membrane of film distillation, film absorption, membrane extraction, steam infiltration, oiliness feed clarification or the preferential saturating organic matter composite membrane of conduct preparation infiltration evaporation.
Compare with the plasma modification method of existing porous diffusion barrier, positive progressive effect of the present invention is:
1. can regulate the hydrophilic, hydrophobic property on porous diffusion barrier surface in larger scope, overcome the drawback that the hydrophilic, hydrophobic property of face tends towards stability with the processing time lengthening in the existing continous way room-temperature plasma modifying process.
2. pass through regulation and control glow discharge time and intermittent time and total processing time, but comprehensive regulation film surface chemistry The Nomenclature Composition and Structure of Complexes pattern.
3. compare with existing pulsed room-temperature plasma method of modifying, method of modifying process provided by the invention is simple, controllability strong and need not special installation, has more economy.
4. have permanent high-hydrophilic or high hydrophobicity and suitable surface pore structure and skin depth with the porous diffusion barrier product after the inventive method modification, film applied range, combination property height have great economic benefit.
Description of drawings
Film surface infrared spectrum figure among Fig. 1 embodiment 1 before and after the polyvinylidene fluoride (PVDF) ultrafiltration membrane hydrophilic modifying
The surface scan electron microscope of polyacrylonitrile ultrafiltration film and contact angle photo among Fig. 2 embodiment 2
Surface scan electron microscope among Fig. 3 embodiment 2 behind the polyacrylonitrile ultrafiltration film hydrophobically modified and contact angle photo
Surface scan electron microscope among Fig. 4 comparative example 2-2 behind the polyacrylonitrile ultrafiltration film hydrophobically modified and contact angle photo
The specific embodiment
The present invention will be further described below in conjunction with specific embodiment, but the present invention is not limited.
Embodiment 1 hydrophilic modifying prepares milipore filter
The steam of selecting acrylamide for use is the hydrophilic modifying that gas carries out polyvinylidene fluoride (PVDF) ultrafiltration membrane.The plain film formula polyvinylidene fluoride (PVDF) ultrafiltration membrane (molecular cut off 70kDa) of 5 * 2.5cm is put into YZDO8-2C type room-temperature plasma chamber, distance between sample and battery lead plate is 4cm, opening vacuum system makes the interior absolute pressure of chamber reach 35～40Pa, open the gas sampling valve, behind the balance 1min, open glow switch 3min(glow discharge power 120w), close glow switch 3min afterwards, 5 times so repeatedly, cool off 5min after finishing, obtain the hydrophilic ultrafiltration membrane of modification.
Fig. 1 is the film surface infrared spectrum figure before and after the polyvinylidene fluoride (PVDF) ultrafiltration membrane hydrophilic modifying, and Modified Membrane is at 3217cm
-1And 1678cm
-1The characteristic absorption peak of acid amides has appearred in the place.(OCA20, Data Physics Instruments Co. Germany) measure, and the surface water contact angle of original polyvinylidene fluoride (PVDF) ultrafiltration membrane is 78 degree, and the surface water contact angle of embodiment 1 Modified Membrane is down to 35 degree through contact angle measurement.In addition, adopt the 0.5g/L bovine serum albumin solution that the static adsorbance of the albumen of film before and after the modification is measured, the result shows that the static adsorbance of the albumen of this polyvinylidene fluoride (PVDF) ultrafiltration membrane is 82 μ g/cm before the modification
2, Modified Membrane is then reduced to 40 μ g/cm
2
Comparative example 1-1
Select material and the operating condition of embodiment 1 for use, difference is continuous glow discharge 3min.Through measuring, Modified Membrane surface water contact angle is 65 degree, and the static adsorbance of albumen is 69 μ g/cm
2
Comparative example 1-2
Select material and the operating condition of embodiment 1 for use, difference is continuous glow discharge 10min.Through measuring, Modified Membrane surface water contact angle is 52 degree, and the static adsorbance of albumen is 57 μ g/cm
2
Comparative example 1-3
Select material and the operating condition of embodiment 1 for use, difference is continuous glow discharge 15min.Through measuring, Modified Membrane surface water contact angle is 49 degree, and the static adsorbance of albumen is 53 μ g/cm
2
Comparative example 1-4
Select material and the operating condition of embodiment 1 for use, difference is continuous glow discharge 20min.Through measuring, Modified Membrane surface water contact angle is 48 degree, and the static adsorbance of albumen is 51 μ g/cm
2
Comparative example 1-5
Select material and the operating condition of embodiment 1 for use, difference is continuous glow discharge 30min.Through measuring, Modified Membrane surface water contact angle is 46 degree, and the static adsorbance of albumen is 47 μ g/cm
2
By above-mentioned comparing result as seen, compare with conventional continous way room-temperature plasma method, adopt method of modifying of the present invention can obtain surface hydrophilicity and the stronger modified polyvinilidene fluoride milipore filter of stain resistance.
Embodiment 2 hydrophobically modifieds prepare film distillation film
Select for use argon gas and carbon tetrafluoride gas to carry out the hydrophobically modified of polyacrylonitrile ultrafiltration film.The plain film formula polyacrylonitrile ultrafiltration film (molecular cut off 20kDa) of 5 * 3cm is put into YZDO8-2C type room-temperature plasma chamber, distance between sample and battery lead plate is 5cm, opening vacuum system makes the interior absolute pressure of chamber reach 850～1000Pa, open the argon gas intake valve, behind the balance 1min, open glow switch 5min(glow discharge power 40w), close glow switch 5min afterwards, close the argon gas intake valve then, open the carbon tetrafluoride intake valve, behind the balance 1min, open glow switch 5min(glow discharge power 100w), close glow switch 5min afterwards, 3 times so repeatedly, cool off 5min after finishing, obtain the hydrophobic film distillation film of modification.
Fig. 2 and Fig. 3 are respectively the surface scan electron micrographs before and after the polyacrylonitrile ultrafiltration film hydrophobically modified, and wherein embedded figure is its water contact angle photo.The surface water contact angle of original polyacrylonitrile ultrafiltration film is 55 degree, and the surface water contact angle of embodiment 2 Modified Membrane is increased to 155 degree.(material liquid is the sodium-chloride water solution of 80 ℃ 3.5wt% to adopt the desalting performance of the film before and after the conventional vacuum membrane distillation process measurement modification, film downstream vacuum is 95kPa), the result shows, original polyacrylonitrile ultrafiltration film is because having than strongly hydrophilic, saline solution penetrates fenestra, can't be applied to film distillation desalination processes; The Modified Membrane that this embodiment obtains can be used for film distillation desalination processes, and membrane flux is 70kg/m
2H, salt rejection rate reaches 99.98%.
Comparative example 2-1
Select material and the operating condition of embodiment 2 for use, difference is continuous glow discharge 15min when the carbon tetrafluoride air inlet.Through measuring, Modified Membrane surface water contact angle is 120 degree, film distillating ventilating amount 65kg/m
2H, salt rejection rate is 96.5%.
Comparative example 2-2
Select material and the operating condition of embodiment 2 for use, difference is continuous glow discharge 30min when the carbon tetrafluoride air inlet.Through measuring, Modified Membrane surface water contact angle is 125 degree, film distillating ventilating amount 63kg/m
2H, salt rejection rate is 99.2%.Fig. 4 is the surface scan electron micrograph of the modification hydrophobic membrane of this comparative example's acquisition, and wherein embedded figure is the water contact angle photo.
By above-mentioned comparing result as seen, compare with conventional continous way room-temperature plasma method, adopt method of modifying of the present invention can obtain surface hydrophobic and the stronger modified polyacrylonitrile hydrophobic membrane distillation film of film distillation desalting performance.
Claims (6)
1. the batch (-type) plasma modification method of a porous diffusion barrier, it is characterized in that comprising the steps, porous diffusion barrier is fixed in the room-temperature plasma chamber that battery lead plate is housed, under certain vacuum degree condition, gas is introduced chamber, adopt glow discharge at intermittence mode to handle the porous diffusion barrier surface under the room temperature and obtain final modified porous diffusion barrier product; Described glow discharge at intermittence mode is: open glow switch 1s～10min when arriving specified requirements, close glow switch 1s～10min afterwards, and then open glow switch 1s～10min, repeatable operation like this, but total processing time be no more than 120min; Described specified requirements is that vacuum can guarantee that room-temperature plasma glow discharge normally takes place in the chamber.
2. method of modifying according to claim 1, described porous diffusion barrier is conventional ultrafiltration film or the micro-filtration membrane of loose structure for surface and section, and the distance between itself and battery lead plate is 1～10cm.
3. method of modifying according to claim 1, described gas is oxygen, air, nitrogen, water vapour, ammonia, the steam of carboxy-containing acid group's acrylic monomer is (as acrylic acid, methacrylic acid etc.), the steam (as maleic anhydride etc.) that contains the anhydrides monomer of anhydride group, the steam of the amide-type monomer of amido-containing group is (as acrylamide, N,N-DMAA etc.), the steam of the acrylic ester monomer of hydroxyl and ester group group is (as hydroxypropyl acrylate, hydroxy-ethyl acrylate etc.), contain the steam of vinylpyridine class monomer of pyridine ring (as the 3-vinylpyridine, 4-vinylpridine etc.) or above-mentioned gas compound.
4. utilize the hydrophilic porous diffusion barrier product of any one method of modifying preparation in the claim 1,2,3, be used for the basement membrane of ultrafiltration, micro-filtration, dialysis procedure or conduct preparation composite membrane.
5. method of modifying according to claim 1, described gas is the compound of the steam (as perfluoro butyl ethyl propylene acid esters, perfluoro capryl ethyl propylene acid esters, perfluoro butyl ethyl-methyl acrylate, perfluoro capryl ethyl-methyl acrylate etc.) of steam (as perfluorobutyl ethylene, perfluor decyl ethylene etc.), acrylate containing fluorine or the fluorine-containing methacrylate class monomer of fluoro-gas (as carbon tetrafluoride, perfluoroethane, octafluorocyclobutane etc.), fluorine-containing vinyl monomer, cinnamic steam or above-mentioned gas.
6. utilize the hydrophobic porous diffusion barrier product of any one method of modifying preparation in the claim 1,2,5, be used for the basement membrane of film distillation, film absorption, membrane extraction, steam infiltration, oiliness feed clarification or conduct preparation composite membrane.
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| CN105688687A (en) * | 2016-02-29 | 2016-06-22 | 江苏久朗高科技股份有限公司 | Preparation technology of hydrophobic and oleophobic film |
| CN107998687A (en) * | 2017-12-08 | 2018-05-08 | 刘丁菡 | A kind of preparation method of intelligent water-oil separating material |
| CN109280205A (en) * | 2018-10-26 | 2019-01-29 | 南京科技职业学院 | The preparation method of polytetrafluoroethylene (PTFE) double-hydropholic film |
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| CN105688687A (en) * | 2016-02-29 | 2016-06-22 | 江苏久朗高科技股份有限公司 | Preparation technology of hydrophobic and oleophobic film |
| CN105688687B (en) * | 2016-02-29 | 2018-09-04 | 江苏久朗高科技股份有限公司 | The preparation process of double-hydropholic film |
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| CN110404412B (en) * | 2019-07-31 | 2021-11-23 | 常州航爵医药科技有限公司 | Molecular sieve membrane for separating ethanol solution pervaporation water and preparation method thereof |
| CN115079317A (en) * | 2021-03-12 | 2022-09-20 | 江苏菲沃泰纳米科技股份有限公司 | Goggles with hydrophilic antifogging film layer and film coating method |
| CN113413932A (en) * | 2021-06-29 | 2021-09-21 | 郑州大学 | Hydrophobic modification method of microfluidic chip material |
| CN113413932B (en) * | 2021-06-29 | 2023-03-14 | 郑州大学 | Hydrophobic modification method of microfluidic chip material |
| CN115337790A (en) * | 2022-07-15 | 2022-11-15 | 上海工程技术大学 | Preparation method of super-hydrophilic polyether sulfone separation membrane and separation membrane prepared by same |
| CN115337790B (en) * | 2022-07-15 | 2023-10-20 | 上海工程技术大学 | Preparation method of super-hydrophilic polyethersulfone separation membrane and separation membrane prepared by same |
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