CN105214511A - A kind of Nano Silver/Graphene/Kynoar hybrid membranes and preparation method thereof - Google Patents
A kind of Nano Silver/Graphene/Kynoar hybrid membranes and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of Nano Silver/Graphene/Kynoar hybrid membranes and preparation method thereof, comprise the steps: (1) by graphene oxide, polyethylene glycol ultrasonic disperse in DMA, obtain solution A; By AgNO
3, polyethylene glycol to be dissolved in DMA to obtain solution B; (2) gained solution A and solution B are mixed in proportion to obtain Nano Silver/graphene complex solution; (3) Kynoar is dissolved in gained Nano Silver/graphene complex solution, after standing and defoaming, obtains casting solution; (4) gained casting solution is prepared Nano Silver/Graphene/Kynoar hybrid membranes by immersion precipitation phase inversion process.Preparation method of the present invention can make nano silver particles, and comparatively uniform load is on Graphene, and Nano Silver/graphene complex can be dispersed in Kynoar hybrid membranes, and obtained hybrid membranes has good antibacterial and antifouling property.
Description
Technical field
The invention belongs to nano composite material and ultrafiltration membrane technique neck city, be specifically related to a kind of preparation method with the Nano Silver/Graphene/Kynoar hybrid membranes of antibacterial and antifouling property.
Background technology
Kynoar is current most widely used ultrafiltration membrane material.Due to the hydrophobicity of polyvinylidene fluoride film, in use pollutant easily adsorbs and is deposited on film surface, and blocking fenestra, causes the pollution of film, wherein especially serious with the pollution of microorganism.Fouling membrane can cause the decay of membrane flux, thus needs to adopt the method such as physics, chemistry to clean polluted membrane; In addition, some pollution will cause the irreversible decay of membrane flux to a certain extent.Fouling membrane will increase operation cost greatly, shorten the service life of film.Therefore, improving the antifouling property of polyvinylidene fluoride (PVDF) ultrafiltration membrane is strengthen one of important measures that polyvinylidene fluoride film applies in the industry, and improve the antibiotic property of polyvinylidene fluoride (PVDF) ultrafiltration membrane, be again one of effective means improving polyvinylidene fluoride (PVDF) ultrafiltration membrane antifouling property.
Silver has efficient antibacterial activity, has been widely used in water body filtration film.Such as, application number be 201410168475.1 Chinese invention patent application document disclose a kind of preparation method of silver orthophosphate decorated nanometer negative ion powder modified polyvinilidene fluoride film.Utilize ion-exchange to obtain nano silver, and modified the negative ion powder that silver is carried in negative ion powder acquisition.Adding in Kynoar casting solution by carrying silver-colored negative ion powder in right amount again, having prepared the modified polyvinilidene fluoride film containing carrying silver-colored negative ion powder by phase inversion.By carrying the distinctive nanometer size effect of silver-colored negative ion powder and surface energy, imparting the effective stable against biological contamination ability of polyvinylidene fluoride film, improve its hydrophily and flux recovery rate.
Application number be 201210541062.4 Chinese invention patent application document disclose a kind of Ag/TiO
2modified polyvinylidene fluoride ultrafiltration membrane and preparation method thereof.By Kynoar, pore creating material, TiO
2the casting solution of homogeneous phase dispersion made by nano particle, silver ion salt, solvent; Again casting solution is cast in mould, scrapes with scraper and paint the uniform film of a layer thickness, be placed in distilled water, after film separation, continue dipping, take out film post-drying and namely obtain Ag/TiO
2modified polyvinylidene fluoride ultrafiltration membrane.
Application number be 201410384455.8 Chinese invention patent application document disclose a kind of preparation method of fabricated in situ Nano Silver modified polyvinylidene fluoride ultrafiltration membrane.Comprise: 1. prepare Kynoar solution; 2. the mixed liquor of preparation containing Nano Silver; 3. casting solution is prepared; 4. casting, film forming; 5. clean, obtain fabricated in situ Nano Silver modified polyvinylidene fluoride ultrafiltration membrane.
Graphene is with sp
2the single carbon atom lamella of hydridization forms a kind of Novel Carbon Nanomaterials.There is oxy radical at its lamella edge to graphene oxide, as carboxylic acid group and carbonyl, base plane has epoxide group and hydroxyl, and therefore graphene oxide can be dispersed in polar solvent well.Graphene also has certain antibacterial action, and when contacting with bacterium, the cell membrane of bacterium can cut by the two-dimension plane structure of Graphene, draws the phospholipid molecule on cell membrane simultaneously.The structures and characteristics of Graphene uniqueness, being doomed this new material will gather around in ultra-filtration and separation film field and have broad application prospects.
Application number be 201410383815.2 Chinese invention application documents disclose the preparation method of a kind of polymer/graphene oxide composite separating film.Graphene oxide for coagulating bath, to be assembled into by inversion of phases process the method that separation membrane surface prepares polymer/graphene oxide composite separating film with the aqueous solution of graphene oxide by the method.
Application number be 201210557266.7 Chinese invention application documents disclose a kind of Polymer/graphene hybridization nanofiltration composite membrane and preparation method thereof.This Nano filtering composite membrane on polysulfone porous support membrane, forms by interfacial polymerization process the polymers function cortex that one deck includes Graphene.
Application number be 201310014691.6 Chinese invention application documents disclose a kind of hydrophilicity kynoar modification diffusion barrier and preparation method thereof.The method strengthens the hydrophily of diffusion barrier on the one hand by the oxygen-containing functional group in oxide/carbon nanometer tube and graphene oxide, the graphene oxide of laminated structure is utilized to enter mutual intercalation in the oxide/carbon nanometer tube network of tubular structure on the other hand, form more stable sandwich hierarchy, therefore the reunion between identical nanostructure can effectively be suppressed, and be conducive to graphene oxide to the migration of composite film surface and assembling, and significantly improve the contact area of oxide/carbon nanometer tube and graphene oxide and macromolecule matrix in composite membrane, thus enhance hydrophily and the contamination resistance of film, the effluent flux of film is greatly enhanced.
Application number be 201510012953.4 Chinese invention application documents disclose the preparation method of a kind of Kynoar-graphene oxide composite hollow fiber membrane, by Kynoar, pore former, solvent, water, stirs and obtains PVDF solution.GO-DMAC mixed liquor is added in Kynoar solution and obtains casting solution; Casting solution is filtered, standing and defoaming.Casting solution and core liquid are extruded by spinning nozzle simultaneously, obtains the hollow fiber ultrafiltration membrane of graphene oxide doped Kynoar.
Application number be 201410241195.9 Chinese invention application documents a kind of carboxylated graphene oxide/polyvinylidenefluoride fluoride composite ultrafiltration membrane and preparation method are disclosed.First by carboxylated graphene oxide dimethylacetylamide and triethyl phosphate composition solvent pairs in ultrasonic disperse, then mix with Kynoar, mechanical agitation is dissolved, knifing on glass plate, soak by deionized water again, naturally dry in air and obtain carboxylated graphene oxide/polyvinylidenefluoride fluoride composite ultrafiltration membrane.Carboxylated graphene oxide/polyvinylidenefluoride fluoride composite ultrafiltration membrane of the present invention has good hydrophily and mechanical strength.
Application number be 201210521585.2 Chinese invention application documents disclose a kind of preparation method utilizing modified graphene to strengthen the milipore filter of antibiotic property and resistance tocrocking.First by Graphene modification, drying, then in modified graphene, add organic solvent, additive, membrane material, after mixing, obtain casting solution, after casting solution vacuum defoamation, be poured over the planar surface of dried flat, knifing, put into coagulant liquid, obtain milipore filter.
Summary of the invention
The invention provides a kind of Nano Silver/Graphene/Kynoar hybrid membranes and preparation method thereof, this preparation method can make nano silver particles comparatively uniform load on Graphene, and Nano Silver/graphene complex can be dispersed in Kynoar hybrid membranes, and obtained hybrid membranes has good antibacterial and antifouling property.
A preparation method for Nano Silver/Graphene/Kynoar hybrid membranes, comprises the steps:
(1) by graphene oxide, polyethylene glycol ultrasonic disperse in DMA, obtain solution A; By AgNO
3, polyethylene glycol to be dissolved in DMA to obtain solution B;
(2) gained solution A and solution B equal-volume are mixed to obtain Nano Silver/graphene complex solution;
(3) Kynoar is dissolved in gained Nano Silver/graphene complex solution, after standing and defoaming, obtains casting solution;
(4) gained casting solution is prepared Nano Silver/Graphene/Kynoar hybrid membranes by immersion precipitation phase inversion process.
First with AgNO
3for presoma, DMA is solvent, and polyethylene glycol is reducing agent and nanoparticle dispersion agent, adopts ultrasonic wave added solvent-thermal process legal system for the DMA solution of Nano Silver/graphene complex; Then in this solution, add Kynoar, after stirring and dissolving, standing and defoaming, form even, stable casting solution; Finally this casting solution is prepared Nano Silver/Graphene/Kynoar hybrid membranes by immersion precipitation phase inversion process.Nano Silver/Graphene/Kynoar hybrid membranes prepared by the present invention has antibacterial, antifouling property preferably.
The present invention takes full advantage of multiple character and the function of polyethylene glycol, and the solvent property of DMA, and in the synthesis of Nano Silver/graphene complex, polyethylene glycol has played the effect of reducing agent, nanoparticle dispersion stabilizing agent; And in the preparation of hybrid membranes, polyethylene glycol serves as again pore-foaming agent and used, DMA is all reused as solvent in the synthesis of Nano Silver/graphene complex and the preparation of hybrid membranes.The present invention is a kind of environmental protection, the fast and convenient method preparing Nano Silver/Graphene/Kynoar hybrid membranes.
Preferably, in described solution A, graphene oxide quality is 5 ~ 15g/L with the ratio of DMA volume, and polyethylene glycol quality is 5 ~ 30g/L with the ratio of DMA volume.
Further preferably, in described solution A, graphene oxide quality is 5 ~ 10g/L with the ratio of DMA volume, and polyethylene glycol quality is 10 ~ 20g/L with the ratio of DMA volume.
Preferably, AgNO in described solution B
3quality is 10 ~ 50g/L with the ratio of DMA volume, and polyethylene glycol quality is 5 ~ 30g/L with the ratio of DMA volume.
Further preferably, AgNO in described solution B
3quality is 10 ~ 25g/L with the ratio of DMA volume, and polyethylene glycol quality is 10 ~ 20g/L with the ratio of DMA volume.
The oxygen content of described graphene oxide is 10 ~ 30wt%, preferably, graphene oxide can select the 800 order graphite powders of AladdinIndustrialCooperation to obtain (Zhao Li by the self-control of Hummers method, Chen Yufei, Wang Ting, Wu Liguang. the in-situ polymerization of graphene oxide/polyurethane hybrid film builds and gas permeability. composite journal, 2015,32,673-682).
The molecular weight of described polyethylene glycol is 800 ~ 20000.
Preferably, the dosage of Kynoar is 150 ~ 250g/L with the ratio of the quality volume of Nano Silver/graphene complex solution.More preferably 190 ~ 230g/L.
Preferably, in step (1), solution A and solution B are all prepared at 50 ~ 70 DEG C.Preferred preparation at 60 DEG C further.
Preferably, in step (2), at 50 ~ 70 DEG C, solution A and solution B mix by ultrasonic process for 2.5 ~ 3.5 hours.Further preferably, ultrasonic process 3 hours at 60 DEG C.
Preferably, described immersion precipitation phase inversion process is: by casting solution overlay film on cleaned glass plate, immerse after overlay film in 25 ~ 35 DEG C of pure water, until film after glass plate Automatic-falling, to be immersed in distilled water 20 ~ 24 hours, pull out nature dry after Nano Silver/Graphene/Kynoar hybrid membranes.
Further preferably, the overlay film thickness of casting solution on cleaned glass plate is 200 ~ 300 μm.Further, overlay film thickness is 250 μm.
Further preferably, immerse in 30 DEG C of pure water after overlay film, until film after glass plate Automatic-falling, to be immersed in distilled water 24 hours.
Most preferably, the preparation method of Nano Silver/Graphene/Kynoar hybrid membranes, comprises the steps:
Step (1): at 60 DEG C ultrasonic by graphene oxide, polyethylene glycol ultrasonic disperse in N, in N-dimethylacetylamide, graphene oxide quality and N, the ratio of N-dimethylacetylamide volume is 6g/L, polyethylene glycol quality and N, the ratio of N-dimethylacetylamide volume is 18g/L, and the graphene oxide oxygen content of use is 19.2wt%, and the molecular weight polyethylene glycol of use is 4000;
Step (2): by AgNO at 60 DEG C
3, polyethylene glycol is dissolved in DMA, AgNO
3quality is 17g/L with the ratio of DMA volume, and polyethylene glycol quality is 18g/L with the ratio of DMA volume.The graphene oxide oxygen content used is 19.2wt%, and the molecular weight polyethylene glycol of use is 4000;
Step (3): the solution equal-volume that solution step (1) prepared and step (2) are prepared mixes, ultrasonic process 3 hours at 60 DEG C, obtained Nano Silver/graphene complex solution.
Step (4): be that Kynoar is joined step (3) by 190g/L by mass volume ratio: in obtained Nano Silver/graphene complex solution, stirring and dissolving, forms even, stable casting solution after standing and defoaming;
Step (5): casting solution is poured on clean glass plate, the film spreading to thickness 250 μm is coated with coating device, immerse in 30 DEG C of pure water by being coated with the glass plate having scraped film after 1 minute, until film after glass plate Automatic-falling, put it in the bucket filling a large amount of distilled water and soak 24 hours, pull out after nature dries and obtain Nano Silver/Graphene/Kynoar composite hyperfiltration membrane.
The present invention also provide a kind of as described in Nano Silver/Graphene/Kynoar hybrid membranes of preparing of preparation method.
Compared with prior art, the present invention has following beneficial effect:
Preparation method of the present invention can make nano silver particles, and comparatively uniform load is on Graphene, and Nano Silver/graphene complex can be dispersed in Kynoar hybrid membranes, and obtained hybrid membranes has good antibacterial and antifouling property.
Accompanying drawing explanation
Fig. 1 is the electromicroscopic photograph preparing Nano Silver/Graphene/Kynoar composite hyperfiltration membrane film surface in embodiment 3.
Fig. 2 is the electromicroscopic photograph preparing Nano Silver/Graphene/Kynoar composite hyperfiltration membrane film cross section in embodiment 3.
Detailed description of the invention
Further illustrating below by way of specific embodiment utilizes the present invention how to prepare Nano Silver/Graphene/Kynoar hybrid membranes, and the performance of prepared milipore filter.
Raw materials usedly in following examples except specified otherwise, all commercial goods can be adopted.
Embodiment 1
1. graphene oxide, polyethylene glycol ultrasonic (frequency 100Hz) are scattered in N at 60 DEG C, in N-dimethylacetylamide, graphene oxide quality is 10g/L with the ratio of DMA volume, polyethylene glycol quality is 12g/L with the ratio of DMA volume.The graphene oxide oxygen content used is 14.6wt%, and the molecular weight polyethylene glycol of use is 800.
2. at 60 DEG C by AgNO
3, polyethylene glycol is dissolved in DMA, AgNO
3quality is 25g/L with the ratio of DMA volume, and polyethylene glycol quality is 12g/L with the ratio of DMA volume.The graphene oxide oxygen content used is 14.6wt%, and the molecular weight polyethylene glycol of use is 800.
3. the solution equal-volume that 2. solution step 1. prepared and step are prepared mixes, and ultrasonic at 60 DEG C (frequency 100Hz) processes 3 hours, obtained Nano Silver/graphene complex solution.
4. be that Kynoar to join in Nano Silver/graphene complex solution that 3. step obtain by 230g/L by mass volume ratio, stirring and dissolving, forms even, stable casting solution after standing and defoaming.
5. casting solution is poured on clean glass plate, the film spreading to thickness 250 μm is coated with coating device, immerse in 30 DEG C of pure water by being coated with the glass plate having scraped film after 1 minute, until film after glass plate Automatic-falling, put it in the bucket filling a large amount of distilled water and soak 24 hours, pull out after nature dries and obtain Nano Silver/Graphene/Kynoar composite hyperfiltration membrane.
Embodiment 2
1. graphene oxide, polyethylene glycol ultrasonic (frequency 100Hz) are scattered in N at 60 DEG C, in N-dimethylacetylamide, graphene oxide quality is 8g/L with the ratio of DMA volume, polyethylene glycol quality is 15g/L with the ratio of DMA volume.The graphene oxide oxygen content used is 16.3wt%, and the molecular weight polyethylene glycol of use is 2000.
2. at 60 DEG C by AgNO
3, polyethylene glycol is dissolved in DMA, AgNO
3quality is 20g/L with the ratio of DMA volume, and polyethylene glycol quality is 15g/L with the ratio of DMA volume.The graphene oxide oxygen content used is 14.6wt%, and the molecular weight polyethylene glycol of use is 2000.
3. the solution equal-volume that 2. solution step 1. prepared and step are prepared mixes, and ultrasonic at 60 DEG C (frequency 100Hz) processes 3 hours, obtained Nano Silver/graphene complex solution.
4. be that Kynoar to join in Nano Silver/graphene complex solution that 3. step obtain by 210g/L by mass volume ratio, stirring and dissolving, forms even, stable casting solution after standing and defoaming.
5. casting solution is poured on clean glass plate, the film spreading to thickness 250 μm is coated with coating device, immerse in 30 DEG C of pure water by being coated with the glass plate having scraped film after 1 minute, until film after glass plate Automatic-falling, put it in the bucket filling a large amount of distilled water and soak 24 hours, pull out after nature dries and obtain Nano Silver/Graphene/Kynoar composite hyperfiltration membrane.
Embodiment 3
1. graphene oxide, polyethylene glycol ultrasonic (frequency 100Hz) are scattered in N at 60 DEG C, in N-dimethylacetylamide, graphene oxide quality is 6g/L with the ratio of DMA volume, polyethylene glycol quality is 18g/L with the ratio of DMA volume.The graphene oxide oxygen content used is 19.2wt%, and the molecular weight polyethylene glycol of use is 4000.
2. at 60 DEG C by AgNO
3, polyethylene glycol is dissolved in DMA, AgNO
3quality is 17g/L with the ratio of DMA volume, and polyethylene glycol quality is 18g/L with the ratio of DMA volume.The graphene oxide oxygen content used is 19.2wt%, and the molecular weight polyethylene glycol of use is 4000.
3. the solution equal-volume that 2. solution step 1. prepared and step are prepared mixes, and ultrasonic at 60 DEG C (frequency 100Hz) processes 3 hours, obtained Nano Silver/graphene complex solution.
4. be that Kynoar to join in Nano Silver/graphene complex solution that 3. step obtain by 190g/L by mass volume ratio, stirring and dissolving, forms even, stable casting solution after standing and defoaming.
5. casting solution is poured on clean glass plate, the film spreading to thickness 250 μm is coated with coating device, immerse in 30 DEG C of pure water by being coated with the glass plate having scraped film after 1 minute, until film after glass plate Automatic-falling, put it in the bucket filling a large amount of distilled water and soak 24 hours, pull out after nature dries and obtain Nano Silver/Graphene/Kynoar composite hyperfiltration membrane.
Embodiment 4
1. graphene oxide, polyethylene glycol ultrasonic (frequency 100Hz) are scattered in N at 60 DEG C, in N-dimethylacetylamide, graphene oxide quality is 6g/L with the ratio of DMA volume, polyethylene glycol quality is 20g/L with the ratio of DMA volume.The graphene oxide oxygen content used is 19.2wt%, and the molecular weight polyethylene glycol of use is 6000.
2. at 60 DEG C by AgNO
3, polyethylene glycol is dissolved in DMA, AgNO
3quality is 15g/L with the ratio of DMA volume, and polyethylene glycol quality is 20g/L with the ratio of DMA volume.The graphene oxide oxygen content used is 19.2wt%, and the molecular weight polyethylene glycol of use is 6000.
3. the solution equal-volume that 2. solution step 1. prepared and step are prepared mixes, and ultrasonic at 60 DEG C (frequency 100Hz) processes 3 hours, obtained Nano Silver/graphene complex solution.
4. be that Kynoar to join in Nano Silver/graphene complex solution that 3. step obtain by 200g/L by mass volume ratio, stirring and dissolving, forms even, stable casting solution after standing and defoaming.
5. casting solution is poured on clean glass plate, the film spreading to thickness 250 μm is coated with coating device, immerse in 30 DEG C of pure water by being coated with the glass plate having scraped film after 1 minute, until film after glass plate Automatic-falling, put it in the bucket filling a large amount of distilled water and soak 24 hours, pull out after nature dries and obtain Nano Silver/Graphene/Kynoar composite hyperfiltration membrane.
Embodiment 5
1. graphene oxide, polyethylene glycol ultrasonic (frequency 100Hz) are scattered in N at 60 DEG C, in N-dimethylacetylamide, graphene oxide quality is 8g/L with the ratio of DMA volume, polyethylene glycol quality is 22g/L with the ratio of DMA volume.The graphene oxide oxygen content used is 22.4wt%, and the molecular weight polyethylene glycol of use is 20000.
2. at 60 DEG C by AgNO
3, polyethylene glycol is dissolved in DMA, AgNO
3quality is 10g/L with the ratio of DMA volume, and polyethylene glycol quality is 22g/L with the ratio of DMA volume.The graphene oxide oxygen content used is 22.4wt%, and the molecular weight polyethylene glycol of use is 20000.
3. the solution equal-volume that 2. solution step 1. prepared and step are prepared mixes, and ultrasonic at 60 DEG C (frequency 100Hz) processes 3 hours, obtained Nano Silver/graphene complex solution.
4. be that Kynoar to join in Nano Silver/graphene complex solution that 3. step obtain by 220g/L by mass volume ratio, stirring and dissolving, forms even, stable casting solution after standing and defoaming.
5. casting solution is poured on clean glass plate, the film spreading to thickness 250 μm is coated with coating device, immerse in 30 DEG C of pure water by being coated with the glass plate having scraped film after 1 minute, until film after glass plate Automatic-falling, put it in the bucket filling a large amount of distilled water and soak 24 hours, pull out after nature dries and obtain Nano Silver/Graphene/Kynoar hybrid membranes.
Comparative example
Kynoar 210g, polyethylene glycol (molecular weight is 2000) 30g, DMA 2L are mixed, stirring and dissolving, forms even, stable casting solution after standing and defoaming.Casting solution is poured on clean glass plate, the film spreading to thickness 250 μm is coated with coating device, immerse in 30 DEG C of pure water by being coated with the glass plate having scraped film after 1 minute, until film after glass plate Automatic-falling, put it in the bucket filling a large amount of distilled water and soak 24 hours, pull out after nature dries and obtain polyvinylidene fluoride (PVDF) ultrafiltration membrane.
The anti-microbial property experiment of film:
Adopt the method for plate culture count, testing example and the Nano Silver/Graphene/Kynoar hybrid membranes prepared by comparative example and polyvinylidene fluoride (PVDF) ultrafiltration membrane are to colibacillary antibacterial effect.Concrete test operating procedure is as follows:
(1) by beef extract 4.5g, peptone 15g, NaCl7.5g, agar 35g, water 2000mL are configured to LB nutrient solution (pH7.0 ~ 7.2).
(2) get 10 conical flasks, be labeled as 1 ~ No. 10, in every conical flask, add the LB nutrient solution of 100mL respectively; Then be placed in high-pressure sterilizing pot together with the test tube bandaged with some by 10 conical flasks, liquid-transfering gun rifle are first-class, 121 DEG C of moist heat sterilization 20min.
(3) conical flask getting No. 1 sterilizing is placed on aseptic, ultra-clean workbench, accesses the Escherichia coli bacteria liquid 1mL activated in bottle, mixing of suitably vibrating, and puts into constant temperature oscillator (30 DEG C, 150r/min) and cultivates 16 hours.
(4) conical flask getting 2 ~ No. 6 sterilizings is placed on aseptic, clean workbench, adds the Nano Silver/Graphene/each 0.25g of Kynoar hybrid membranes of embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5 preparation in 2 ~ No. 5 conical flasks respectively; Polyvinylidene fluoride (PVDF) ultrafiltration membrane 0.25g as a control group 1 prepared by comparative example 1 is added in No. 7 conical flasks; Any material (blank) as a control group 2 is not added in No. 8 conical flasks.
(5) Escherichia coli bacteria liquid cultivated 16 hours in No. 1 conical flask is respectively got 0.10mL to access respectively in 2 ~ No. 8 conical flask nutrient solutions, carry out constant-temperature table cultivation (150r/min, 30 DEG C).
(6) constant-temperature table cultivates count plate after 24 hours, calculates antibiotic rate.
The antifouling property experiment of film:
The bovine serum albumin(BSA) adopting 1g/L is pollutant, carries out antifouling property evaluation to milipore filter obtained in embodiment and comparative example.
Test process is as follows: at 25 DEG C, milipore filter to be placed in cup type ultrafilter under 0.15MPa pressure precompressed 1 hour, under 0.1MPa pressure, then to measure the pure water flux J of milipore filter
w, 1, with the bovine serum albumin(BSA) of 1g/L for object, under 0.1MPa after ultrafiltration 30min, the milipore filter 15 minutes after polluting by washed with de-ionized water, then repeats above pre-compaction process, then under 0.1MPa, measures the pure water flux J of milipore filter
w, 2.And with initial pure water flux J
w, 1contrast obtains pure water flux recovery rate (FRR).
Milipore filter antifouling property uses the pure water flux recovery rate (FRR) of film to characterize usually.
FRR＝J
w,2/J
w,1
FRR is larger, shows that the antifouling property of film is better.
The anti-microbial property test result of film:
Nano Silver/Graphene/Kynoar the hybrid membranes of embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5 preparation all reaches more than 92% to Escherichia coli antibiotic rate.And polyvinylidene fluoride (PVDF) ultrafiltration membrane prepared by comparative example does not have antibacterial action to Escherichia coli.
The antifouling property test result of film:
Pure water flux recovery rate (FRR) rate that Nano Silver/Graphene/Kynoar hydridization prepared by embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5 surpasses is all higher than 83%.And the pure water flux recovery rate (FRR) of polyvinylidene fluoride (PVDF) ultrafiltration membrane prepared by comparative example is about 60%.
In addition, the pure water flux that Nano Silver/Graphene/Kynoar hydridization that prepared by embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5 surpasses all can reach 200L/m
2more than hr, is all greater than 96% to the rejection of bovine serum albumin(BSA), is also better than polyvinylidene fluoride (PVDF) ultrafiltration membrane prepared by comparative example.
Claims (9)
1. a preparation method for Nano Silver/Graphene/Kynoar hybrid membranes, is characterized in that, comprise the steps:
(1) by graphene oxide, polyethylene glycol ultrasonic disperse in DMA, obtain solution A; By AgNO
3, polyethylene glycol to be dissolved in DMA to obtain solution B;
(2) gained solution A and solution B equal-volume are mixed to obtain Nano Silver/graphene complex solution;
(3) Kynoar is dissolved in gained Nano Silver/graphene complex solution, after standing and defoaming, obtains casting solution;
(4) gained casting solution is prepared Nano Silver/Graphene/Kynoar hybrid membranes by immersion precipitation phase inversion process.
2. preparation method according to claim 1, it is characterized in that, in described solution A, graphene oxide quality is 5 ~ 15g/L with the ratio of DMA volume, and polyethylene glycol quality is 5 ~ 30g/L with the ratio of DMA volume.
3. preparation method according to claim 1, is characterized in that, AgNO in described solution B
3quality is 10 ~ 50g/L with the ratio of DMA volume, and polyethylene glycol quality is 5 ~ 30g/L with the ratio of DMA volume.
4. preparation method according to claim 1, it is characterized in that, the dosage of Kynoar is 150 ~ 250g/L with the ratio of the quality volume of Nano Silver/graphene complex solution.
5. preparation method according to claim 1, is characterized in that, in step (1), solution A and solution B are all prepared at 50 ~ 70 DEG C.
6. preparation method according to claim 1, it is characterized in that, in step (2), at 50 ~ 70 DEG C, solution A and solution B mix by ultrasonic process for 2.5 ~ 3.5 hours.
7. preparation method according to claim 1, it is characterized in that, described immersion precipitation phase inversion process is: by casting solution overlay film on cleaned glass plate, immerse after overlay film in 25 ~ 35 DEG C of pure water, until film after glass plate Automatic-falling, to be immersed in distilled water 20 ~ 24 hours, pull out nature dry after Nano Silver/Graphene/Kynoar hybrid membranes.
8. preparation method according to claim 7, it is characterized in that, the overlay film thickness of casting solution on cleaned glass plate is 200 ~ 300 μm.
9. Nano Silver/Graphene/Kynoar hybrid membranes that as described in a claim as any in claim 1 ~ 8, preparation method prepares.
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| CN108479424A (en) * | 2018-04-02 | 2018-09-04 | 合肥国轩高科动力能源有限公司 | Preparation method of modified polyvinylidene fluoride membrane |
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| CN112316726A (en) * | 2020-10-22 | 2021-02-05 | 海瑞膜科技南通有限公司 | Graphene ultrafiltration membrane and preparation method thereof |
| CN113144919A (en) * | 2020-11-23 | 2021-07-23 | 兰州大学 | 3D printing multifunctional filter membrane for sewage treatment and preparation method and application thereof |
| CN113372809A (en) * | 2021-04-23 | 2021-09-10 | 浙江工商大学 | Intelligent heat-insulating coating and preparation and application thereof |
| CN114307691A (en) * | 2021-12-28 | 2022-04-12 | 上海普利特复合材料股份有限公司 | Hollow nano-silver/graphene/PE ultrafiltration membrane and preparation method thereof |
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