CN103849906A - Preparation method of super-hydrophobic porous mesh for oil water separation - Google Patents
Preparation method of super-hydrophobic porous mesh for oil water separation Download PDFInfo
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- CN103849906A CN103849906A CN201410114818.6A CN201410114818A CN103849906A CN 103849906 A CN103849906 A CN 103849906A CN 201410114818 A CN201410114818 A CN 201410114818A CN 103849906 A CN103849906 A CN 103849906A
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Abstract
The invention discloses a preparation method of a super-hydrophobic porous mesh for oil water separation. A porous meshy Sn film is prepared by using a hydrogen bubble template method. The concrete steps are realized under the following conditions that a platinum sheet is used as an anode, a copper wire mesh is used as an electrode cathode, a plating solution comprises the following components: 0.01-0.2mol.L<-1> of SnSO4 and 0.01-0.2mol.L<-1> of H2SO4, the pH value is equal to 4.0+/-0.5, the current density is 0.1-6.0A.cm<-2>, and the deposition time is 5-40s. The hydrogen bubble template method for preparing a porous material has the advantages of simplicity, convenience, low cost and parameter controllability; a three-dimensional porous meshy film can be obtained through depositing on the copper wire mesh by using the method; the porous film is prepared by taking a dynamic hydrogen bubble as a template; compared with a hard template method, the method has the advantages that the template is not needed to be removed, the problems such as high cost, complexity in operation and serious film pollution in the traditional method are solved, and the industrial production is expected to be realized.
Description
Technical field
The present invention relates to a kind of preparation method of super hydrophobic porous reticulated film.
Background technology
Oily(waste)water is a kind of common waste water in industry, and directly discharge meeting causes serious harm to environment, indirectly atmosphere and soil is polluted also serious harm human health.Oily water separation technique has important impact in field of petrochemical industry, comprises recovery, the separation of organic solvent etc. of sea sump oil, oil extraction waste water.Because the surface tension between general water and oil differs greatly, select to the water surface different with oil immersion lubricant nature can selectivity to wherein one adsorbing mutually, another is repelled mutually, strengthen surperficial wetting property and can improve separation efficiency.
The ubiquitous super-hydrophobic phenomenon of occurring in nature, the principal element that affects its wettability is surface chemical composition and surface microstructure, can prepare the super hydrophobic film of oily water separation according to these two kinds of influence factors.Wenzel theory thinks that surperficial roughness can strengthen the wetting property of solid surface, according to Wenzel equation: cos θ *=γ cos θ, wherein θ is the intrinsic contact angle of drop at solid surface, and γ is roughness factor, and θ * is apparent contact angle.The surface that is greater than 90 ° for the intrinsic contact angle of water droplet, in the time that roughness acquires a certain degree, the contact angle of water droplet can be greater than 150 °; Because oil surface tension is low, if be less than 90 ° at the oily intrinsic contact angle on same surface, after roughness increases, the contact angle of oil droplet is close to 0 °.The surface of super-hydrophobic super oleophylic can effectively be adsorbed oil, and then oil-water mixture is realized and being separated.
The traditional treatment method of oily(waste)water mainly contains gravity and mechanical phonograph recorder separation, By Bubble-floating Method, absorption method, flocculence, microbial method and membrane separation process etc.Wherein membrane separation process is widely used, but exist in actual applications, film is seriously polluted, the problem such as easy cleaning, working cost height not.Overcome these problems, investigators are devoted to development of new mould material, as super hydrophobic film, super oleophobic membrane, super-hydrophobic super oil-wet film etc.Utilize surperficial special wetting property to carry out the hot issue that oily water separation is present material scientific research.
Summary of the invention
The object of this invention is to provide a kind of preparation method of the porous super hydrophobic net for oily water separation, adopt bubble hydrogen template to prepare holey based superhydrophobic thin films in conjunction with pickling process.Bubble hydrogen template synthesis porous material is a kind of simple, the method that convenient, cost is low, parameter is controlled, the method can obtain three-dimensional porous reticulated film in copper mesh deposition, preparing porous membrane is take dynamic bubble hydrogen as template, be compared to hard template method, the advantage of the method is without removing template, solved that existing method cost is high, the problem such as complicated operation, film are seriously polluted, be expected to realize suitability for industrialized production.
The object of the invention is to be achieved through the following technical solutions:
For a preparation method for the porous super hydrophobic net of oily water separation, adopt the mesh structural porous Sn film of bubble hydrogen template synthesis, its concrete steps are as follows: with platinized platinum make anode, copper mesh is done electrode cathode, plating solution forms and comprises 0.01-0.2molL
-1snSO
4and 0.01-0.2molL
-1h
2sO
4, pH=4.0 ± 0.5, current density is 0.1-6.0Acm
-2, depositing time is 5-40s.
In order further to improve the super-hydrophobic super-oleophilic of mesh structural porous Ni film, after depositing treatment, to its modifying surface, its step is as follows:
Above-mentioned mesh structural porous Sn film is dipped in the ethanolic soln that contains the positive Dodecyl Mercaptan of 1-10mmol/L and 0.5-4mmol/L TETRADECONIC ACID, be placed in 30-80 ℃ of loft drier, after 0.2-5h, take out, with a large amount of deionized water rinsings, dry, obtain super hydrophobic porous reticulated film.
The area of mesh structural porous Sn film prepared by the present invention is 3*3cm
2, mesh structural porous Sn film substrate aperture is 100-500 μ m, secondary aperture (that is: the aperture of the vesicular structure of electroplating in mesh substrate) is 50-400 μ m.
The preparation method of super hydrophobic porous reticulated film of the present invention is simple to operate, and experiment parameter is controlled, and cost is low, can be used for manufacturing oily water separation material, and this material has super-hydrophobic super-oleophilic, good mechanical stability.
Accompanying drawing explanation
Fig. 1 is the mesh structural porous Sn membrane unit of bubble hydrogen template synthesis schematic diagram;
Fig. 2 is the mesh structural porous Sn thin-film process of bubble hydrogen template galvanic deposit schematic diagram;
Fig. 3 is porous Sn microscopic appearance Electronic Speculum figure prepared by embodiment two;
Fig. 4 is porous Sn microscopic appearance Electronic Speculum figure prepared by embodiment three;
Fig. 5 is porous Sn microscopic appearance Electronic Speculum figure prepared by embodiment four;
Fig. 6 is the contact angle test pattern of embodiment two resulting materials and water.
Embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is further described; but be not limited to this; every technical solution of the present invention is modified or is equal to replacement, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
Embodiment one: present embodiment is prepared super-hydrophobic mesh structural porous film in accordance with the following steps:
As shown in Figure 2, the mesh structural porous Sn film of bubble hydrogen template galvanic deposit is with platinized platinum (1cm
2) make anode, electrode is adopted to copper mesh (aperture 300 μ m, area 3*3cm
2) be negative electrode, its electroplanting device is as shown in Figure 1.In experiment, the pre-treatment of copper mesh is comprised to polishing, oil removing, acid etch, water flushing, soaked in absolute ethyl alcohol, acetone clean, low temperature air blast is dried.Plating solution consists of 0.01-0.2molL
-1snSO
4and 0.01-0.2molL
-1h
2sO
4, pH is controlled in 4.0 ± 0.5 scope, and the current density range of galvanic deposit is 0.1-6.0Acm
-2, depositing time is 5-40s.Construct the structural form of mesh structural porous Sn rete by regulating the deposition parameters such as current density, depositing time, plating solution composition.Post-depositional reticulated film should be used distilled water flushing immediately, dry after soaked in absolute ethyl alcohol, obtains mesh structural porous Sn film.
Control for micro array structure can be by regulating current density, reaction times, main salt concentration and adding additive.The additive that can add is separately polyoxyethylene glycol, Triton X-100 (OP), phenyl aldehyde, acetic acid, hydrochloric acid, NaCl, dodecyl phenenyl sulfate, dioctyl sodium sulfosuccinate (A Luosuo-OT), cetyl trimethylammonium bromide (CTAB).
In order further to improve the super-hydrophobic super-oleophilic of mesh structural porous Ni film, depositing treatment is afterwards to its modifying surface, its step is as follows: above-mentioned mesh structural porous Sn film is dipped in the ethanolic soln that contains the positive Dodecyl Mercaptan of 1-10mmol/L and 0.5-4mmol/L TETRADECONIC ACID, be placed in 30-80 ℃ of loft drier, after 0.2-5h, take out, with a large amount of deionized water rinsings, dry, obtain super hydrophobic porous reticulated film.
Embodiment two: present embodiment is prepared super-hydrophobic mesh structural porous film in accordance with the following steps:
The mesh structural porous Sn film of bubble hydrogen template galvanic deposit is with platinized platinum (1cm
2) make anode, electrode is adopted to copper mesh (aperture 300 μ m, area 3*3cm
2) be negative electrode.In experiment, the pre-treatment of copper mesh is comprised to polishing, oil removing, acid etch, water flushing, soaked in absolute ethyl alcohol, acetone clean, low temperature air blast is dried.Plating solution consists of 0.05molL
-1snSO
4and 1.5molL
-1h
2sO
4, pH is controlled in 4.0 ± 0.5 scope, and the current density of galvanic deposit is 2.0Acm
-2, depositing time is 10s.Post-depositional reticulated film should be used distilled water flushing immediately, dry after soaked in absolute ethyl alcohol, obtains mesh structural porous Sn film.
The area of the super-hydrophobic mesh structural porous Sn thin-film network that as shown in Figure 3, prepared by present embodiment is 3*3cm
2, reticulated film substrate aperture, aperture is 400 μ m, and secondary aperture is 50 μ m, and inner aperture is 15 μ m, hole wall dendroid particle stacking, length is 5 μ m.As shown in Figure 6, resulting materials and water contact angle are 153 °.
Embodiment three: present embodiment is prepared super-hydrophobic mesh structural porous film in accordance with the following steps:
The mesh structural porous Sn film of bubble hydrogen template galvanic deposit is with platinized platinum (1cm
2) make anode, electrode is adopted to copper mesh (aperture 300 μ m, area 3*3cm
2) be negative electrode.In experiment, the pre-treatment of copper mesh is comprised to polishing, oil removing, acid etch, water flushing, soaked in absolute ethyl alcohol, acetone clean, low temperature air blast is dried.Plating solution consists of 0.1molL
-1snSO
4and 1.5molL
-1h
2sO
4, pH is controlled in 4.0 ± 0.5 scope, and the current density of galvanic deposit is 2.0Acm
-2, depositing time is 10s.Post-depositional reticulated film should be used distilled water flushing immediately, dry after soaked in absolute ethyl alcohol, obtains mesh structural porous Sn film.
Above-mentioned mesh structural porous Ni film is dipped in the ethanolic soln that contains the positive Dodecyl Mercaptan of 5mmol/L and 2mmol/L TETRADECONIC ACID, is placed in 50 ℃ of loft drier, after 1h, take out, dry with a large amount of deionized water rinsings, obtain super-hydrophobic mesh structural porous thin-film network.
The area of the super-hydrophobic mesh structural porous Sn thin-film network that as shown in Figure 4, prepared by present embodiment is 3*3cm
2, reticulated film substrate aperture, aperture is 400 μ m, aperture is 50 μ m, and hole wall dendroid particle stacking, length is 5 μ m.Resulting materials and water contact angle are 157 °.
Embodiment four: present embodiment is prepared super-hydrophobic mesh structural porous film in accordance with the following steps:
Bubble hydrogen template galvanic deposit holey Sn film is with platinized platinum (1cm
2) make anode, electrode is adopted to copper mesh (aperture 300 μ m, area 3*3cm
2) be negative electrode.In experiment, the pre-treatment of copper mesh is comprised to polishing, oil removing, acid etch, water flushing, soaked in absolute ethyl alcohol, acetone clean, low temperature air blast is dried.Plating solution consists of 0.2molL
-1snSO
4and 1.5molL
-1h
2sO
4, pH is controlled in 4.0 ± 0.5 scope, and the current density of galvanic deposit is 2.0Acm
-2, depositing time is 10s.Post-depositional reticulated film should be used distilled water flushing immediately, dry after soaked in absolute ethyl alcohol, obtains mesh structural porous Sn film.
The area of the super-hydrophobic mesh structural porous Sn thin-film network that as shown in Figure 5, prepared by present embodiment is 3*3cm
2, reticulated film substrate aperture, aperture is 300 μ m, and aperture is 40 μ m hole wall dendroid particle stackings, and length is 5 μ m.
Claims (9)
1. the preparation method for the porous super hydrophobic net of oily water separation, it is characterized in that described method adopts the mesh structural porous Sn film of bubble hydrogen template synthesis, its concrete steps are as follows: with platinized platinum make anode, copper mesh is done electrode cathode, plating solution composition comprises 0.01-0.2molL
-1snSO
4and 0.01-0.2molL
-1h
2sO
4, pH=4.0 ± 0.5, current density is 0.1-6.0Acm
-2, depositing time is 5-40s, obtains mesh structural porous Sn film.
2. the preparation method of the porous super hydrophobic net for oily water separation according to claim 1, is characterized in that described plating solution consists of 0.05molL
-1snSO
4and 1.5molL
-1h
2sO
4.
3. the preparation method of the porous super hydrophobic net for oily water separation according to claim 1, is characterized in that described plating solution consists of 0.1molL
-1snSO
4and 1.5molL
-1h
2sO
4.
4. the preparation method of the porous super hydrophobic net for oily water separation according to claim 1, is characterized in that described plating solution consists of 0.2molL
-1snSO
4and 1.5molL
-1h
2sO
4.
5. the preparation method of the porous super hydrophobic net for oily water separation according to claim 1, is characterized in that described current density is 2.0Acm
-2.
6. the preparation method of the porous super hydrophobic net for oily water separation according to claim 1, is characterized in that described depositing time is 10s.
7. the preparation method of the porous super hydrophobic net for oily water separation according to claim 1, it is characterized in that described method also comprises the steps: mesh structural porous Sn film to be dipped in the ethanolic soln that contains the positive Dodecyl Mercaptan of 1-10mmol/L and 0.5-4mmol/L TETRADECONIC ACID, be placed in 30-80 ℃ of loft drier, after 0.2-5h, take out, with a large amount of deionized water rinsings, dry, obtain super hydrophobic porous reticulated film.
8. the preparation method of the porous super hydrophobic net for oily water separation according to claim 7, is characterized in that containing in described ethanolic soln the positive Dodecyl Mercaptan of 5mmol/L and 2mmol/L TETRADECONIC ACID.
9. the preparation method of the porous super hydrophobic net for oily water separation according to claim 7, is characterized in that described drying temperature is 50 ℃, and be 1h time of drying.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105148562A (en) * | 2015-08-10 | 2015-12-16 | 中国海洋大学 | Candle-ash-assisted super-hydrophobic and super-oleophilic oil-water separation mesh film as well as preparation method and application of mesh film |
| CN105386090A (en) * | 2015-11-09 | 2016-03-09 | 广东工业大学 | Method for manufacturing ultra-oleophobic metal surface with recessed micropores |
| CN105568327A (en) * | 2015-12-18 | 2016-05-11 | 西安科技大学 | Electrochemical method for preparing super-hydrophobic surface of copper dendritic crystal |
| JP2016204738A (en) * | 2015-04-28 | 2016-12-08 | オーエム産業株式会社 | Production method of plated article |
| CN106987876A (en) * | 2017-03-03 | 2017-07-28 | 四川农业大学 | A kind of preparation method of super-hydrophobic/oleophylic water-oil separating Ni Cu composite deposite nethike embranes |
| CN109232969A (en) * | 2018-08-27 | 2019-01-18 | 济南大学 | A kind of preparation method and application of super-hydrophobic maleimide polyureas porous material |
| CN109628963A (en) * | 2019-01-22 | 2019-04-16 | 浙江工贸职业技术学院 | Galvanoplastic prepare the device and its processing technology of foam metal |
| CN114504880A (en) * | 2020-11-16 | 2022-05-17 | 清华大学 | Hydrophobic modified metal net and preparation method and application thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016204738A (en) * | 2015-04-28 | 2016-12-08 | オーエム産業株式会社 | Production method of plated article |
| CN105148562A (en) * | 2015-08-10 | 2015-12-16 | 中国海洋大学 | Candle-ash-assisted super-hydrophobic and super-oleophilic oil-water separation mesh film as well as preparation method and application of mesh film |
| CN105386090A (en) * | 2015-11-09 | 2016-03-09 | 广东工业大学 | Method for manufacturing ultra-oleophobic metal surface with recessed micropores |
| CN105568327A (en) * | 2015-12-18 | 2016-05-11 | 西安科技大学 | Electrochemical method for preparing super-hydrophobic surface of copper dendritic crystal |
| CN105568327B (en) * | 2015-12-18 | 2018-06-29 | 西安科技大学 | A kind of electrochemical method for preparing copper dendrite super hydrophobic surface |
| CN106987876A (en) * | 2017-03-03 | 2017-07-28 | 四川农业大学 | A kind of preparation method of super-hydrophobic/oleophylic water-oil separating Ni Cu composite deposite nethike embranes |
| CN109232969A (en) * | 2018-08-27 | 2019-01-18 | 济南大学 | A kind of preparation method and application of super-hydrophobic maleimide polyureas porous material |
| CN109232969B (en) * | 2018-08-27 | 2021-06-22 | 济南大学 | Preparation method and application of super-hydrophobic maleimide polyurea porous material |
| CN109628963A (en) * | 2019-01-22 | 2019-04-16 | 浙江工贸职业技术学院 | Galvanoplastic prepare the device and its processing technology of foam metal |
| CN109628963B (en) * | 2019-01-22 | 2020-01-07 | 浙江工贸职业技术学院 | Device for preparing foam metal by electroplating method and processing technology thereof |
| CN114504880A (en) * | 2020-11-16 | 2022-05-17 | 清华大学 | Hydrophobic modified metal net and preparation method and application thereof |
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