CN107970789A - Hydrophobic membrane with micro-and nano-structural surface functional layer and preparation method thereof - Google Patents
Hydrophobic membrane with micro-and nano-structural surface functional layer and preparation method thereof Download PDFInfo
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- CN107970789A CN107970789A CN201711212515.8A CN201711212515A CN107970789A CN 107970789 A CN107970789 A CN 107970789A CN 201711212515 A CN201711212515 A CN 201711212515A CN 107970789 A CN107970789 A CN 107970789A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/364—Membrane distillation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0016—Coagulation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/04—Hydrophobization
Abstract
A kind of hydrophobic membrane with micro-and nano-structural surface functional layer and preparation method thereof, which includes：1) will crystallization or semi-crystalline polymer powder or particle drying；2) it is by weight percentage polymer 8 20% by additive, organic solvent and by dry polymer, additive 0 8%, organic solvent 70 90% mixed, constant temperature stirring a period of time, to being uniformly mixed, homogeneous casting solution was formed after constant temperature deaeration under the conditions of 20 70 DEG C at 20 70 DEG C；3) by gained casting solution by scraping film device striking film forming, and a period of time is stayed at 50 80 DEG C in the air of certain humidity to promote part solid liquid phase conversion；4) primary membrane of step 3) is immersed in 15 50 DEG C of coagulating baths, is dried after soaking a period of time.Obtained hydrophobic film surface has the micro-nano bulge-structure of specific dimensions, improves the hydrophobic performance of hydrophobic membrane, solves film wetting phenomena during hydrophobic membrane.
Description
Technical field
The invention belongs to hydrophobic membrane preparing technical field, is related to a kind of dredging with micro-nano prominent body structure surface functional layer
Moisture film and preparation method thereof.
Background technology
Membrane separating process based on hydrophobic membrane has obtained extensive concern, membrane distillation, infiltration evaporation, film knot over the past decade
The development of the processes such as crystalline substance proposes the requirement of higher for the performance of hydrophobic membrane.Vinylidene is the common system for preparing hydrophobic membrane
Membrane material, it has obtained extensive concern in terms of hydrophobic film preparation.In recent years, for example inclined fluorine second of the copolymer based on vinylidene
The materials such as alkene-hexafluoroethylene, vinylidene-chlorotrifluoroethylene are also applied in hydrophobic membrane preparation and application.
At present phase inversion due to it is easy to operate, be easily achieved engineering, be vinylidene and its copolymer hydrophobic membrane system
A kind of standby important method.But its film forming procedure is influenced by many factors, especially for crystallization or semi-crystalline polymer
Speech, solid-liquid inversion of phases and liquid liquid-phase conversion come across inversion of phases process at the same time, its competition process finally determines film pattern and structure.
The optimization of film pattern and structure can be realized by the adjustment of the approach and speed of inversion of phases, and then is prepared with ideal performance
Film.Presently, by being film-made the adjustment of system such as the selection of solvent and adding for additive/additive package；Environmental condition
Adjustment such as humidity and temperature control；The modes such as the optimization of coagulation bath composition and temperature can realize inversion of phases in film forming procedure
The control of process.
But for hydrophobic membrane, film wetting at present and fouling membrane are still most important problem, it causes film properties unstable
The fixed and service life is shorter.To solve the problems, such as these, film hydrophobically modified is a kind of widely used method.Membrane modifying refers to pass through physics
Or chemistry method shaped film is surface-treated, including chemical group grafting, ultraviolet light/corona treatment,
The processes such as in-situ chemical reaction, increase film surface hydrophobic functional group or change membrane superficial tissue and realize hydrophobic raising.But
It is that modified process is more complicated and not easy to control, the non-uniform phenomenon of film surface easily occurs.Meanwhile membrane modifying may influence
The original structure of film, impacts film strength and other performances.
The content of the invention
In view of this, the main object of the present invention be to provide a kind of hydrophobic membrane with micro-and nano-structural surface functional layer and
Its preparation method, to solve at least one of above-mentioned technical problem referred at least in part.
To achieve the above object, technical scheme is as follows：
As an aspect of of the present present invention, there is provided a kind of preparation of the hydrophobic membrane with micro-nano prominent body structure surface functional layer
Method, the preparation method are phase inversion, are comprised the steps of：
1) will crystallization or semi-crystalline polymer powder or particle drying, to remove shadow of the moisture removal to casting solution thermodynamic property
Ring；
2) it is polymer 8- by weight percentage by the polymer in additive, organic solvent and step 1) by drying
20%th, additive 0-8%, organic solvent 70-90% are mixed, and constant temperature stirring a period of time is equal to mixing at 20-70 DEG C
It is even, form homogeneous casting solution after constant temperature deaeration under the conditions of 20-70 DEG C；
3) by the casting solution in step 2) by scraping film device striking film forming, and certain humidity is stayed at 50-80 DEG C
Air in a period of time to promote the conversion of part solid liquid phase, form primary membrane；
4) primary membrane of step 3) is immersed in 15-50 DEG C of coagulating bath, is dried after soaking a period of time, that is, obtained described
Hydrophobic membrane.
Preferably, in step 1), it is described crystallization or semi-crystalline polymer for Kynoar (PVDF), Kynoar-
Hexafluoropropylene copolymer (PVDF-HFP), Kynoar-chlorotrifluoroethylene (PVDF-CTFE) or Kynoar-
Trifluoro-ethylene copolymer (PVDF-TrFE).
Preferably, in step 2), constant temperature mixing time for 5-24 it is small when, constant temperature inclined heated plate when 12 is small more than, deaeration
Mode includes standing degassing and vacuum outgas.
Preferably, in step 2), the organic solvent be selected from dimethylformamide, dimethylacetylamide, triethyl phosphate,
One or more in 1-methyl-2-pyrrolidinone, dimethyl sulfoxide (DMSO), diethyl acetamide and acetone；
The additive is selected from the variety classeses such as inorganic non-solvent, inorganic salts, small organic molecule and larger molecular organics
Film for additive in one or more, it is preferable that including water, polyethylene glycol, acetone, ethanol, glycerine, tripotassium phosphate
One or more in ester, oxalic acid, lithium chloride, lithium perchlorate, lithium bromide, sodium chloride and phosphoric acid.
Preferably, the evaporation of the solvent environment in step 3) is 30-80 DEG C, solvent evaporation time 5-1800s, is preferably
30-600s, evaporitic environment humidity 0-80%.
Preferably, in step 4), the coagulating bath is further included at least selected from ethanol, diformazan based on non-solvent water
Base formamide, dimethylacetylamide, triethyl phosphate, 1-methyl-2-pyrrolidinone, dimethyl sulfoxide (DMSO), diethyl acetamide and acetone
In one or more organic solvents.
Preferably, in step 4), soaking time for 2 it is small when more than.
As another aspect of the present invention, there is provided a kind of preparation method as described above is obtained to have micro-nano prominent knot
The hydrophobic membrane of structure surface functional layer, the surface of the hydrophobic membrane form micro/nano level crystalline texture, and contact angle is 85-150 degree, table
Surface roughness is 20-150nm, and maximum peak valley distance is 40-400nm.
Compared with prior art, beneficial effects of the present invention are as follows：
1st, hydrophobic membrane of the present invention realizes constructing for film surface micro nano structure by simple phase inversion, passes through
The time control of exposure phase (evaporation of the solvent stage) is controlled to protrude the size of structure；
2nd, hydrophobic membrane of the present invention significantly improves film hydrophobic performance, slows down film wetting phenomena during hydrophobic membrane；
3rd, hydrophobic membrane of the present invention constructing due to surface protrusion structure, can increase film surface turbulent flow, Jin Eryi
Determine to reduce fouling membrane phenomenon in degree；
4th, hydrophobic membrane of the present invention, can be applied in various hydrophobic membrane separating process, including membrane distillation, gas point
From film, infiltration evaporation etc..
Brief description of the drawings
Fig. 1 is polymer film surface electromicroscopic photograph made from embodiment 1；
Fig. 2 is polymer film surface atomic force microscopy made from embodiment 1；
Fig. 3 is polymer film surface electromicroscopic photograph made from embodiment 2；
Fig. 4 is polymer film surface atomic force microscopy made from embodiment 2；
Fig. 5 is polymer film surface electromicroscopic photograph made from embodiment 3；
Fig. 6 is polymer film surface atomic force microscopy made from embodiment 3.
Embodiment
For the object, technical solutions and advantages of the present invention are more clearly understood, below in conjunction with specific embodiment, and reference
Attached drawing, the present invention is described in further detail.
In recent years, under the enlightenment of lotus leaf, roseleaf and pleuston, the preparation of Biomimetic membranes becomes hydrophobic membrane
An or even direction to receive much concern prepared by super-hydrophobic film.One distinguishing feature of these biological surfaces is with micron or nanometer
The protrusion structure of level, according to Cassie-Baxter equations, this structure can improve contact angle when being contacted with water, so as to be in
Reveal hydrophobic property.Under the inspiration of this biological structure, constructing as hydrophobic at present for the micro-nano prominent structure of film surface is carried out
One important research direction of film preparation.At present, constructing for this biomimetic features is mainly added by electrostatic spinning, nano material
Realized etc. mode, obtained more research and achieved preferable effect.
This method can be realized in film forming procedure poly- based on vinylidene and its copolymer by the control of certain condition
This feature of the formation of compound crystallization, is considered as preparing the method that solvent guiding inversion of phases and submergence inversion of phases are combined and dredges
Moisture film.In solvent volatilization period, on primary membrane top layer, polymer crystallization process takes place, and guiding carries out solid liquid phase conversion.And
With the growth of process-exposed, film surface layer is formed, and crystalline texture starts reunion and becomes larger, and forms nanometer or even micron-sized knot
Structure, improves the hydrophobic performance of film.When primary membrane is immersed into coagulating bath, due to the fast exchange of solvent and non-solvent, liquid liquid divides
Phase process is immediately begun to, and forms polymer-poor phase and polymer richness phase, polymer start to cure.But due to the evaporation of the solvent stage
Cause solution viscosity to improve and form crystallization, hinder solvent and non-solvent exchange process, crystallization process is still carrying out.Therefore, will
Evaporation of the solvent trigger inversion of phases with submerge inversion of phases be combined can realize surface micronano structure construct and film mechanicalness
The guarantee of energy, and pass through the control of two step inversion of phases processes, it is possible to achieve surface functional layer protrudes the regulation and control of structure size.
The preparation method of the hydrophobic membrane with micro-nano prominent body structure surface functional layer of the present invention, this method include following
Step：
Step 1) will crystallize or semi-crystalline polymer powder or particle drying, to remove moisture removal (non-solvent) to casting solution heat
The influence of mechanical property；
The crystallization or semi-crystalline polymer, include but not limited to PVDF, PVDF-HFP, PVDF-CTFE, PVDF-TrFE
Deng.
Polymer in additive, organic solvent and step 1) by drying is polymer by weight percentage by step 2)
8-20%, additive 0-8%, organic solvent 70-90% are mixed, and constant temperature is with 50-1400 revs/min at 20-70 DEG C
Speed is uniformly mixed, when constant temperature deaeration 12 is small under the conditions of 20-70 DEG C more than after form homogeneous casting solution；
Wherein, the organic solvent includes but not limited to dimethylformamide, dimethylacetylamide, triethyl phosphate, N-
One or more in methyl pyrrolidone, dimethyl sulfoxide (DMSO), diethyl acetamide and acetone；
The additive includes but not limited to inorganic non-solvent, inorganic salts, small organic molecule and larger molecular organics etc.
Different types of film for additive, it is preferable that including water, polyethylene glycol, acetone, ethanol, glycerine, trimethyl phosphate, oxalic acid,
One or more in lithium chloride, lithium perchlorate and phosphoric acid；
Deaeration mode includes standing degassing and vacuum outgas.
Step 3) forms a film the casting solution in step 2) by scraping film device striking, and 5- is placed in 50-80 DEG C of baking oven
1800s is converted with achievement unit split-phase, 30-600s, the ambient humidity 0-80% is preferably placed, wherein it is ability to scrape film device
The conventional equipment of polymer film is prepared in domain, and therefore not to repeat here；
In addition, it can also can ensure to carry out evaporation of the solvent in the device of corresponding thermostat temperature at other in addition to baking oven.
Step 4) by primary membrane of the step 3) after certain evaporation process be immersed in 15-50 DEG C of coagulating bath 24 it is small when after
Dried in air ambient, that is, obtain the new hydrophobic film；The coagulating bath is further included and is at least selected from based on non-solvent water
Ethanol, dimethylformamide, dimethylacetylamide, triethyl phosphate, 1-methyl-2-pyrrolidinone, dimethyl sulfoxide (DMSO), diethyl second
One or more organic solvents in acid amides and acetone, coagulating bath is mixed with water composition.
Micro/nano level crystalline texture is formed through hydrophobic film surface made from above-mentioned preparation method, contact angle is 85-150 degree,
Surface roughness is 20-150nm, and maximum peak valley distance is 40-400nm.
Specific embodiment is exemplified below, to be described further to technical scheme.
Embodiment 1
Dried PVDF, lithium chloride, organic solvent DMAc are pressed 12：5：83 mass ratio is under 30 DEG C of constant temperatures
With 200 revs/min of rotating speeds stir 24 it is small when；Then casting solution is obtained when standing and defoaming 24 is small under constant temperature at 30 DEG C；Recycle
Laboratory make by oneself scraper by casting solution on the glass for be stained with non-woven fabrics striking into primary membrane；Finally by primary membrane in 50 DEG C of baking ovens
It is middle stop 10 seconds after when immersion 24 is small in 30 DEG C of water coagulating baths after take out and dry in atmosphere, that is, obtain hydrophobic membrane.The film table
Face forms certain nano crystals structure (as shown in Figure 2), surface roughness 112.12nm, contact angle 95.0
Degree, average pore size is 0.15 micron, using 3.5%NaCl solution as stoste, hot cold-side temperature and flow be respectively 56 degrees Celsius,
65 ls/h；Run under conditions of 24 degrees Celsius, 50 ls/h, rejection is up to more than 99%, permeant flux 16.96kg/
(m2·h)。
Fig. 1 is film surface electromicroscopic photograph made from the present embodiment；Fig. 2 is film surface atomic force microscopy made from the present embodiment
Mirror photo.
Embodiment 2
PVDF-CTFE powder, lithium chloride and dimethylacetylamide after drying is mixed by 12: 5: 83 mass ratio
Close, under 25 DEG C of constant temperatures with 1400 revs/min of rotating speeds stir 36 it is small when；Then when vacuum defoamation 8 is small under 25 DEG C of constant temperature
Obtain casting solution；Recycling flat membrane casting equipment, striking, finally will just into primary membrane on the glass for be stained with non-woven fabrics by casting solution
Filming when immersion 24 is small in 25 DEG C of tap water coagulating baths after 50 DEG C of baking ovens stop 60 seconds after take out and dry in atmosphere, to obtain the final product
To hydrophobic membrane.The film surface forms obvious nanometer to micron scale construction (attached drawing 4), surface roughness 135.4nm, the film
Contact angle be 97.8 degree, average pore size is 0.1086 micron, using 3.5%NaCl solution as stoste, hot cold-side temperature and stream
Amount is respectively 56 degrees Celsius, 65 ls/h；Run under conditions of 24 degrees Celsius, 50 ls/h, rejection is produced up to more than 99%
Water flux is 22.78kg/ (m2·h)。
Fig. 3 is film surface electromicroscopic photograph made from the present embodiment；Fig. 4 is film surface atomic force microscopy made from the present embodiment
Mirror photo.
Embodiment 3
PVDF-CTFE copolymer powders, lithium chloride, polyethylene glycol and dimethylacetylamide press 12: 4: 4 after first drying:
80 mass ratio mixing, under 25 DEG C of constant temperatures with 1400 revs/min of rotating speeds stir 36 it is small when；Then under 25 DEG C of constant temperature
Standing and defoaming 24 obtains casting solution when small；Recycle flat membrane casting equipment by casting solution on the glass for be stained with non-woven fabrics striking into first
Filming, in 25 DEG C of coagulating bath (water: ethanol=60 after finally primary membrane is stopped 300 seconds in 60 DEG C of baking ovens：40) immersion 24 in
Take out after hour and dry in atmosphere, that is, obtain hydrophobic membrane.The contact angle of the film is 103.7 degree, and surface roughness is
40.87nm, average pore size are 0.1266 micron, and using 3.5%NaCl solution as stoste, hot cold-side temperature and flow are respectively 56
Degree Celsius, 65 ls/h；Run under conditions of 24 degrees Celsius, 50 ls/h, rejection is up to more than 99%, permeant flux
24.78kg/(m2·h)。
Fig. 5 is film surface electromicroscopic photograph made from the present embodiment；Fig. 6 is film surface atomic force microscopy made from the present embodiment
Mirror photo.
Embodiment 4-7 and comparative example 1
Embodiment 4-7 changes polymeric material, additive and organic solvent using the preparation method described in this patent
Species and composition, change the evaporation of the solvent stage and submerge the condition in stage, using conventional wet preparation method, i.e., not comparative example is
Through evaporation process, submergence obtains pvdf membrane directly in coagulating bath.Design parameter and experimental result are see shown in table 1 below.
The test parameters and result of the test table of 1 embodiment 4-7 of table
To sum up, dredged as made from the preparation method of the bionical hydrophobic membrane with micro-and nano-structural surface functional layer of the present invention
Moisture film, while mass-transfer performance is permeated with good film, also with good hydrophobic performance.
Particular embodiments described above, has carried out the purpose of the present invention, technical solution and beneficial effect further in detail
Describe in detail bright, it should be understood that the foregoing is merely the present invention specific embodiment, be not intended to limit the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done, should be included in the protection of the present invention
Within the scope of.
Claims (8)
- A kind of 1. preparation method of the hydrophobic membrane with micro-nano prominent body structure surface functional layer, it is characterised in that the preparation Method is phase inversion, is comprised the steps of：1) will crystallization or semi-crystalline polymer powder or particle drying, to go influence of the moisture removal to casting solution thermodynamic property；To by dry polymer be by weight percentage 2) polymer 8-20% in additive, organic solvent and step 1), Additive 0-8%, organic solvent 70-90% are mixed, at 20-70 DEG C constant temperature stirring a period of time to be uniformly mixed, Homogeneous casting solution is formed under the conditions of 20-70 DEG C after constant temperature deaeration；3) casting solution in step 2) is formed a film by scraping film device striking, and the sky of certain humidity is stayed at 50-80 DEG C A period of time is to promote the conversion of part solid liquid phase in gas；4) primary membrane for obtaining step 3) is immersed in 15-50 DEG C of coagulating bath, is dried after soaking a period of time, that is, is obtained described Hydrophobic membrane.
- 2. preparation method according to claim 1, it is characterised in that in step 1), the crystallization or semi-crystalline polymer For Kynoar, Kynoar-hexafluoropropylene copolymer, Kynoar-chlorotrifluoroethylene or polyvinylidene fluoride Alkene-trifluoro-ethylene copolymer.
- 3. preparation method according to claim 1, it is characterised in that in step 2), when constant temperature mixing time is 5-24 small, Constant temperature inclined heated plate when 12 is small more than, deaeration mode include stand degassing and vacuum outgas.
- 4. preparation method according to claim 1, it is characterised in that in step 2), the organic solvent is selected from dimethyl In formamide, dimethylacetylamide, triethyl phosphate, 1-methyl-2-pyrrolidinone, dimethyl sulfoxide (DMSO), diethyl acetamide and acetone One or more；In film for additive of the additive selected from inorganic non-solvent, inorganic salts, small organic molecule and larger molecular organics One or more, be preferably selected from water, polyethylene glycol, acetone, ethanol, glycerine, trimethyl phosphate, oxalic acid, lithium chloride, high chlorine One or more in sour lithium, lithium bromide, sodium chloride and phosphoric acid.
- 5. preparation method according to claim 1, it is characterised in that the evaporation of the solvent environment in step 3) is 30-80 DEG C, Solvent evaporation time is 5-1800s, is preferably 30-600s, evaporitic environment humidity 0-80%.
- 6. preparation method according to claim 1, it is characterised in that in step 4), the coagulating bath is with non-solvent water For main body, further include at least selected from ethanol, dimethylformamide, dimethylacetylamide, triethyl phosphate, N- crassitudes One or more organic solvents in ketone, dimethyl sulfoxide (DMSO), diethyl acetamide and acetone.
- 7. preparation method according to claim 1, it is characterised in that in step 4), soaking time for 2 it is small when more than.
- 8. there is micro-nano prominent body structure surface work(made from a kind of preparation method as described in claim 1 to 7 any one The hydrophobic membrane of ergosphere, it is characterised in that the surface of the hydrophobic membrane forms micro/nano level crystalline texture, contact angle 85-150 Degree, surface roughness 20-150nm, maximum peak valley distance is 40-400nm.
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| CN112295409B (en) * | 2019-07-31 | 2022-04-05 | 天津工业大学 | Super-hydrophobic membrane with open network surface structure and preparation method thereof |
| CN112973451A (en) * | 2019-12-12 | 2021-06-18 | 中国石油化工股份有限公司 | Polymer microfiltration membrane with micro-nano composite network pore structure and preparation method and application thereof |
| CN114950151A (en) * | 2022-04-28 | 2022-08-30 | 中南大学 | Flat sheet membrane, membrane module, membrane distillation device and method for concentrating copper-containing wastewater |
| CN114950151B (en) * | 2022-04-28 | 2023-09-29 | 中南大学 | Flat membrane, membrane assembly, membrane distillation device and method for concentrating copper-containing wastewater |
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