CN110368718A - A kind of superoleophobic nethike embrane of the super-hydrophilic and underwater of 3 D-printing and preparation method thereof - Google Patents
A kind of superoleophobic nethike embrane of the super-hydrophilic and underwater of 3 D-printing and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 69
- 238000007639 printing Methods 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 59
- 229920002301 cellulose acetate Polymers 0.000 claims abstract description 14
- 230000001112 coagulating effect Effects 0.000 claims abstract description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 12
- 239000002105 nanoparticle Substances 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 75
- 238000007711 solidification Methods 0.000 claims description 20
- 230000008023 solidification Effects 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000004513 sizing Methods 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 229940113088 dimethylacetamide Drugs 0.000 claims 1
- 239000012046 mixed solvent Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 235000019476 oil-water mixture Nutrition 0.000 abstract description 7
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 32
- 239000003502 gasoline Substances 0.000 description 20
- 235000019198 oils Nutrition 0.000 description 20
- 238000012360 testing method Methods 0.000 description 19
- 239000010408 film Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 239000012528 membrane Substances 0.000 description 14
- 238000000926 separation method Methods 0.000 description 12
- 239000002283 diesel fuel Substances 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 10
- 239000010687 lubricating oil Substances 0.000 description 10
- 235000015112 vegetable and seed oil Nutrition 0.000 description 10
- 239000008158 vegetable oil Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000010146 3D printing Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 230000005660 hydrophilic surface Effects 0.000 description 5
- 230000002207 retinal effect Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 206010054949 Metaplasia Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000009300 dissolved air flotation Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
-
- 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
-
- 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
-
- 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
- B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Thermal Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses superoleophobic nethike embranes of the super-hydrophilic and underwater of a kind of 3 D-printing and preparation method thereof, it is uniformly mixed by the way that inorganic nanoparticles, polyvinyl alcohol and cellulose acetate to be added in organic solvent with certain proportion, ink solution will be prepared later to be placed in syringe, then the bubble in ink is removed by centrifugal process；The netted structure of right-angled intersection of the marking ink of preparation on substrate according to loop cycle is depicted as the nethike embrane with network using three-dimensional ink direct write printing technique；Printed nethike embrane is put into coagulating bath and is further solidified, the nethike embrane with network and excellent mechanical performances is finally obtained.Nethike embrane prepared by the present invention has network, the size of grid is 50-500 μm, there is the superoleophobic characteristic of excellent super-hydrophilic and underwater simultaneously, it has high separative efficiency to oil-water mixture, the quick separating of oil-water mixture can be achieved, and this method has preparation process simple, raw material is easy to get, the advantages of can carrying out large-scale production and application.
Description
Technical field
Present invention relates particularly to superoleophobic nethike embranes of the super-hydrophilic and underwater of a kind of 3 D-printing and preparation method thereof, belong to film
Field of material preparation.
Background technique
Currently, since being continuously increased for industrial oily waste water produces greatly with Oil spills Frequent Accidents etc. in world wide
The oily waste water of amount, if these waste water, which cannot obtain effectively handling, will cause serious environment and ecological problem, therefore needle
The oily water separation technique of oiliness sewage treatment is had received widespread attention.Currently, the superoleophobic perforated membrane of super-hydrophilic and underwater can
To be selectively over drainage, while repelling oil contaminants completely again；Therefore, have in terms of realizing high efficiency oil-water separation very big
Potentiality, and with current existing Gravity separate, it is centrifugal separate, adsorbing separation, traditional water-oil separating such as dissolved air flotation
Technology is compared, and the superoleophobic perforated membrane of super-hydrophilic and underwater has at low cost, easy to operate, high water flux, good oil resistant dirt
The advantages that energy and high separating efficiency, and have broad application prospects in water-oil separating field.
Currently, the main method of the preparation superoleophobic membrane material of super-hydrophilic and underwater is surface-modification method, i.e., in commodity membrane material
Material surface coats one layer of super-hydrophilic and underwater super oleophobic coating and then obtains the grease with the superoleophobic characteristic of super-hydrophilic and underwater
Seperation film, Chinese patent 106422421A disclose a kind of preparation method and application of paper modification water-oil separationg film, this method
A strata DA Mediated layer is coated in surface, the polyethylene glycol with active aliphatic radical group is then retell or amphoteric ion is poly-
It closes object and is coated to surface, and then obtain the water-oil separationg film of hydrophilic and underwater oleophobic, but there are preparation processes for this method
Therefore how complicated disadvantage realizes that low cost, the preparation superoleophobic membrane material of super-hydrophilic and underwater is still efficiently, on a large scale
One huge challenge.
Three-dimensional printing technology is developed from increases material manufacturing technology at the end of the 20th century, it can according to design efficiently,
The fiber web material for printing different scale of low cost, therefore it is super hydrophilic and superoleophobic more in being applied to water-oil separating field
Pore membrane manufacture view has very high application potential.A kind of filter disclosed in Chinese patent CN102824654B uses porous ceramic film
3 D-printing molding method for preparing, this method is to print porous ceramics green body by three-dimensional printer, then will be more after printing
Hole ceramic body is dried, dumping and sintering, finally obtains the porous ceramic film with specific shape structure, the ceramic membrane pair
Sewage has very high treatment effeciency.A kind of 3 D-printing template disclosed in Chinese patent CN106182770A prepares pattern can
Hydrophobic or super-hydrophobic film the method for control, this method design the template with different hole looks, and root by three-dimensional printing technology
Template complex provides the hydrophobic or super thin film of raised structures accordingly, and Koh et al. is prepared by three-dimensional printing technology first will
Cellulose acetate solution ink printed removes net at a kind of cellulose acetate nethike embrane with network, then by hot setting
The nethike embrane is finally immersed in strong base solution by the solvent in film, and then obtains a kind of fiber that super-hydrophilic and underwater is superoleophobic
Plain nethike embrane, the nethike embrane have good water-oil separating efficiency and oil resistant pollution (Koh J J, Lim Jia Hao G, Zhou X,
et al.3D-Printed Anti-Fouling Cellulose Mesh for Highly Efficient Oil/Water
Separation Applications [J] .ACS Appl.Mater.Interfaces2019,11,13787-13795.), but
It is that alkali process in the preparation method can destroy the structure of material and then reduce the mechanical strength of material；Letters patent disclosed above
Bright three-dimensional printing technology has very high application value in the separation membrane manufacturing field for being applied to water process.
Summary of the invention
The purpose of the invention is to overcome the deficiencies in the prior art, by will with a certain proportion of inorganic nanoparticles,
Polyvinyl alcohol and cellulose acetate, which are added in solvent, to be uniformly mixed to recycle three-dimensional ink direct write printing as marking ink
The netted structure of right-angled intersection of the marking ink of preparation on substrate according to loop cycle is depicted as with network by technology
Nethike embrane, and the superoleophobic nethike embrane of super-hydrophilic and underwater is further obtained by coagulating bath method, the nethike embrane of this method preparation has oil
The advantages of water separation high-efficient, at low cost, structure-controllable, while the Method of printing is easy to operate, it is high-efficient, it is suitable for industry metaplasia
It produces.
Realize the technical solution of the object of the invention are as follows:
A kind of superoleophobic nethike embrane of the super-hydrophilic and underwater of 3 D-printing and preparation method thereof, it is characterised in that: specific preparation
Method includes following processing steps:
(1) the preparation of marking ink: being inorganic nanoparticles 5-25wt%, polyvinyl alcohol 10- by each component content
30wt%, cellulose acetate 10-30wt%, remaining is organic solvent, is uniformly mixed, and removes the gas in ink by centrifugal process
Bubble；
(2) 3 D-printing membrane material: using three-dimensional ink direct write printing technique by the marking ink of preparation on substrate according to
The netted structure of the right-angled intersection of loop cycle is depicted as the nethike embrane with network；
(3) the solidification process of nethike embrane: printed nethike embrane is put into people into coagulating bath and is further solidified, is finally put into water
It saves to get the nethike embrane with network and excellent mechanical performances is arrived.
The inorganic nanoparticles include but is not limited to nano-titanium dioxide, nano silica, nano-Ag particles, nanometer
Aluminium oxide, nanometer calcium carbonate, etc. nano-particle diameter 10-100nm.
The organic solvent is but is not limited to dimethylformamide, dimethyl sulfoxide, acetone, tetrahydrofuran, dimethyl second
The mixed solution of one or more of amide.
The molecular weight of the polyvinyl alcohol is 5000-100000, and the molecular weight of cellulose acetate is 5000-50000.
The sizing grid of the nethike embrane of the preparation is 50-500 μm.
The coagulating bath is but is not limited to one or more of water, ethyl alcohol, polyethylene glycol, methanol mixed solution.Solidification
Time be 10-180min, solidification temperature be 10-50 DEG C.
The invention has the following advantages that
1, the present invention is by will be with the mixed solution of a certain proportion of inorganic nanoparticles, polyvinyl alcohol and cellulose acetate
As marking ink, using three-dimensional ink direct write printing technique by the marking ink of preparation on substrate according to the ten of loop cycle
Word cross network structure is depicted as the nethike embrane with network, and by coagulating bath method solidifies to obtain super-hydrophilic and underwater super thin
Oil network film, the porous composite film surface of this method preparation less than 30 °, are greater than the contact angle of water to the contact angle of oil under water
150°。
2, the nethike embrane that the present invention can be prepared by three-dimensional printing technology has that water-oil separating is high-efficient, stability
By force, high to the rejection of oil.
3, the advantages of preparation method of the present invention is simple, at low cost, can carry out large-scale production and application.
4, polyethylene excellent hydrophilic and oil resistant polluting property, nano particle can be improved poly- in the ink of the bright preparation of this law
Close the intensity of object, acetate fiber have excellent shaping characteristic and mechanical strength its can rapid shaping in organic solvent, because
The nethike embrane that this compound ink that joined three of the above substance prints can only be obtained by simple coagulating bath solidification method
Has many advantages, such as the oil-water separation mesh film of the superoleophobic characteristic of super-hydrophilic and underwater, high mechanical strength, structure stable homogeneous, and not
Need further last handling process such as basic treatment etc..
5, the equal freezing method phase of the organic solvent coagulating bath solidification method that uses of the present invention and existing hot setting, chemical crosslinking
Than have many advantages, such as it is at low cost, be easy to large-scale production.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is field emission scanning electron microscope figure of the superoleophobic nethike embrane of super-hydrophilic and underwater prepared by the present invention under 100 multiples.
Specific embodiment
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit
Determine the scope of the present invention.
Embodiment 1
A kind of superoleophobic nethike embrane of the super-hydrophilic and underwater of 3 D-printing and preparation method thereof, steps are as follows:
(1) the preparation of marking ink: the inorganic nano silica dioxide granule 25wt% for being 100nm by each component content partial size,
Molecular weight is 10000 polyvinyl alcohol 10wt%, and molecular weight is 50000 cellulose acetate 10wt%, remaining is tetrahydrofuran solvent,
It is uniformly mixed, the bubble in ink is removed by centrifugal process；
(2) 3 D-printing nethike embrane process: using three-dimensional direct write printing technique by the marking ink of preparation on substrate according to week
It is 50 μm of nethike embrane that the netted structure of right-angled intersection of phase circulation, which is depicted as having sizing grid,；
(3) the solidification process of nethike embrane: putting people into water coagulating bath for printed nethike embrane and solidify, curing time 10min,
Solidification temperature is 50 DEG C, is finally put into water and saves to get the porous nethike embrane with network and excellent mechanical performances is arrived.
Hydrophilic and underwater oleophobic experiment test is carried out to the superoleophobic nethike embrane of super-hydrophilic and underwater of this method preparation:
Water contact angle most can directly react, and material surface is to the hydrophilicity of water and oil, i.e. water contact angle is smaller, film
More hydrophilic surface, so the water of the superoleophobic retinal surface of the super-hydrophilic and underwater for testing preparation by water contact angle measuring instrument
Contact angle and under water to diesel oil, gasoline, lubricating oil, vegetable oil contact angle.The porous complexes membrane of the 3 D-printing is to water
Contact angle is 19.3 °, under water to diesel oil, gasoline, lubricating oil, vegetable oil contact angle be respectively 159.3 °, 151.7 °,
150.9°、161.2°。
The test of oil mixing with water separating experiment is carried out to the superoleophobic nethike embrane of super-hydrophilic and underwater of this method preparation:
The superoleophobic nethike embrane of the super-hydrophilic and underwater of preparation is placed among vertical filter and is fixed with clip, by volume
Mixed liquor than gasoline and water for 1:1 pours into filter, and water is quickly through the grid of nethike embrane in mixed liquor, and gasoline is hindered
Keeping off cannot pass through in the top of separation nethike embrane, show that the nethike embrane realizes efficient water-oil separating, pass through total organic carbon analyzer
It is 99.1% to the separative efficiency of oil-water mixture that detection, which obtains the nethike embrane,.
Embodiment 2
A kind of superoleophobic nethike embrane of the super-hydrophilic and underwater of 3 D-printing and preparation method thereof, steps are as follows:
(1) the preparation of marking ink: the inorganic nano Argent grain 5wt% for being 10nm by each component content partial size, molecular weight are
100000 polyvinyl alcohol 30wt%, molecular weight are 10000 cellulose acetate 15wt%, remaining is acetone solvent, are uniformly mixed, and are led to
Cross the bubble in centrifugal process removing ink；
(2) 3 D-printing nethike embrane process: using three-dimensional direct write printing technique by the marking ink of preparation on substrate according to week
It is 500 μm of nethike embrane that the netted structure of right-angled intersection of phase circulation, which is depicted as having sizing grid,；
(3) printed nethike embrane the solidification process of nethike embrane: is put into people's solidification into alcohol solidification bath further, curing time
For 180min, solidification temperature is 10 DEG C, is finally put into and is saved in water to get to more with network and excellent mechanical performances
Hole nethike embrane.
Hydrophilic and underwater oleophobic experiment test is carried out to the superoleophobic nethike embrane of super-hydrophilic and underwater of this method preparation:
Water contact angle most can directly react, and material surface is to the hydrophilicity of water and oil, i.e. water contact angle is smaller, film
More hydrophilic surface, so testing the superoleophobic retinal surface of super-hydrophilic and underwater of test preparation by water contact angle measuring instrument
Water contact angle and under water to diesel oil, gasoline, lubricating oil, vegetable oil contact angle.The porous complexes membrane pair of the 3 D-printing
The contact angle of water is 13.9 °, under water to diesel oil, gasoline, lubricating oil, vegetable oil contact angle be respectively 161.1 °, 158.4 °,
154.1°、159.3°。
The test of oil mixing with water separating experiment is carried out to the superoleophobic nethike embrane of super-hydrophilic and underwater of this method preparation:
The superoleophobic nethike embrane of the super-hydrophilic and underwater of preparation is placed among vertical filter and is fixed with clip, by volume
Mixed liquor than gasoline and water for 1:1 pours into filter, and water is quickly through the grid of nethike embrane in mixed liquor, and gasoline is hindered
Keeping off cannot pass through in the top of separation nethike embrane, show that the nethike embrane realizes efficient water-oil separating, pass through total organic carbon analyzer
It is 98.7% to the separative efficiency of oil-water mixture that detection, which obtains the nethike embrane,.
Embodiment 3
A kind of superoleophobic nethike embrane of the super-hydrophilic and underwater of 3 D-printing and preparation method thereof, steps are as follows:
(1) the preparation of marking ink: the inorganic nano aluminium oxide Argent grain 15wt% for being 55nm by each component content partial size,
Molecular weight is 30000 polyvinyl alcohol 21wt%, and molecular weight is 5000 cellulose acetate 30wt%, remaining is molten for dimethyl sulfoxide
Agent is uniformly mixed, and removes the bubble in ink by centrifugal process；
(2) 3 D-printing nethike embrane process: using three-dimensional direct write printing technique by the marking ink of preparation on substrate according to week
It is 250 μm of nethike embrane that the netted structure of right-angled intersection of phase circulation, which is depicted as having sizing grid,；
(3) the solidification process of nethike embrane: putting people into methanol coagulating bath for printed nethike embrane and further solidify, curing time
For 120min, solidification temperature is 30 DEG C, is finally put into and is saved in water to get to more with network and excellent mechanical performances
Hole nethike embrane.
Hydrophilic and underwater oleophobic experiment test is carried out to the superoleophobic nethike embrane of super-hydrophilic and underwater of this method preparation:
Water contact angle most can directly react, and material surface is to the hydrophilicity of water and oil, i.e. water contact angle is smaller, film
More hydrophilic surface, so testing the superoleophobic retinal surface of super-hydrophilic and underwater of test preparation by water contact angle measuring instrument
Water contact angle and under water to diesel oil, gasoline, lubricating oil, vegetable oil contact angle.The porous complexes membrane pair of the 3 D-printing
The contact angle of water is 10.4 °, under water to diesel oil, gasoline, lubricating oil, vegetable oil contact angle be respectively 164.3 °, 159.9 °,
158.3°、162.7°。
The test of oil mixing with water separating experiment is carried out to the superoleophobic nethike embrane of super-hydrophilic and underwater of this method preparation:
The superoleophobic nethike embrane of the super-hydrophilic and underwater of preparation is placed among vertical filter and is fixed with clip, by volume
Mixed liquor than gasoline and water for 1:1 pours into filter, and water is quickly through the grid of nethike embrane in mixed liquor, and gasoline is hindered
Keeping off cannot pass through in the top of separation nethike embrane, show that the nethike embrane realizes efficient water-oil separating, pass through total organic carbon analyzer
It is 99.5% to the separative efficiency of oil-water mixture that detection, which obtains the nethike embrane,.
Embodiment 4
A kind of superoleophobic nethike embrane of the super-hydrophilic and underwater of 3 D-printing and preparation method thereof, steps are as follows:
(1) the preparation of marking ink: the inorganic nano titanium dioxide granule 10wt% for being 30nm by each component content partial size,
Molecular weight is 8000 polyvinyl alcohol 18wt%, and molecular weight is 40000 cellulose acetate 13wt%, remaining is molten for dimethylformamide
Agent is uniformly mixed, and removes the bubble in ink by centrifugal process；
(2) 3 D-printing nethike embrane process: using three-dimensional direct write printing technique by the marking ink of preparation on substrate according to week
It is 280 μm of nethike embrane that the netted structure of right-angled intersection of phase circulation, which is depicted as having sizing grid,；
(3) the solidification process of nethike embrane: putting people into isopropanol coagulating bath for printed nethike embrane and further solidify, when solidification
Between be 60min, solidification temperature is 45 DEG C, is finally put into and is saved in water to get to network and excellent mechanical performances
Porous nethike embrane.
Hydrophilic and underwater oleophobic experiment test is carried out to the superoleophobic nethike embrane of super-hydrophilic and underwater of this method preparation:
Water contact angle most can directly react, and material surface is to the hydrophilicity of water and oil, i.e. water contact angle is smaller, film
More hydrophilic surface, so testing the superoleophobic retinal surface of super-hydrophilic and underwater of test preparation by water contact angle measuring instrument
Water contact angle and under water to diesel oil, gasoline, lubricating oil, vegetable oil contact angle.The porous complexes membrane pair of the 3 D-printing
The contact angle of water is 26.6 °, under water to diesel oil, gasoline, lubricating oil, vegetable oil contact angle be respectively 153.9 °, 157.7 °,
160.9°、151.9°。
The test of oil mixing with water separating experiment is carried out to the superoleophobic nethike embrane of super-hydrophilic and underwater of this method preparation:
The superoleophobic nethike embrane of the super-hydrophilic and underwater of preparation is placed among vertical filter and is fixed with clip, by volume
Mixed liquor than gasoline and water for 1:1 pours into filter, and water is quickly through the grid of nethike embrane in mixed liquor, and gasoline is hindered
Keeping off cannot pass through in the top of separation nethike embrane, show that the nethike embrane realizes efficient water-oil separating, pass through total organic carbon analyzer
It is 98.8% to the separative efficiency of oil-water mixture that detection, which obtains the nethike embrane,.
Embodiment 5
A kind of superoleophobic nethike embrane of the super-hydrophilic and underwater of 3 D-printing and preparation method thereof, steps are as follows:
(1) the preparation of marking ink: the inorganic nano Argent grain 7wt% for being 80nm by each component content partial size, molecular weight are
15000 polyvinyl alcohol 16wt%, molecular weight are 9000 cellulose acetate 11wt%, remaining is dimethylacetamide solvent, mixing
Uniformly, the bubble in ink is removed by centrifugal process；
(2) 3 D-printing nethike embrane process: using three-dimensional direct write printing technique by the marking ink of preparation on substrate according to week
It is 130 μm of nethike embrane that the netted structure of right-angled intersection of phase circulation, which is depicted as having sizing grid,；
(3) the solidification process of nethike embrane: printed nethike embrane is put in the coagulating bath that people is 1:1 to the volume ratio of water and ethyl alcohol
Further solidification, curing time 160min, are finally put into water and save to get to network by 25 DEG C of solidification temperature
With the porous nethike embrane of excellent mechanical performances.
Hydrophilic and underwater oleophobic experiment test is carried out to the superoleophobic nethike embrane of super-hydrophilic and underwater of this method preparation:
Water contact angle most can directly react, and material surface is to the hydrophilicity of water and oil, i.e. water contact angle is smaller, film
More hydrophilic surface, so testing the superoleophobic retinal surface of super-hydrophilic and underwater of test preparation by water contact angle measuring instrument
Water contact angle and under water to diesel oil, gasoline, lubricating oil, vegetable oil contact angle.The porous complexes membrane pair of the 3 D-printing
The contact angle of water is 9.9 °, under water to diesel oil, gasoline, lubricating oil, vegetable oil contact angle be respectively 165.5 °, 161.2 °,
159.4°、161.3°。
The test of oil mixing with water separating experiment is carried out to the superoleophobic nethike embrane of super-hydrophilic and underwater of this method preparation:
The superoleophobic nethike embrane of the super-hydrophilic and underwater of preparation is placed among vertical filter and is fixed with clip, by volume
Mixed liquor than gasoline and water for 1:1 pours into filter, and water is quickly through the grid of nethike embrane in mixed liquor, and gasoline is hindered
Keeping off cannot pass through in the top of separation nethike embrane, show that the nethike embrane realizes efficient water-oil separating, pass through total organic carbon analyzer
It is 99.7% to the separative efficiency of oil-water mixture that detection, which obtains the nethike embrane,.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
In the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the superoleophobic nethike embrane of the super-hydrophilic and underwater of 3 D-printing, it is characterised in that: including following techniques
Step:
(1) by 5-25wt% inorganic nanoparticles, 10-30wt% polyvinyl alcohol, 10-30wt% cellulose acetate and organic solvent
It is uniformly mixed and marking ink is made；
Using three-dimensional ink direct write printing technique by the marking ink of preparation on substrate according to the right-angled intersection of loop cycle
Reticular structure is depicted as the nethike embrane with network；
(3) printed nethike embrane is put into coagulating bath and is solidified, be finally put into water save to get to have network with
The nethike embrane of excellent mechanical performances.
2. the preparation method of the superoleophobic nethike embrane of the super-hydrophilic and underwater of 3 D-printing according to claim 1, feature exist
In: inorganic nanoparticles described in step (1) be nano-titanium dioxide, it is nano silica, nano-Ag particles, nano oxidized
One or more kinds of mixtures of aluminium, nanometer calcium carbonate.
3. the preparation method of the superoleophobic nethike embrane of the super-hydrophilic and underwater of 3 D-printing according to claim 1, feature exist
In: inorganic nanoparticles diameter is 10-100nm.
4. the preparation method of the superoleophobic nethike embrane of the super-hydrophilic and underwater of 3 D-printing according to claim 1, feature exist
In: organic solvent described in step (1) is dimethylformamide, dimethyl sulfoxide, acetone, tetrahydrofuran, dimethyl acetamide
One or more of mixed solvent.
5. the preparation method of the superoleophobic nethike embrane of the super-hydrophilic and underwater of 3 D-printing according to claim 1, feature exist
In: the molecular weight of polyvinyl alcohol described in step (1) is 5000-100000.
6. the preparation method of the superoleophobic nethike embrane of the super-hydrophilic and underwater of 3 D-printing according to claim 1, feature exist
In: the molecular weight of cellulose acetate described in step (1) is 5000-50000.
7. the preparation method of the superoleophobic nethike embrane of the super-hydrophilic and underwater of 3 D-printing according to claim 1, feature exist
In: the sizing grid of the nethike embrane of step (2) preparation is 50-500 μm.
8. the preparation method of the superoleophobic nethike embrane of the super-hydrophilic and underwater of 3 D-printing according to claim 1, feature exist
In: step (3) coagulating bath is one or more of water, ethyl alcohol, polyethylene glycol, methanol mixed solution.
9. the preparation method of the superoleophobic nethike embrane of the super-hydrophilic and underwater of 3 D-printing according to claim 1, feature exist
In: it is 10-50 DEG C that step (3) the cured time, which is 10min-180min solidification temperature,.
10. the superoleophobic net of super-hydrophilic and underwater that a kind of method described in claim 1~9 any claim is prepared
Film.
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| CN115770481A (en) * | 2022-11-03 | 2023-03-10 | 北京理工大学 | Method for preparing nano thin-layer separation membrane based on 3D printing technology |
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