CN103861465A - Method for modifying surface super-hydrophilicity of hydrophobic separation membrane material - Google Patents
Method for modifying surface super-hydrophilicity of hydrophobic separation membrane material Download PDFInfo
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Abstract
The invention provides a method for modifying the surface super-hydrophilicity of a hydrophobic separation membrane material. The method is characterized by comprising the following specific steps: first step: placing a hydrophobic separation membrane into a plasma device and carrying out surface plasma discharging treatment, and then putting the membrane into the air to be oxidized; second step: putting the membrane treated in the first step into a toluene solution containing trimesoyl chloride and reacting, and after the reaction, taking out a product for proceeding the third step; and third step: putting the membrane into a toluene solution containing terminal amino modified hydrophilic silicon dioxide nano-particles and a sodium alginate water solution in sequence and circulating for a plurality of times to obtain the modified separation membrane with surface hydrophilicity. With the adoption of the method, the super-hydrophilic modification of the surface of the hydrophobic separation membrane is realized so that the application energy consumption of the hydrophobic separation membrane is reduced and the pollution-resisting performance of the hydrophobic separation membrane is improved.
Description
Technical field
The invention belongs to diffusion barrier modification field, be specifically related to the super hydrophilic modifying of separation membrane surface, by hydrophobic separation membrane surface construction organic-inorganic stratiform double team structure, prepare super hydrophilic membrane surface.
Background technology
In recent years, diffusion barrier has been brought into play increasing effect aspect water resources development and utilization, comprise that sewage disposal, desalinization, ultra-pure water the aspect such as prepare, and also there is great application market in fields such as chemical industry, food, medical treatment, new forms of energy, more and more known by masses.Conventional separation membrane material has polypropylene (PP), polyether sulfone (PES), polysulfones (PSF), polytetrafluoroethylene (PTFE) (PTFE), Kynoar (PVDF) etc., be mainly hydrophobic macromolecular material, this type of material has the characteristic of good mechanical stability, heat endurance, chemical stability and easy machine-shaping, and therefore also impelling in commercial diffusion barrier is hydrophobic separation membrane material greatly.But there is the problem that inevitably exists film to pollute in actual separation application as the aspect such as sewage disposal, drink water purifying compared with the hydrophobic film material of low-surface-energy, because its hydrophobic surface very easily with isolating environment in the pollutant such as protein, colloid, large biological molecule produce hydrophobic effect, make its adhesion and be gathered in film surface and fenestra, cause the continuous decrease of the separating property of diffusion barrier own, shortened its service life.The resistance when hydrophobic effect of another outer membrane face makes hydrone see through film is larger, has increased separating energy consumption.Above two reasons have increased hydrophobic separation membrane operation cost in actual use greatly, have limited it and have further applied.
For addressing the above problem, present stage, except by optimizing membrane module and operating condition, carries out surface hydrophilic modification to separation membrane material and becomes the focus of researcher research.A large amount of researchs show; the hydrophily on film surface increases; being conducive to hydrone is preferentially adsorbed on film surface and sees through film; and be conducive to form hydrophilic layer structure on film surface; form the nearly water layer structure of film surface protection; all kinds of macromolecule contaminants can be repelled and come, effectively reduce the pollution level in film practical application, extend its service life.Film surface is surpassed to hydrophilic modifying, can improve to the full extent the membrane pollution problem that hydrophobic separation membrane faces, promote its separative efficiency.
Present stage is mainly applied to master with blend amphipathic nature block polymer, surface grafting hydrophilic polymer and surface to the surface hydrophilic modification side of diffusion barrier; after said method exists modification, hydrophilic effect is not obvious; modified condition harshness; modified effect is inhomogeneous, is unfavorable for the various unfavorable factors such as large-scale production.The plasma technique using in the present invention acts on the top layer of membrane material uniformly can reserved materials ontological property time, make inert coating Surface Creation reactable avtive spot, and utilize the electrostatic absorption principle of very easily having an effect, by orderly the modified hydrophilic Nano particles of silicon dioxide of hydrophilic polyanion electrolyte sodium alginate and the positively charged film surface that is incorporated into, and the extensive agglomeration traits that can effectively avoid nano particle very easily to produce, form the super hydrophilic layer of equally distributed nano silicon on film surface, realize the super hydrophilic modifying in the surface of hydrophobic film material.
Summary of the invention
The object of this invention is to provide a kind of method of hydrophobic separation membrane material being carried out to the super hydrophilic modifying in surface.
In order to achieve the above object, the invention provides the method for the super hydrophilic modifying of a kind of hydrophobic separation membrane material surface, it is characterized in that, concrete steps comprise:
The first step: hydrophobic separation membrane is placed in to plasma device, carries out surface plasma discharge process, be placed in air and be oxidized, generate active reaction sites;
Second step: the toluene solution that is placed in pyromellitic trimethylsilyl chloride through first step film after treatment is reacted, take out and carry out the 3rd step after reaction;
The 3rd step: film is first placed in the toluene solution and sodium alginate aqueous solution of the amino modified hydrophilic silicon dioxide nano particle of end, obtains the hydrophobic separation membrane after modification.
Preferably, the method for the described super hydrophilic modifying of hydrophobic separation membrane material surface also comprises:
The 4th step: repeat the 3rd step until obtain the surperficial double team number of plies needing, finally film is placed in to distilled water and fully cleans.
More preferably, described number of repetition is not less than 3 times.
Preferably, the plasma device in the described first step is low pressure or atmospheric plasma equipment, 50～500 watts of discharge powers, and the discharge process time is 10～300 seconds.
Preferably, the oxidization time in the described first step is 10～120 minutes.
Preferably, the hydrophobic separation membrane in the described first step is PP, PES, PSF, PVDF or PTFE film.
Preferably, the weight concentration of the toluene solution of the pyromellitic trimethylsilyl chloride in described second step is 0.1%～1%.
Preferably, the weight concentration of the toluene solution of the hydrophilic silicon dioxide nano particle in the 3rd described step is 0.5%～2%, and the weight concentration of sodium alginate aqueous solution is 0.1%～1%.
Preferably, after film being placed in to the toluene solution or sodium alginate aqueous solution of the amino modified hydrophilic silicon dioxide nano particle of end, need clean film with straight alcohol solution, remove unnecessary toluene or water in film surface and duct.
Compared with prior art, the invention has the beneficial effects as follows:
The present invention carries out surface preparation by plasma technique to hydrophobic separation membrane, introduce reaction site, and introduce the further activating surface of pyromellitic trimethylsilyl chloride, finally alternately in the hydrophilic silicon dioxide nano-particle solution of surface amino groups modification and sodium alginate soln, react absorption, prepare the super hydrophilic nanoparticle layers of film surface coverage organic-inorganic double team structure, realize the super hydrophilic modifying of hydrophobic separation membrane surface, thereby reduce the application energy consumption of hydrophobic diffusion barrier and promote its antifouling property.A kind of membrane surface modification method that is simple, energy-conserving and environment-protective, be applicable to carry out large-scale production.
The specific embodiment
Below in conjunction with specific embodiment, describe the present invention in detail, should be appreciated that, these embodiment can be used to illustrate the present invention but are not limited to scope of the present invention.Each solution concentration in following instance is weight concentration, and surface contact angle is static hydrolysis feeler.The amino modified hydrophilic silicon dioxide nano particle of end in embodiment is by hydrophilic silicon dioxide nano particle (Shanghai Shi Fan Chemical Co., Ltd., 20nm) surface modification preparation, concrete grammar is by the hydrophilic silicon dioxide nano particle through ultrasonic dispersion: 3-aminopropyl triethoxysilane: toluene refluxes and prepares for 3 hours with mass ratio 2:1:100 blend and at 100 ℃.
Embodiment 1
A method for the super hydrophilic modifying of hydrophobic separation membrane material surface, concrete steps are:
(1) the PVDF Flat Membrane of 8 × 8cm is placed in to cold plasma and processes processing instrument, plasma discharge is carried out in film surface and process 30 seconds, 100 watts of discharge powers, are placed in air and are fully oxidized 10 minutes, generate hydroxyl isoreactivity reaction site;
(2) again film is dipped in the toluene solution of 0.5% pyromellitic trimethylsilyl chloride and fully reacts 15min, take out and carry out step (3);
(3) film is first placed in 1% hydrophilic silicon dioxide nano particle toluene solution and 0.1% sodium alginate soln, after film being placed in to the toluene solution or sodium alginate aqueous solution of the amino modified hydrophilic silicon dioxide nano particle of end, need clean film with straight alcohol solution, remove unnecessary toluene or water in film surface and duct;
(4) repeat step (3) 4 times, finally film is placed in to distilled water and fully cleans, obtain modification pvdf membrane, adopt the method for dripping of lying to test its surface water contact angle, above-mentioned method of modifying, makes film surface contact angle drop to 12 ° by 105 °.
Embodiment 2
A method for the super hydrophilic modifying of hydrophobic separation membrane material surface, concrete steps are:
(1) the PP Flat Membrane of 10 × 10cm is placed in to atmospheric dielectric barrier discharge plasma, plasma discharge is carried out in film surface and process 10 seconds, 500 watts of discharge powers, are placed in air and are fully oxidized 60 minutes, generate hydroxyl isoreactivity reaction site;
(2) again film is dipped in the toluene solution of 0.1% pyromellitic trimethylsilyl chloride and carries out fully reaction 30 minutes, take out and carry out step (3);
(3) film is first placed in 0.5% hydrophilic silicon dioxide nano particle toluene solution and 0.2% sodium alginate soln, after film being placed in to the toluene solution or sodium alginate aqueous solution of the amino modified hydrophilic silicon dioxide nano particle of end, need clean film with straight alcohol solution, remove unnecessary toluene or water in film surface and duct;
(4) repeat step (3) 4 times, finally film is placed in to distilled water and fully cleans, obtain MODIFIED PP film, adopt the method for dripping of lying to test its surface water contact angle, above-mentioned method of modifying, makes film surface contact angle drop to 10 ° by 125 °.
Embodiment 3
A method for the super hydrophilic modifying of hydrophobic separation membrane material surface, concrete steps are:
(1) the PP Flat Membrane of 10 × 10cm is placed in to atmospheric dielectric barrier discharge plasma, plasma discharge is carried out in film surface and process 300 seconds, 50 watts of discharge powers, are placed in air and are fully oxidized 120 minutes, generate hydroxyl isoreactivity reaction site;
(2) again film is dipped in the toluene solution of 0.1% pyromellitic trimethylsilyl chloride and carries out fully reaction 30 minutes, take out and carry out step (3);
(3) film is first placed in 2% hydrophilic silicon dioxide nano particle toluene solution and 0.4% sodium alginate soln, after film being placed in to the toluene solution or sodium alginate aqueous solution of the amino modified hydrophilic silicon dioxide nano particle of end, need clean film with straight alcohol solution, remove unnecessary toluene or water in film surface and duct;
(4) repeat step (3) 3 times, finally film is placed in to distilled water and fully cleans, obtain MODIFIED PP film, adopt the method for dripping of lying to test its surface water contact angle, above-mentioned method of modifying, makes film surface contact angle drop to 15 ° by 125 °.
Embodiment 4
A method for the super hydrophilic modifying of hydrophobic separation membrane material surface, concrete steps are:
(1) the PP Flat Membrane of 10 × 10cm is placed in to atmospheric dielectric barrier discharge plasma, discharge process is carried out to 90 seconds in film surface, 200 watts of discharge powers, are placed in air and are fully oxidized 100 minutes, generate hydroxyl isoreactivity reaction site;
(2) again film is dipped in the toluene solution of 0.6% pyromellitic trimethylsilyl chloride and carries out fully reaction 10 minutes, take out and carry out step (3);
(3) film is first placed in 1.5% hydrophilic silicon dioxide nano particle toluene solution and 0.5% sodium alginate soln, after film being placed in to the toluene solution or sodium alginate aqueous solution of the amino modified hydrophilic silicon dioxide nano particle of end, need clean film with straight alcohol solution, remove unnecessary toluene or water in film surface and duct;
(4) repeat step (3) 6 times, finally film is placed in to distilled water and fully cleans, obtain MODIFIED PP film, adopt the method for dripping of lying to test its surface water contact angle, above-mentioned method of modifying, makes film surface contact angle drop to 9 ° by 125 °.
Embodiment 5
A method for the super hydrophilic modifying of hydrophobic separation membrane material surface, concrete steps are:
(1) the PVDF Flat Membrane of 10 × 10cm is placed in to atmospheric dielectric barrier discharge plasma, discharge process is carried out to 100 seconds in film surface, 300 watts of discharge powers, are placed in air and are fully oxidized 20 minutes, generate hydroxyl isoreactivity reaction site;
(2) again film is dipped in the toluene solution of 1% pyromellitic trimethylsilyl chloride and carries out fully reaction 30 minutes, take out and carry out step (3);
(3) film is first placed in 1% hydrophilic silicon dioxide nano particle toluene solution and 0.6% sodium alginate soln, after film being placed in to the toluene solution or sodium alginate aqueous solution of the amino modified hydrophilic silicon dioxide nano particle of end, need clean film with straight alcohol solution, remove unnecessary toluene or water in film surface and duct;
(4) repeat step (3) 5 times, finally film is placed in to distilled water and fully cleans, obtain modification pvdf membrane, adopt the method for dripping of lying to test its surface water contact angle, above-mentioned method of modifying, makes film surface contact angle drop to 5 ° by 105 °.
Embodiment 6
A method for the super hydrophilic modifying of hydrophobic separation membrane material surface, concrete steps are:
(1) the PSF Flat Membrane of 10 × 10cm is placed in to atmospheric dielectric barrier discharge plasma, discharge process is carried out to 30 seconds in film surface, 100 watts of discharge powers, are placed in air and are fully oxidized 30 minutes, generate hydroxyl isoreactivity reaction site;
(2) again film is dipped in the toluene solution of 0.5% pyromellitic trimethylsilyl chloride and carries out fully reaction 20 minutes, take out and carry out step (3);
(3) film is first placed in 0.5% hydrophilic silicon dioxide nano particle toluene solution and 0.2% sodium alginate soln, after film being placed in to the toluene solution or sodium alginate aqueous solution of the amino modified hydrophilic silicon dioxide nano particle of end, need clean film with straight alcohol solution, remove unnecessary toluene or water in film surface and duct;
(4) repeat step (3) 4 times, finally film is placed in to distilled water and fully cleans, obtain modification PSF film, adopt the method for dripping of lying to test its surface water contact angle, above-mentioned method of modifying, makes film surface contact angle drop to 7 ° by 105 °.
Embodiment 7
A method for the super hydrophilic modifying of hydrophobic separation membrane material surface, concrete steps are:
(1) the PTFE Flat Membrane of 10 × 10cm is placed in to atmospheric dielectric barrier discharge plasma, discharge process is carried out to 150 seconds in film surface, 250 watts of discharge powers, are placed in air and are fully oxidized 40 minutes, generate hydroxyl isoreactivity reaction site;
(2) again film is dipped in the toluene solution of 0.2% pyromellitic trimethylsilyl chloride and carries out fully reaction 30 minutes, take out and carry out step (3);
(3) film is first placed in 1.5% hydrophilic silicon dioxide nano particle toluene solution and 1% sodium alginate soln, after film being placed in to the toluene solution or sodium alginate aqueous solution of the amino modified hydrophilic silicon dioxide nano particle of end, need clean film with straight alcohol solution, remove unnecessary toluene or water in film surface and duct;
(4) repeat step (3) 4 times, finally film is placed in to distilled water and fully cleans, obtain modified ptfe film, adopt the method for dripping of lying to test its surface water contact angle, above-mentioned method of modifying, makes film surface contact angle drop to 10 ° by 135 °.
Embodiment 8
A method for the super hydrophilic modifying of hydrophobic separation membrane material surface, concrete steps are:
(1) the PES Flat Membrane of 10 × 10cm is placed in to atmospheric dielectric barrier discharge plasma, discharge process is carried out to 200 seconds in film surface, 200 watts of discharge powers, are placed in air and are fully oxidized 80 minutes, generate hydroxyl isoreactivity reaction site;
(2) again film is dipped in the toluene solution of 0.8% pyromellitic trimethylsilyl chloride and carries out fully reaction 30 minutes, take out and carry out step (3);
(3) film is first placed in 1% hydrophilic silicon dioxide nano particle toluene solution and 0.6% sodium alginate soln, after film being placed in to the toluene solution or sodium alginate aqueous solution of the amino modified hydrophilic silicon dioxide nano particle of end, need clean film with straight alcohol solution, remove unnecessary toluene or water in film surface and duct;
(4) repeat step (3) 4 times, finally film is placed in to distilled water and fully cleans, obtain modified PES film, adopt the method for dripping of lying to test its surface water contact angle, above-mentioned method of modifying, makes film surface contact angle drop to 11 ° by 95 °.
Embodiment 9
A method for the super hydrophilic modifying of hydrophobic separation membrane material surface, concrete steps are:
(1) the PP Flat Membrane of 10 × 10cm is placed in to atmospheric dielectric barrier discharge plasma, discharge process is carried out to 180 seconds in film surface, 300 watts of discharge powers, are placed in air and are fully oxidized 30 minutes, generate hydroxyl isoreactivity reaction site;
(2) again film is dipped in the toluene solution of 0.5% pyromellitic trimethylsilyl chloride and carries out fully reaction 30 minutes, take out and carry out step (3);
(3) film is first placed in 1.2% hydrophilic silicon dioxide nano particle toluene solution and 0.1% sodium alginate soln, after film being placed in to the toluene solution or sodium alginate aqueous solution of the amino modified hydrophilic silicon dioxide nano particle of end, need clean film with straight alcohol solution, remove unnecessary toluene or water in film surface and duct;
(4) repeat step (3) 4 times, finally film is placed in to distilled water and fully cleans, obtain MODIFIED PP film, adopt the method for dripping of lying to test its surface water contact angle, above-mentioned method of modifying, makes film surface contact angle drop to 15 ° by 125 °.
Embodiment 10
A method for the super hydrophilic modifying of hydrophobic separation membrane material surface, concrete steps are:
(1) the PP Flat Membrane of 10 × 10cm is placed in to atmospheric dielectric barrier discharge plasma, discharge process is carried out to 300 seconds in film surface, 100 watts of discharge powers, are placed in air and are fully oxidized 30 minutes, generate hydroxyl isoreactivity reaction site;
(2) again film is dipped in the toluene solution of 1% pyromellitic trimethylsilyl chloride and carries out fully reaction 30 minutes, take out and carry out step (3);
(3) film is first placed in 1% hydrophilic silicon dioxide nano particle toluene solution and 0.8% sodium alginate soln, after film being placed in to the toluene solution or sodium alginate aqueous solution of the amino modified hydrophilic silicon dioxide nano particle of end, need clean film with straight alcohol solution, remove unnecessary toluene or water in film surface and duct;
(4) repeat step (3) 8 times, finally film is placed in to distilled water and fully cleans, obtain MODIFIED PP film, adopt the method for dripping of lying to test its surface water contact angle, above-mentioned method of modifying, makes film surface contact angle drop to 5 ° by 125 °.
Embodiment 11
A method for the super hydrophilic modifying of hydrophobic separation membrane material surface, concrete steps are:
(1) the PVDF Flat Membrane of 10 × 10cm is placed in to atmospheric dielectric barrier discharge plasma, discharge process is carried out to 120 seconds in film surface, 50 watts of discharge powers, are placed in air and are fully oxidized 20 minutes, generate hydroxyl isoreactivity reaction site;
(2) again film is dipped in the toluene solution of 0.5% pyromellitic trimethylsilyl chloride and carries out fully reaction 10 minutes, take out and carry out step (3);
(3) film is first placed in 2% hydrophilic silicon dioxide nano particle toluene solution and 0.3% sodium alginate soln, after film being placed in to the toluene solution or sodium alginate aqueous solution of the amino modified hydrophilic silicon dioxide nano particle of end, need clean film with straight alcohol solution, remove unnecessary toluene or water in film surface and duct;
(4) repeat step (3) 4 times, finally film is placed in to distilled water and fully cleans, obtain modification pvdf membrane, adopt the method for dripping of lying to test its surface water contact angle, above-mentioned method of modifying, makes film surface contact angle drop to 3 ° by 105 °.
Claims (9)
1. a method for the super hydrophilic modifying of hydrophobic separation membrane material surface, is characterized in that, concrete steps comprise:
The first step: hydrophobic separation membrane is placed in to plasma device, carries out surface plasma discharge process, be placed in air and be oxidized, generate active reaction sites;
Second step: the toluene solution that is placed in pyromellitic trimethylsilyl chloride through first step film after treatment is reacted, take out and carry out the 3rd step after reaction;
The 3rd step: film is first placed in the toluene solution and sodium alginate aqueous solution of the amino modified hydrophilic silicon dioxide nano particle of end, obtains the hydrophobic separation membrane after modification.
2. the method for the super hydrophilic modifying of hydrophobic separation membrane material surface as claimed in claim 1, is characterized in that, also comprises:
The 4th step: repeat the 3rd step until obtain the surperficial double team number of plies needing, finally film is placed in to distilled water and fully cleans.
3. the method for the super hydrophilic modifying of hydrophobic separation membrane material surface as claimed in claim 2, is characterized in that, described number of repetition is not less than 3 times.
4. the method for the super hydrophilic modifying of hydrophobic separation membrane material surface as claimed in claim 1, it is characterized in that, plasma device in the described first step is low pressure or atmospheric plasma equipment, 50～500 watts of discharge powers, and the discharge process time is 10～300 seconds.
5. the method for the super hydrophilic modifying of hydrophobic separation membrane material surface as claimed in claim 1, is characterized in that, the oxidization time in the described first step is 10～120 minutes.
6. the method for the super hydrophilic modifying of hydrophobic separation membrane material surface as claimed in claim 1, is characterized in that, the hydrophobic separation membrane in the described first step is PP, PES, PSF, PVDF or PTFE film.
7. the method for the super hydrophilic modifying of hydrophobic separation membrane material surface as claimed in claim 1, is characterized in that, the weight concentration of the toluene solution of the pyromellitic trimethylsilyl chloride in described second step is 0.1%～1%.
8. the method for the super hydrophilic modifying of hydrophobic separation membrane material surface as claimed in claim 1, it is characterized in that, the weight concentration of the toluene solution of the hydrophilic silicon dioxide nano particle in the 3rd described step is 0.5%～2%, and the weight concentration of sodium alginate aqueous solution is 0.1%～1%.
9. the method for the super hydrophilic modifying of hydrophobic separation membrane material surface as claimed in claim 1, it is characterized in that, after film being placed in to the toluene solution or sodium alginate aqueous solution of the amino modified hydrophilic silicon dioxide nano particle of end, need clean film with straight alcohol solution, remove unnecessary toluene or water in film surface and duct.
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| CN106268370A (en) * | 2016-08-29 | 2017-01-04 | 同济大学 | Poly tetrafluoroethylene low temperature plasma hydrophilic modifying and timeliness modification processing method |
| CN110052176A (en) * | 2019-04-04 | 2019-07-26 | 天津工业大学 | A kind of preparation method of the hydrogel filter membrane of hollow microsphere enhancing mechanical performance raising flux |
| CN110052175A (en) * | 2019-04-04 | 2019-07-26 | 天津工业大学 | A kind of preparation method of silicon dioxide hollow microsphere Ag-carried antibacterial hydrogel filter membrane |
| CN111725420A (en) * | 2020-06-02 | 2020-09-29 | 武汉华星光电半导体显示技术有限公司 | Display panel and preparation method thereof |
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| CN106268370A (en) * | 2016-08-29 | 2017-01-04 | 同济大学 | Poly tetrafluoroethylene low temperature plasma hydrophilic modifying and timeliness modification processing method |
| CN110052176A (en) * | 2019-04-04 | 2019-07-26 | 天津工业大学 | A kind of preparation method of the hydrogel filter membrane of hollow microsphere enhancing mechanical performance raising flux |
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| CN110052176B (en) * | 2019-04-04 | 2021-04-30 | 天津工业大学 | Preparation method of hollow microsphere-reinforced mechanical property-improved flux hydrogel filtering membrane |
| CN110052175B (en) * | 2019-04-04 | 2021-04-30 | 天津工业大学 | Preparation method of silicon dioxide hollow microsphere silver-loaded antibacterial hydrogel filtering membrane |
| CN111725420A (en) * | 2020-06-02 | 2020-09-29 | 武汉华星光电半导体显示技术有限公司 | Display panel and preparation method thereof |
| CN111725420B (en) * | 2020-06-02 | 2021-08-03 | 武汉华星光电半导体显示技术有限公司 | Display panel and preparation method thereof |
| CN115073795A (en) * | 2022-07-14 | 2022-09-20 | 佛山科学技术学院 | Hydrophobic polymer material surface hydrophilic modification method based on carbon dioxide plasma |
| CN115073795B (en) * | 2022-07-14 | 2023-12-05 | 佛山科学技术学院 | Hydrophobic polymer material surface hydrophilic modification method based on carbon dioxide plasma |
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