CN106582332A - Method for preparing superhydrophobic composite microporous membrane - Google Patents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
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Abstract
The invention relates to a method for preparing a superhydrophobic composite microporous membrane. The method comprises the following steps: firstly, preparing a polyvinylidene fluoride (PVDF) high-hydrophobic microporous membrane as a basal membrane by a coarse substrate assisted phase inversion method, then, preparing a multi-walled carbon nanotube (MWCNTs) uniform dispersion solution, filtering the MWCNTs dispersion solution with the prepared PVDF basal membrane at constant pressure by adopting a constant-pressure filtering method so as to prepare a PVDF/MWCNTs composite membrane, and carrying out coating with an n-hexane solution of polydimethylsiloxane (PDMS), thereby preparing the PVDF/MWCNTs/PDMS superhydrophobic composite microporous membrane. According to the composite microporous membrane obtained by the method, the static water contact angle can reach 162 degrees, the angle of roll is 10 to 20 degrees, the nitrogen gas flux at the pressure of 100kPa is greater than 0.3m<3>/(m<2>.s), the tensile strength is higher than 2.6MPa, and the elongation at break is higher than 96%, so that the superhydrophobic composite microporous membrane can be applied to membrane contact procedures such as membrane distillation and membrane absorption.
Description
Technical field
The present invention relates to a kind of preparation method of super-hydrophobic composite micro porous film, specifically one kind are under constant-pressure conditions, use
PVDF basement membranes filter multi-walled carbon nano-tubes uniform dispersion and prepare PVDF/MWCNTs composite membranes, then Jing polydimethylsiloxane
(PDMS) hexane solution coating, the method for preparing the super-hydrophobic composite micro porous films of PVDF/MWCNTs/PDMS.
Background technology
In recent years, super hydrophobic surface (being more than 150 ° of surface with the contact angle of water) receives the extensive concern of people.Grind
Study carefully and show, construction super hydrophobic surface can be started with from increase surface roughness and in terms of reducing surface energy two.Kynoar
(PVDF) because its excellent physical and chemical performance is widely used in preparative separation film, but PVDF hydrophobic membrane is yet suffered from the application
The problems such as hydrophilic infiltration of film, non-anti-pollution, therefore, carry out modifying super hydrophobicity to improve its hydrophobicity and resistance tocrocking to pvdf membrane
Become key issue urgently to be resolved hurrily.With the development of functional material, inorganic nano material is combined into preparation with polymer compound
Material causes the extensive concern of people.CNT (CNTs) because the particularity in structure and uniqueness physical and chemical performance,
Become one of most popular nano material of people's research.At present, there are many reports with regard to carbon nanotube/polymer composite membrane
Road, wherein mostly is that CNT is added to blending in polymer solution to prepare composite membrane, its effect mainly changes polymer
Overall performance, for using other preparation methoies and paying close attention to which and be also rarely reported on research that surface property affects.
The content of the invention
Present invention aims to not enough present in current techniques, there is provided a kind of system of super-hydrophobic composite micro porous film
Preparation Method.Multi-walled carbon nano-tubes is inserted PVDF very hydrophobic basement membranes using constant pressure filtration method by the method (with the contact angle of water about
120 °) micropore in, build nanoscale structures on the basis of the original micron scale construction in film surface, form the compound rank of micro-nano
Rotating fields increase film surface roughness, then by coating the free energy on PDMS solution reduction film surface, two aspect synergism increase
The contact angle on big film surface, while reducing the roll angle on film surface, is prepared for PVDF/MWCNTs/PDMS super-hydrophobic composite microporous
Film.
A kind of preparation method of super-hydrophobic composite micro porous film, comprises the following steps：
(1) PVDF very hydrophobic microporous membranes are prepared using rough base auxiliary phase inversion：By casting solution Jing dissolvings, stand
After deaeration, it is placed in substrate, the liquid film of 0.15 μm of -0.2 μ m-thick of striking in substrate, the induction of liquid film Jing water vapour, solidification
Bath split-phase, removes after being solidified into solid film from substrate, soaks, dry, obtain under room temperature in being sequentially placed into deionized water, ethanol
PVDF very hydrophobic microporous membranes；Described substrate has the aluminium alloy plate of micron order coarse structure for surface；Described casting solution
Quality percentage composition be Kynoar (PVDF) 10%-14%, n-octyl alcohol 6%-10%, remaining is solvent；
(2) multi-walled carbon nano-tubes (MWCNTs) and Carbon nano-tube dispersant are dissolved in deionized water, after stirring, first
Supersound process 30min-60min, then centrifugal treating 30min-60min, obtain the carbon nanometer that concentration is 0.01wt%-0.05wt%
Pipe dispersion liquid；The quality of Carbon nano-tube dispersant is the 25%-35% of carbon nanotube mass used；
(3) under constant 0.05MPa-0.25MPa filtration pressure differences, with PVDF basement membranes obtained in step (1) in the filter
The MWCNTs uniform dispersions that filtration step (2) is configured while stirring, wherein, contact micron order coarse structure aluminium alloy plate
PVDF membrane surfaces, are uniformly divided after the completion of filtration towards on the film surface of MWCNTs dispersion liquids side towards MWCNTs dispersion liquids side
MWCNTs is furnished with, PVDF/MWCNTs composite membranes are obtained, will be dried under gained PVDF/MWCNTs composite membrane room temperatures, it is stand-by；
(4) polydimethylsiloxane (PDMS) is dissolved in normal hexane, configure PDMS concentration for 1wt%-8wt% just oneself
Alkane solution is used as coating liquid；PVDF/MWCNTs composite membranes obtained in step (3) are fixed on smooth glass plate, are distributed with
The film surface of MWCNTs is upward；Then glass plate level is submerged in coating liquid, be stained with film one faces up, water after 2s-5s
It is flat to take out, obtain the super-hydrophobic composite micro porous films of PVDF/MWCNTs/PDMS.
Described Carbon nano-tube dispersant is specially CNT water dispersant (TNWDIS), sodium lauryl sulphate
(SDS), one kind in Triton X-100 (Triton X-100).
In described step (1), the solvent of casting solution is DMAC N,N' dimethyl acetamide (DMAc), N,N-dimethylformamide
Or N-Methyl pyrrolidone (NMP) (DMF).
Described CNT is multi-walled carbon nano-tubes, hydroxyl multi-walled carbon nano-tube or functionalized multi-wall carbonnanotubes.
The aluminium alloy plate that described surface has micron order coarse structure is obtained by following steps：Compound concentration is
The hydrochloric acid solution of the oxalic acid solution and 1mol/L of 0.08mol/L, with 1:1 volume ratio blending is obtained nitration mixture, and aluminium alloy plate is existed
Obtain after soaking 6h-10h in mixed acid solution.
Beneficial effects of the present invention are：
The method that conventional CNT prepares carbon nanotube/polymer composite membrane with polymer solution blend is different from,
The present invention is pressed into multi-walled carbon nano-tubes in the micropore of PVDF basement membranes using constant pressure filtration method and prepares composite membrane, original on film surface
Micron scale construction on the basis of build nanoscale structures, to form the compound hierarchical structure of micro-nano.With other nanoparticle phases
Than, while being added in increase film surface roughness of MWCNTs, the tubular structure having due to itself still can ensure that film
Permeability.PVDF/MWCNTs composite film surfaces coat low-surface-energy PDMS, reduce film surface free energy, MWCNTs and
Both PDMS synergism, increases the contact angle on film surface, while reducing the roll angle on film surface, improves the hydrophobicity of film
Energy.The composite micro porous film prepared according to the present invention possesses super-hydrophobicity, and up to 162 °, roll angle is for the contact angle of film surface and water
10 ° -20 °, the nitrogen flux under 100kPa>0.3m3/(m2S), tensile strength>2.6MPa, elongation at break>96%.
Description of the drawings
Fig. 1 is the schematic flow sheet of the present invention；
Fig. 2 is the schematic device that constant pressure filtration method prepares PVDF/MWCNTs composite membranes；
Fig. 3 is the surface SEM figures of the PVDF basement membranes that embodiment 3 is obtained and PVDF/MWCNTs composite membranes；Wherein, Fig. 3 (a)
Surface SEM for PVDF basement membranes schemes, and Fig. 3 (b) is schemed for the surface SEM of PVDF/MWCNTs composite membranes；
Fig. 4 is surface A FM of the PVDF basement membranes that embodiment 3 is obtained and the super-hydrophobic composite micro porous films of PVDF/MWCNTs/PDMS
Figure, wherein, Fig. 4 (a) is schemed for surface A FM of PVDF basement membranes, surface As FM of the Fig. 4 (b) for PVDF/MWCNTs/PDMS composite membranes
Figure；
Fig. 5 is respectively the water on the super-hydrophobic composite micro porous film surfaces of PVDF/MWCNTs/PDMS that embodiment 2,3,4 is obtained and connects
Feeler test chart；
Specific embodiment
The present invention is described further with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
Configuration quality composition respectively Kynoar (PVDF) -10%, N,N-dimethylacetamide (DMAc) -84%,
The casting solution of n-octyl alcohol (1-Octanol) -6% is placed in 70 DEG C of vacuum drying oven, and casting solution is completely dissolved and is sufficiently mixed
Temperature is adjusted to into 35 DEG C of standing and defoamings 2 days after uniform, with scraper by casting solution uniform striking chemical etching 8h aluminium alloy plate
On, the liquid film of 0.15 μm of -0.2 μ m-thick is onboard formed, liquid film is placed on into the climatic chamber that relative humidity is 95%
Middle water vapour induces 5min, then immerses liquid film in 35 DEG C of pure water coagulating bath after split-phase 0.5h, and liquid film is solidified into
State film, removes to be placed in deionized water from aluminium alloy plate and soaks 2 days, then immerses immersion 1 day in ethanol, takes out solid film room temperature
Under dry, obtain PVDF very hydrophobic microporous membranes.
In described step (1), substrate is that (model S6061, the main element containing Mg and Si, is a kind of cold place to aluminium alloy plate
Reason aluminium forging product) be concentration for the oxalic acid solution and 1mol/L of 0.08mol/L hydrochloric acid solution with 1:1 volume ratio blending
The aluminium alloy plate obtained after soaking 8h in obtained mixed acid solution, its surface has micron order coarse structure.
Weigh 0.01g functionalized multi-wall carbonnanotubes (MWCNTs) and 0.003g CNT water dispersants (TNWDIS) is molten
In the deionized water of 99.987g, after stirring, first supersound process 40min (25 DEG C, 120W), then centrifugal treating 40min
(5000r/min), obtain uniform carbon nano tube dispersion liquid.It is under the filtration pressure difference of 0.15MPa, micro- with above-mentioned PVDF very hydrophobics
Pore membrane is basement membrane, and basement membrane is installed in the filter, the film surface direction of micron order coarse structure on aluminium alloy plate is replicated
MWCNTs dispersion liquids side, filters the uniform dispersion when (400r/min) is stirred, after the completion of filtration, obtains PVDF/MWCNTs
Composite membrane, is evenly distributed with MWCNTs towards on the film surface of MWCNTs dispersion liquids side, and another side does not have MWCNTs distributions, will
Dry under gained PVDF/MWCNTs composite membrane room temperatures, it is stand-by.
7.8ml PDMS are dissolved in 252.2ml normal hexane and configure coating liquid.Regular PVDF/ will be cut out with adhesive tape
MWCNTs composite membranes are fixed on smooth glass plate, and the film surface of MWCNTs is distributed with upward, and another side is close to glass plate, it is ensured that
Adhesive tape is sternly left no gaps the surrounding of film and glass plate viscous.Then glass plate level is submerged in coating liquid, is stained with the one of film
Face up, after 3s, level is taken out, and dries and obtain the super-hydrophobic composite micro porous films of PVDF/MWCNTs/PDMS under room temperature.
Measured the super-hydrophobic composite micro porous films of PVDF/MWCNTs/PDMS and with the contact angle of water be with dynamic/static contact angle instrument
159 °, roll angle is 19 °；It is 0.31m that the nitrogen flux under 100kPa is measured with flux measuring device3/(m2S), use electronics list
Yarn strength tester measures the tensile strength and elongation at break of the super-hydrophobic composite micro porous films of PVDF/MWCNTs/PDMS
2.62MPa, 96.8%.
Embodiment 2
Configuration quality composition respectively Kynoar (PVDF) -10%, N,N-dimethylacetamide (DMAc) -84%,
The casting solution of n-octyl alcohol (1-Octanol) -6% is placed in 70 DEG C of vacuum drying oven, and casting solution is completely dissolved and is sufficiently mixed
Temperature is adjusted to into 35 DEG C of standing and defoamings 2 days after uniform, with scraper by casting solution uniform striking chemical etching 8h aluminium alloy plate
On, the liquid film of 0.15 μm of -0.2 μ m-thick is onboard formed, liquid film is placed on into the climatic chamber that relative humidity is 95%
Middle water vapour induces 5min, then immerses liquid film in 35 DEG C of pure water coagulating bath after split-phase 0.5h, and liquid film is solidified into
State film, removes to be placed in deionized water from aluminium alloy plate and soaks 2 days, then immerses immersion 1 day in ethanol, takes out solid film room temperature
Under dry, obtain PVDF very hydrophobic microporous membranes.
Weigh 0.03g functionalized multi-wall carbonnanotubes (MWCNTs) and 0.009g CNT water dispersants (TNWDIS) is molten
In the deionized water of 99.961g, after stirring, first supersound process 40min (25 DEG C, 120W), then centrifugal treating 40min
(5000r/min), obtain uniform carbon nano tube dispersion liquid.It is under the filtration pressure difference of 0.2MPa, micro- with above-mentioned PVDF very hydrophobics
Pore membrane is basement membrane, and basement membrane is installed in the filter, the film surface direction of micron order coarse structure on aluminium alloy plate is replicated
MWCNTs dispersion liquids side, filters the uniform dispersion when (400r/min) is stirred, after the completion of filtration, obtains PVDF/MWCNTs
Composite membrane, is evenly distributed with MWCNTs towards on the film surface of MWCNTs dispersion liquids side, and another side does not have MWCNTs distributions, will
Dry under gained PVDF/MWCNTs composite membrane room temperatures, it is stand-by.
7.8ml PDMS are dissolved in 252.2ml normal hexane and configure coating liquid.Regular PVDF/ will be cut out with adhesive tape
MWCNTs composite membranes are fixed on smooth glass plate, and the film surface of MWCNTs is distributed with upward, and another side is close to glass plate, it is ensured that
Adhesive tape is sternly left no gaps the surrounding of film and glass plate viscous.Then glass plate level is submerged in coating liquid, is stained with the one of film
Face up, after 3s, level is taken out, and dries and obtain the super-hydrophobic composite micro porous films of PVDF/MWCNTs/PDMS under room temperature.
The method and identical in embodiment 1, the super-hydrophobic composite micro porous film films of PVDF/MWCNTs/PDMS of test film properties
Surface is 161 ° with the contact angle of water, and roll angle is 16 °, and the nitrogen flux under 100kPa is 0.34m3/(m2S), stretch-proof is strong
Spend for 2.61MPa, elongation at break is 97.0%.
Embodiment 3
Configuration quality composition respectively Kynoar (PVDF) -10%, N,N-dimethylacetamide (DMAc) -84%,
The casting solution of n-octyl alcohol (1-Octanol) -6% is placed in 70 DEG C of vacuum drying oven, and casting solution is completely dissolved and is sufficiently mixed
Temperature is adjusted to into 35 DEG C of standing and defoamings 2 days after uniform, with scraper by casting solution uniform striking chemical etching 8h aluminium alloy plate
On, the liquid film of 0.15 μm of -0.2 μ m-thick is onboard formed, liquid film is placed on into the climatic chamber that relative humidity is 95%
Middle water vapour induces 5min, then immerses liquid film in 35 DEG C of pure water coagulating bath after split-phase 0.5h, and liquid film is solidified into
State film, removes to be placed in deionized water from aluminium alloy plate and soaks 2 days, then immerses immersion 1 day in ethanol, takes out solid film room temperature
Under dry, obtain PVDF very hydrophobic microporous membranes.
Weigh 0.03g functionalized multi-wall carbonnanotubes (MWCNTs) and 0.009g CNT water dispersants (TNWDIS) is molten
In the deionized water of 99.961g, after stirring, first supersound process 40min (25 DEG C, 120W), then centrifugal treating 40min
(5000r/min), obtain uniform carbon nano tube dispersion liquid.It is under the filtration pressure difference of 0.15MPa, micro- with above-mentioned PVDF very hydrophobics
Pore membrane is basement membrane, and basement membrane is installed in the filter, the film surface direction of micron order coarse structure on aluminium alloy plate is replicated
MWCNTs dispersion liquids side, filters the uniform dispersion when (400r/min) is stirred, after the completion of filtration, obtains PVDF/MWCNTs
Composite membrane, is evenly distributed with MWCNTs towards on the film surface of MWCNTs dispersion liquids side, and another side does not have MWCNTs distributions, will
Dry under gained PVDF/MWCNTs composite membrane room temperatures, it is stand-by.
7.8ml PDMS are dissolved in 252.2ml normal hexane and configure coating liquid.Regular PVDF/ will be cut out with adhesive tape
MWCNTs composite membranes are fixed on smooth glass plate, and the film surface of MWCNTs is distributed with upward, and another side is close to glass plate, it is ensured that
Adhesive tape is sternly left no gaps the surrounding of film and glass plate viscous.Then glass plate level is submerged in coating liquid, is stained with the one of film
Face up, after 3s, level is taken out, and dries and obtain the super-hydrophobic composite micro porous films of PVDF/MWCNTs/PDMS under room temperature.
The method and identical in embodiment 1, the super-hydrophobic composite micro porous film films of PVDF/MWCNTs/PDMS of test film properties
The contact angle of face water is 162 °, and roll angle is 12 °, and the nitrogen flux under 100kPa is 0.33m3/(m2S), tensile strength is
2.65MPa, elongation at break are 97.4%.
Embodiment 4
Configuration quality composition respectively Kynoar (PVDF) -10%, N,N-dimethylacetamide (DMAc) -84%,
The casting solution of n-octyl alcohol (1-Octanol) -6% is placed in 70 DEG C of vacuum drying oven, and casting solution is completely dissolved and is sufficiently mixed
Temperature is adjusted to into 35 DEG C of standing and defoamings 2 days after uniform, with scraper by casting solution uniform striking chemical etching 8h aluminium alloy plate
On, the liquid film of 0.15 μm of -0.2 μ m-thick is onboard formed, liquid film is placed on into the climatic chamber that relative humidity is 95%
Middle water vapour induces 5min, then immerses liquid film in 35 DEG C of pure water coagulating bath after split-phase 0.5h, and liquid film is solidified into
State film, removes to be placed in deionized water from aluminium alloy plate and soaks 2 days, then immerses immersion 1 day in ethanol, takes out solid film room temperature
Under dry, obtain PVDF very hydrophobic microporous membranes.
Weigh 0.03g functionalized multi-wall carbonnanotubes (MWCNTs) and 0.009g CNT water dispersants (TNWDIS) is molten
In the deionized water of 99.961g, after stirring, first supersound process 40min (25 DEG C, 120W), then centrifugal treating 40min
(5000r/min), obtain uniform carbon nano tube dispersion liquid.It is under the filtration pressure difference of 0.15MPa, micro- with above-mentioned PVDF very hydrophobics
Pore membrane is basement membrane, and basement membrane is installed in the filter, the film surface direction of micron order coarse structure on aluminium alloy plate is replicated
MWCNTs dispersion liquids side, filters the uniform dispersion when (400r/min) is stirred, after the completion of filtration, obtains PVDF/MWCNTs
Composite membrane, is evenly distributed with MWCNTs towards on the film surface of MWCNTs dispersion liquids side, and another side does not have MWCNTs distributions, will
Dry under gained PVDF/MWCNTs composite membrane room temperatures, it is stand-by.
13.0mlPDMS is dissolved in 247.0ml normal hexane and configures coating liquid.Regular PVDF/ will be cut out with adhesive tape
MWCNTs composite membranes are fixed on smooth glass plate, and the film surface of MWCNTs is distributed with upward, and another side is close to glass plate, it is ensured that
Adhesive tape is sternly left no gaps the surrounding of film and glass plate viscous.Then glass plate level is submerged in coating liquid, is stained with the one of film
Face up, after 3s, level is taken out, and dries and obtain the super-hydrophobic composite micro porous films of PVDF/MWCNTs/PDMS under room temperature.
The method and identical in embodiment 1, the super-hydrophobic composite micro porous film films of PVDF/MWCNTs/PDMS of test film properties
Face is 160 ° with the contact angle of water, and roll angle is 18 °, and the nitrogen flux under 100kPa is 0.30m3/(m2S), tensile strength
For 2.64MPa, elongation at break is 98.6%.
Above the separate embodiment of the present invention is described in detail, but the content has been only the preferable enforcement of the present invention
Example, it is impossible to be considered as limiting practical range of the invention.All impartial changes made according to the present patent application scope and improvement
Deng, still all should belong to the present invention patent covering scope within.
Unaccomplished matter of the present invention is known technology.
Claims (5)
1. a kind of preparation method of super-hydrophobic composite micro porous film, it is characterized by comprising the following steps：
(1) PVDF very hydrophobic microporous membranes are prepared using rough base auxiliary phase inversion：By casting solution Jing dissolvings, standing and defoaming
Afterwards, it is placed in substrate, the thick liquid films of 0.15 m-0.2 m, the induction of liquid film Jing water vapour, coagulating bath point is formed in substrate
Phase, removes after being solidified into solid film from substrate, soaks, dry, obtain PVDF under room temperature in being sequentially placed into deionized water, ethanol
Very hydrophobic microporous membrane；Described substrate has the aluminium alloy plate of micron order coarse structure for surface；The matter of described casting solution
Amount percentage composition is Kynoar (PVDF) 10%-14%, n-octyl alcohol 6%-10%, and remaining is solvent；
(2) by multi-walled carbon nano-tubes（MWCNTs）It is dissolved in deionized water with Carbon nano-tube dispersant, it is after stirring, first ultrasonic
30min-60min, then centrifugal treating 30min-60min are processed, the CNT that concentration is 0.01wt%-0.05wt% is obtained uniform
Dispersion liquid；The quality of Carbon nano-tube dispersant is the 25%-35% of carbon nanotube mass used；
(3) cross under mould difference in constant 0.05MPa-0.25MPa, with PVDF basement membranes obtained in step (1), side is stirred in the filter
The MWCNTs uniform dispersions that side filtration step (2) is configured are mixed, wherein, contact the PVDF bases of micron order coarse structure aluminium alloy plate
Film surface, is evenly distributed with after the completion of filtration towards on the film surface of MWCNTs dispersion liquids side towards MWCNTs dispersion liquids side
MWCNTs, obtains PVDF/MWCNTs composite membranes, will dry under gained PVDF/MWCNTs composite membrane room temperatures, stand-by；
(4) by polydimethylsiloxane（PDMS）It is dissolved in normal hexane, configures hexane solution of the PDMS concentration for 1wt%-8wt%
As coating liquid；PVDF/MWCNTs composite membranes obtained in step (3) are fixed on smooth glass plate, are distributed with MWCNTs's
Film surface is upward；Then glass plate level is submerged in coating liquid, be stained with film one faces up, after 2s-5s, level is taken out, and obtains
To the super-hydrophobic composite micro porous films of PVDF/MWCNTs/PDMS.
2. the preparation method of super-hydrophobic composite micro porous film as claimed in claim 1, it is characterized by described CNT dispersion
Agent is specially CNT water dispersant（TNWDIS）, sodium lauryl sulphate（SDS）, Triton X-100（Triton X-100）
In one kind.
3. the preparation method of super-hydrophobic composite micro porous film as claimed in claim 1, it is characterized by casting film in described step (1)
The solvent of liquid is DMAC N,N' dimethyl acetamide（DMAc）, N,N-dimethylformamide (DMF) or N-Methyl pyrrolidone (NMP).
4. the preparation method of super-hydrophobic composite micro porous film as claimed in claim 1, it is characterized by described CNT is many
Wall carbon nano tube, hydroxyl multi-walled carbon nano-tube or functionalized multi-wall carbonnanotubes.
5. the preparation method of super-hydrophobic composite micro porous film as claimed in claim 1, it is characterized by described surface has micron
The aluminium alloy plate of level coarse structure is obtained by following steps：Salt of the compound concentration for the oxalic acid solution and 1mol/L of 0.08mol/L
Acid solution, with 1:1 volume ratio blending is obtained nitration mixture, obtains after aluminium alloy plate is soaked 6h-10h in mixed acid solution.
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