CN110368718B - Three-dimensional printed super-hydrophilic and underwater super-oleophobic net film and preparation method thereof - Google Patents
Three-dimensional printed super-hydrophilic and underwater super-oleophobic net film and preparation method thereof Download PDFInfo
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- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 11
- 239000008158 vegetable oil Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
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- 238000002474 experimental method Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- 239000000203 mixture Substances 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 230000003075 superhydrophobic effect Effects 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
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- 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
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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
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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
- 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
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- 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
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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
- B01D2325/36—Hydrophilic membranes
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Abstract
The invention discloses a three-dimensional printed super-hydrophilic and underwater super-oleophobic net film and a preparation method thereof, which comprises the steps of adding inorganic nano-particles, polyvinyl alcohol and cellulose acetate into an organic solvent according to a certain proportion, uniformly mixing, then placing a prepared ink solution into an injector, and removing bubbles in ink by a centrifugal method; drawing the prepared printing ink on a substrate according to a periodically circulating cross-shaped net structure into a net film with a grid structure by using a three-dimensional ink direct writing printing technology; and (3) placing the printed net film into a coagulating bath for further solidification to finally obtain the net film with a grid structure and good mechanical properties. The prepared net film has a grid structure, the size of the grid is 50-500 mu m, the net film has excellent super-hydrophilic and underwater super-oleophobic characteristics, the net film has extremely high separation efficiency on oil-water mixed liquid, and the quick separation of the oil-water mixed liquid can be realized.
Description
Technical Field
The invention particularly relates to a three-dimensional printed super-hydrophilic and underwater super-oleophobic net film and a preparation method thereof, belonging to the field of preparation of film materials.
Background
At present, due to the increasing industrial oily wastewater and frequent petroleum leakage accidents worldwide, etc., a great deal of oily wastewater is generated, and if the wastewater cannot be effectively treated, serious environmental and ecological problems are caused, so that the oil-water separation technology for treating the oily wastewater is in wide attention. Currently, superhydrophilic and underwater superoleophobic porous membranes can selectively filter water while completely repelling oil contaminants; therefore, the super-hydrophilic and underwater super-oleophobic porous membrane has great potential in the aspect of realizing high-efficiency oil-water separation, and compared with the conventional oil-water separation technologies such as gravity separation, centrifugal separation, adsorption separation, air flotation separation and the like, the super-hydrophilic and underwater super-oleophobic porous membrane has the advantages of low cost, simplicity in operation, high water flux, good oil fouling resistance, high separation efficiency and the like, and has wide application prospect in the field of oil-water separation.
At present, the main method for preparing the super-hydrophilic and underwater super-oleophobic membrane material is a surface modification method, namely, a layer of super-hydrophilic and underwater super-oleophobic coating is coated on the surface of a commercial membrane material to obtain an oil-water separation membrane with super-hydrophilic and underwater super-oleophobic characteristics, and Chinese patent 106422421A discloses a preparation method and application of a filter paper modified oil-water separation membrane.
The three-dimensional printing technology is developed from an additive manufacturing technology at the end of the 20 th century, and can print net membrane materials with different scales efficiently and at low cost according to design, so that the three-dimensional printing technology has high application potential in the aspect of manufacturing super-hydrophilic and super-oleophobic porous membranes in the field of oil-water separation. The three-dimensional printing and forming preparation method of the porous ceramic membrane for filtering disclosed in the Chinese patent CN102824654B comprises the steps of printing a porous ceramic blank by a three-dimensional printer, and drying, removing glue and sintering the printed porous ceramic blank to finally obtain the porous ceramic membrane with a specific shape structure, wherein the ceramic membrane has high treatment efficiency on sewage. Chinese patent CN106182770A discloses a method for preparing a hydrophobic or super-hydrophobic membrane with controllable morphology by a three-dimensional printing template method, which designs templates with different pore appearances by a three-dimensional printing technology, and reforms the hydrophobic or super-hydrophobic membrane with a protruding structure according to the templates, Koh et al firstly prepares Cellulose acetate solution ink by the three-dimensional printing technology to be Printed into a Cellulose acetate Mesh membrane with a Mesh structure, then removes solvent in the Mesh membrane by high-temperature curing, finally immerses the Mesh membrane into strong alkali solution, and further obtains a Cellulose Mesh membrane with super-hydrophilicity and super-lipophobicity under Water, and the Mesh membrane has good Oil-Water Separation efficiency and Oil pollution resistance (Koh J, Lim Jia Hao G, Zhou X, et al 3D-Printed Anti-Fouling-filtration Mesh for high efficiency Oil/Water Separation application [ J.ACS. App. device, Mat9, 11,13787-; the above-disclosed patents prove that the three-dimensional printing technology has high application value in the field of manufacturing membrane separation materials applied to water treatment.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, inorganic nano particles, polyvinyl alcohol and cellulose acetate in a certain proportion are added into a solvent and uniformly mixed to be used as printing ink, then the prepared printing ink is drawn on a substrate according to a periodically circulating cross-shaped net structure by utilizing a three-dimensional ink direct writing printing technology to form a net film with a net structure, and a super-hydrophilic and underwater super-oleophobic net film is further obtained by a coagulating bath method.
The technical scheme for realizing the purpose of the invention is as follows:
a three-dimensional printed super-hydrophilic and underwater super-oleophobic net film and a preparation method thereof are characterized in that: the preparation method comprises the following process steps:
preparing printing ink: uniformly mixing 5-25wt% of inorganic nano particles, 10-30wt% of polyvinyl alcohol, 10-30wt% of cellulose acetate and the balance of organic solvent, and removing bubbles in the ink by a centrifugal method;
the three-dimensional printing film material: drawing the prepared printing ink on a substrate according to a periodically circulating cross-shaped net structure into a net film with a grid structure by using a three-dimensional ink direct writing printing technology;
the curing process of the net film: and (3) placing the printed net film into a coagulating bath for further solidification, and finally placing the net film into water for preservation to obtain the net film with a grid structure and good mechanical properties.
The inorganic nanoparticles include, but are not limited to, nano titanium dioxide, nano silicon dioxide, nano silver particles, nano aluminum oxide, nano calcium carbonate, etc., and the diameter of the nanoparticles is 10-100 nm.
The organic solvent is one or a mixture of several of dimethylformamide, dimethyl sulfoxide, acetone, tetrahydrofuran and dimethylacetamide.
The molecular weight of the polyvinyl alcohol is 5000-100000, and the molecular weight of the cellulose acetate is 5000-50000.
The mesh size of the prepared omentum is 50-500 μm.
The coagulating bath is one or a mixture of water, ethanol, polyethylene glycol and methanol. The curing time is 10-180 min, and the curing temperature is 10-50 ℃.
The invention has the following advantages:
1. the method comprises the steps of using a mixed solution of inorganic nanoparticles, polyvinyl alcohol and cellulose acetate in a certain proportion as printing ink, drawing the prepared printing ink on a substrate according to a periodically-circulating cross-shaped net structure by using a three-dimensional ink direct writing printing technology to form a net film with a net structure, and curing by a coagulating bath method to obtain the super-hydrophilic and underwater super-oleophobic net film, wherein the contact angle of the surface of the porous composite film prepared by the method to water is less than 30 degrees, and the contact angle to oil underwater is more than 150 degrees.
2. The net film prepared by the three-dimensional printing technology has high oil-water separation efficiency, strong stability and high oil retention rate.
3. The preparation method has the advantages of simplicity, low cost and capability of large-scale production and application.
4. The polyvinyl alcohol in the ink prepared by the method has excellent hydrophilic and anti-oil pollution characteristics, the nano particles can improve the strength of the polymer, the acetate fiber has excellent forming characteristics and mechanical strength and can be quickly formed in an organic solvent, so that an oil-water separation mesh membrane with the advantages of super-hydrophilic and underwater super-oleophobic characteristics, high mechanical strength, uniform and stable structure and the like can be obtained by a mesh membrane printed by the composite ink added with the three substances through a simple coagulating bath curing method, and further post-treatment processes such as alkaline treatment and the like are not needed.
5. Compared with the existing high-temperature curing and chemical crosslinking equal curing method, the organic solvent coagulating bath curing method adopted by the invention has the advantages of low cost, easy large-scale production and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a field emission scanning electron microscope image of the super-hydrophilic and underwater super-oleophobic net film prepared by the invention under the multiple of 100.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
A three-dimensional printed super-hydrophilic and underwater super-oleophobic net film and a preparation method thereof are disclosed, which comprises the following steps:
preparing printing ink: uniformly mixing 25wt% of inorganic nano silica particles with the particle size of 100nm, 10 wt% of polyvinyl alcohol with the molecular weight of 10000, 10 wt% of cellulose acetate with the molecular weight of 50000 and the balance of tetrahydrofuran solvent, and removing bubbles in the ink by a centrifugal method;
the net film three-dimensional printing process: drawing the prepared printing ink on a substrate into a net film with the mesh size of 50 mu m according to a periodically circulating cross net structure by using a three-dimensional direct writing printing technology;
the curing process of the net film: and (3) placing the printed net film into a water coagulation bath for curing, wherein the curing time is 10min, the curing temperature is 50 ℃, and finally placing the net film into water for storage to obtain the porous net film with a grid structure and good mechanical properties. The super-hydrophilic and underwater super-oleophobic net film prepared by the method is subjected to hydrophilic and underwater oleophobic experiment tests:
the water contact angle can react most directly, and the surface of the material has hydrophilic performance to water and oil, namely the smaller the water contact angle is, the more hydrophilic the surface of the membrane is, so that the water contact angle of the surface of the prepared super-hydrophilic and underwater super-oleophobic net membrane and the contact angle of the surface of the underwater super-hydrophilic and underwater super-oleophobic net membrane to diesel oil, gasoline, lubricating oil and vegetable oil are tested by a water contact angle measuring instrument. The contact angle of the three-dimensional printing porous composite membrane to water is 19.3 degrees, and the contact angles to diesel oil, gasoline, lubricating oil and vegetable oil under water are 159.3 degrees, 151.7 degrees, 150.9 degrees and 161.2 degrees respectively.
The super-hydrophilic and underwater super-oleophobic net film prepared by the method is subjected to oil-water mixing separation experiment test:
the prepared super-hydrophilic and underwater super-oleophobic net membrane is placed in the middle of a vertical filter and fixed by a clamp, mixed liquid of gasoline and water with the volume ratio of 1:1 is poured into the filter, the water in the mixed liquid rapidly passes through the grids of the net membrane, and the gasoline is blocked above a separation net membrane and cannot pass through the separation net membrane, so that the net membrane realizes efficient oil-water separation, and the separation efficiency of the net membrane on the oil-water mixed liquid is 99.1% through detection of a total organic carbon analyzer.
Example 2
A three-dimensional printed super-hydrophilic and underwater super-oleophobic net film and a preparation method thereof are disclosed, which comprises the following steps:
preparing printing ink: uniformly mixing 5wt% of inorganic nano silver particles with the particle size of 10 nm, 30wt% of polyvinyl alcohol with the molecular weight of 100000, 15 wt% of cellulose acetate with the molecular weight of 10000 and the balance of acetone solvent, and removing bubbles in the ink by a centrifugal method;
the net film three-dimensional printing process: drawing the prepared printing ink on a substrate into a net film with the grid size of 500 mu m according to a periodically circulating cross net structure by using a three-dimensional direct writing printing technology;
the curing process of the net film: and (3) placing the printed net film into an ethanol coagulating bath for further solidification, wherein the solidification time is 180min, the solidification temperature is 10 ℃, and finally placing the net film into water for storage to obtain the porous net film with a grid structure and good mechanical properties.
The super-hydrophilic and underwater super-oleophobic net film prepared by the method is subjected to hydrophilic and underwater oleophobic experiment tests:
the water contact angle can react most directly, and the surface of the material has hydrophilic performance to water and oil, namely the smaller the water contact angle is, the more hydrophilic the surface of the membrane is, so that the water contact angle of the surface of the prepared super-hydrophilic and underwater super-oleophobic net membrane and the contact angle of the surface of the underwater super-hydrophilic and underwater super-oleophobic net membrane to diesel oil, gasoline, lubricating oil and vegetable oil are tested and tested by a water contact angle measuring instrument. The contact angle of the three-dimensional printing porous composite membrane to water is 13.9 degrees, and the contact angles to diesel oil, gasoline, lubricating oil and vegetable oil under water are 161.1 degrees, 158.4 degrees, 154.1 degrees and 159.3 degrees respectively.
The super-hydrophilic and underwater super-oleophobic net film prepared by the method is subjected to oil-water mixing separation experiment test:
the prepared super-hydrophilic and underwater super-oleophobic net membrane is placed in the middle of a vertical filter and fixed by a clamp, mixed liquid of gasoline and water with the volume ratio of 1:1 is poured into the filter, the water in the mixed liquid rapidly passes through the grids of the net membrane, and the gasoline is blocked above a separation net membrane and cannot pass through the separation net membrane, so that the net membrane realizes efficient oil-water separation, and the separation efficiency of the net membrane on the oil-water mixed liquid is detected by a total organic carbon analyzer to be 98.7%.
Example 3
A three-dimensional printed super-hydrophilic and underwater super-oleophobic net film and a preparation method thereof are disclosed, which comprises the following steps:
preparing printing ink: uniformly mixing 15 wt% of inorganic nano alumina particles with the particle size of 55 nm, 21 wt% of polyvinyl alcohol with the molecular weight of 30000, 30wt% of cellulose acetate with the molecular weight of 5000 and the balance of dimethyl sulfoxide solvent, and removing bubbles in the ink by a centrifugal method;
the net film three-dimensional printing process: drawing the prepared printing ink on a substrate into a net film with the grid size of 250 mu m according to a periodically circulating cross net structure by using a three-dimensional direct writing printing technology;
the curing process of the net film: and (3) placing the printed net film into a methanol coagulating bath for further solidification, wherein the solidification time is 120min, the solidification temperature is 30 ℃, and finally placing the net film into water for storage to obtain the porous net film with a grid structure and good mechanical properties.
The super-hydrophilic and underwater super-oleophobic net film prepared by the method is subjected to hydrophilic and underwater oleophobic experiment tests:
the water contact angle can react most directly, and the surface of the material has hydrophilic performance to water and oil, namely the smaller the water contact angle is, the more hydrophilic the surface of the membrane is, so that the water contact angle of the surface of the prepared super-hydrophilic and underwater super-oleophobic net membrane and the contact angle of the surface of the underwater super-hydrophilic and underwater super-oleophobic net membrane to diesel oil, gasoline, lubricating oil and vegetable oil are tested and tested by a water contact angle measuring instrument. The contact angle of the three-dimensional printing porous composite membrane to water is 10.4 degrees, and the contact angles to diesel oil, gasoline, lubricating oil and vegetable oil under water are 164.3 degrees, 159.9 degrees, 158.3 degrees and 162.7 degrees respectively.
The super-hydrophilic and underwater super-oleophobic net film prepared by the method is subjected to oil-water mixing separation experiment test:
the prepared super-hydrophilic and underwater super-oleophobic net membrane is placed in the middle of a vertical filter and fixed by a clamp, mixed liquid of gasoline and water with the volume ratio of 1:1 is poured into the filter, the water in the mixed liquid rapidly passes through the grids of the net membrane, and the gasoline is blocked above a separation net membrane and cannot pass through the separation net membrane, so that the net membrane realizes efficient oil-water separation, and the separation efficiency of the net membrane on the oil-water mixed liquid is detected by a total organic carbon analyzer to be 99.5%.
Example 4
A three-dimensional printed super-hydrophilic and underwater super-oleophobic net film and a preparation method thereof are disclosed, which comprises the following steps:
preparing printing ink: uniformly mixing 10 wt% of inorganic nano titanium dioxide particles with the particle size of 30 nm, 18 wt% of polyvinyl alcohol with the molecular weight of 8000, 13 wt% of cellulose acetate with the molecular weight of 40000 and the balance of dimethylformamide solvent, and removing bubbles in the ink by a centrifugal method;
the net film three-dimensional printing process: drawing the prepared printing ink on a substrate into a net film with the grid size of 280 mu m according to a periodically circulating cross net structure by using a three-dimensional direct writing printing technology;
the curing process of the net film: and (3) placing the printed net film into an isopropanol coagulating bath for further solidification, wherein the solidification time is 60min, the solidification temperature is 45 ℃, and finally placing the net film into water for storage to obtain the porous net film with a grid structure and good mechanical properties.
The super-hydrophilic and underwater super-oleophobic net film prepared by the method is subjected to hydrophilic and underwater oleophobic experiment tests:
the water contact angle can react most directly, and the surface of the material has hydrophilic performance to water and oil, namely the smaller the water contact angle is, the more hydrophilic the surface of the membrane is, so that the water contact angle of the surface of the prepared super-hydrophilic and underwater super-oleophobic net membrane and the contact angle of the surface of the underwater super-hydrophilic and underwater super-oleophobic net membrane to diesel oil, gasoline, lubricating oil and vegetable oil are tested and tested by a water contact angle measuring instrument. The contact angle of the three-dimensional printing porous composite membrane to water is 26.6 degrees, and the contact angles to diesel oil, gasoline, lubricating oil and vegetable oil under water are 153.9 degrees, 157.7 degrees, 160.9 degrees and 151.9 degrees respectively.
The super-hydrophilic and underwater super-oleophobic net film prepared by the method is subjected to oil-water mixing separation experiment test:
the prepared super-hydrophilic and underwater super-oleophobic net membrane is placed in the middle of a vertical filter and fixed by a clamp, mixed liquid of gasoline and water with the volume ratio of 1:1 is poured into the filter, the water in the mixed liquid rapidly passes through the grids of the net membrane, and the gasoline is blocked above a separation net membrane and cannot pass through the separation net membrane, so that the net membrane realizes efficient oil-water separation, and the separation efficiency of the net membrane on the oil-water mixed liquid is detected by a total organic carbon analyzer to be 98.8%.
Example 5
A three-dimensional printed super-hydrophilic and underwater super-oleophobic net film and a preparation method thereof are disclosed, which comprises the following steps:
preparing printing ink: uniformly mixing 7 wt% of inorganic nano silver particles with the particle size of 80nm, 16 wt% of polyvinyl alcohol with the molecular weight of 15000, 11 wt% of cellulose acetate with the molecular weight of 9000 and the balance of a dimethylacetamide solvent, and removing bubbles in the ink by a centrifugal method;
the net film three-dimensional printing process: drawing the prepared printing ink on a substrate into a net film with the mesh size of 130 mu m according to a periodically circulating cross net structure by using a three-dimensional direct writing printing technology;
the curing process of the net film: and (3) placing the printed net film into a coagulating bath with the volume ratio of water to ethanol being 1:1 for further solidification, wherein the solidification time is 160min, the solidification temperature is 25 ℃, and finally placing the net film into water for storage to obtain the porous net film with a grid structure and good mechanical properties.
The super-hydrophilic and underwater super-oleophobic net film prepared by the method is subjected to hydrophilic and underwater oleophobic experiment tests:
the water contact angle can react most directly, and the surface of the material has hydrophilic performance to water and oil, namely the smaller the water contact angle is, the more hydrophilic the surface of the membrane is, so that the water contact angle of the surface of the prepared super-hydrophilic and underwater super-oleophobic net membrane and the contact angle of the surface of the underwater super-hydrophilic and underwater super-oleophobic net membrane to diesel oil, gasoline, lubricating oil and vegetable oil are tested and tested by a water contact angle measuring instrument. The contact angle of the three-dimensional printing porous composite membrane to water is 9.9 degrees, and the contact angles to diesel oil, gasoline, lubricating oil and vegetable oil under water are 165.5 degrees, 161.2 degrees, 159.4 degrees and 161.3 degrees respectively.
The super-hydrophilic and underwater super-oleophobic net film prepared by the method is subjected to oil-water mixing separation experiment test:
the prepared super-hydrophilic and underwater super-oleophobic net membrane is placed in the middle of a vertical filter and fixed by a clamp, mixed liquid of gasoline and water with the volume ratio of 1:1 is poured into the filter, the water in the mixed liquid rapidly passes through the grids of the net membrane, and the gasoline is blocked above a separation net membrane and cannot pass through the separation net membrane, so that the net membrane realizes efficient oil-water separation, and the separation efficiency of the net membrane on the oil-water mixed liquid is detected by a total organic carbon analyzer to be 99.7%.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (1)
1. A preparation method of a three-dimensional printed super-hydrophilic and underwater super-oleophobic net film is characterized by comprising the following steps: the method comprises the following process steps:
preparing printing ink: uniformly mixing 7 wt% of inorganic nano silver particles with the particle size of 80nm, 16 wt% of polyvinyl alcohol with the molecular weight of 15000, 11 wt% of cellulose acetate with the molecular weight of 9000 and the balance of dimethyl acetamide solvent, and removing bubbles in the ink by a centrifugal method;
the net film three-dimensional printing process: drawing the prepared printing ink on a substrate into a net film with the mesh size of 130 mu m according to a periodically circulating cross net structure by using a three-dimensional direct writing printing technology;
the curing process of the net film: placing the printed net film into a coagulating bath with the volume ratio of water to ethanol being 1:1 for further solidification, wherein the solidification time is 160min, the solidification temperature is 25 ℃, and finally placing the net film into water for preservation to obtain the porous net film with a grid structure and good mechanical properties;
the contact angle of the three-dimensional printing porous composite membrane to water is 9.9 degrees, and the contact angles to diesel oil, gasoline, lubricating oil and vegetable oil under water are respectively 165.5 degrees, 161.2 degrees, 159.4 degrees and 161.3 degrees;
the prepared super-hydrophilic and underwater super-oleophobic net membrane is placed in the middle of a vertical filter and fixed by a clamp, mixed liquid of gasoline and water with the volume ratio of 1:1 is poured into the filter, the water in the mixed liquid rapidly passes through the grids of the net membrane, and the gasoline is blocked above a separation net membrane and cannot pass through the separation net membrane, so that the net membrane realizes efficient oil-water separation, and the separation efficiency of the net membrane on the oil-water mixed liquid is detected by a total organic carbon analyzer to be 99.7%.
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| CN112057900B (en) * | 2020-09-09 | 2022-03-25 | 珠海钛然科技有限公司 | Preparation method of oil-water separation material with excellent stability |
| CN112548114B (en) * | 2020-11-09 | 2023-01-31 | 季华实验室 | Method for directly writing and printing metal part by adopting ink |
| CN113144919A (en) * | 2020-11-23 | 2021-07-23 | 兰州大学 | 3D printing multifunctional filter membrane for sewage treatment and preparation method and application thereof |
| CN114633468B (en) * | 2020-12-16 | 2024-02-27 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for preparing stereoscopic aramid aerogel by suspension 3D printing and application |
| CN115970663A (en) * | 2022-11-03 | 2023-04-18 | 福州大学 | Preparation method and application of super-amphiphobic titanium-based three-dimensional porous material |
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Effective date of registration: 20231130 Address after: 300000 2-3039, No. 88, Huanhe South Road, pilot free trade zone (Airport Economic Zone), Binhai New Area, Tianjin Patentee after: TIANJIN HYDROKING SCI & TECH Ltd. Address before: 300072 Tianjin City, Nankai District Wei Jin Road No. 92 Patentee before: Tianjin University |