CN103567456A - Metallic silver surface super-hydrophobicity material and preparation method thereof - Google Patents
Metallic silver surface super-hydrophobicity material and preparation method thereof Download PDFInfo
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- CN103567456A CN103567456A CN201310463063.6A CN201310463063A CN103567456A CN 103567456 A CN103567456 A CN 103567456A CN 201310463063 A CN201310463063 A CN 201310463063A CN 103567456 A CN103567456 A CN 103567456A
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Abstract
The invention discloses a metallic silver surface super-hydrophobicity material and a preparation method thereof. The method comprises the steps: putting a metal sheet copper base material with the cleaned-up surface into prepared 0.01 - 0.1mol/L silver acetate solution for chemical reaction, and adjusting the PH value thereof to 4 - 6 with acetic acid and ammonium hydroxide, wherein the reaction time is 1 - 60min, and the reaction temperature is 10 - 90DEG C; obtaining the metallic silver surface super-hydrophobicity material after hydrophobing agent self-assembly reaction. According to the preparation method of the metallic silver surface super-hydrophobicity material, disclosed by the invention, direct reaction is performed between the metal sheet copper base material and the silver acetate solution in the first step of chemical reaction, the acetic acid and the ammonium hydroxide are used for adjusting the PH value, the temperature and the concentration, a silver micro-nano structure is formed on the surface of sheet copper, and the acetas coordinated ion better controls the reaction speed. Compared with the conventional method, the step is simplified, and newly-prepared silver-ammonia solution and aldehyde group-containing reducing agent are not required to be used.
Description
Technical field
The present invention relates to noble metal super hydrophobic surface of a kind of metal material technical field and preparation method thereof, particularly a kind of metal silver surface super-hydrophobicity material and preparation method thereof.
Background technology
Super hydrophobic surface refers to the surface that contact angle is greater than 150 °, super hydrophobic surface mainly by two because usually controlling, one is surface topography, another is surperficial chemical state.Due to super hydrophobic surface, there is the features such as waterproof, antifog, automatically cleaning, significant in basic research and commercial Application at present, caused widely and paid close attention to.
In Chinese application number is called the application for a patent for invention of " method of preparing super-hydrophobic high reflecting material " for " 200810063478.3 " name and Chinese application number for " 200810034864.X " name, be called the preparation method who has all related to the super hydrophobic surface of argent in the application for a patent for invention of " preparation method of hydrophobic silver surface ", in the method, used silver ammino solution and containing the reducing agent of aldehyde radical.
Summary of the invention
The invention provides a kind of metal silver surface super-hydrophobicity material and preparation method thereof, this preparation method has simplified step for the preparation method of at present conventional argent super hydrophobic surface, needn't adopt the silver ammino solution of new configuration and containing the reducing agent of aldehyde radical.The key step of the method is: first direct with the metallic copper plate substrate after oil removing and removal oxide and silver acetate solution reaction, by adjusting pH value with acetic acid and ammoniacal liquor, temperature and concentration, on copper sheet surface, form silver-colored micro nano structure, and acetate coordination ion has been controlled reaction rate preferably, and then utilize Chemical self-assembly principle at silver-colored micro nano structure surface-assembled one deck organic sulfur alcohols hydrophobic substance, thereby obtain metal silver surface super-hydrophobicity material, reach the super-hydrophobicity of whole material.
Technical scheme of the present invention is as follows:
A kind of preparation method of metal silver surface super-hydrophobicity material, the method comprises: the clean metallic copper plate substrate of surface clean is put into the 0.01～0.1mol/L silver acetate solution configuring and carry out chemical reaction, and adjust its PH to 4～6 with acetic acid and ammoniacal liquor, reaction time is 1～60min, 10～90 ℃ of reaction temperatures; And then after water-repelling agent self-assembling reaction, obtain metal silver surface super-hydrophobicity material.
Further, the more conventional temperature that described metallic copper plate substrate carries out chemical reaction in silver acetate solution is further 25～35 ℃, and pH value is 4～5.
Further preferably, the concentration of described silver acetate solution is further 0.02～0.1mol/L.
Described water-repelling agent self-assembling reaction can adopt current any conventional means, the preferred water-repelling agent self-assembling reaction of the present invention is: by the metal copper sheet washing obtaining after chemical reaction, dry, then immerse in the water-repelling agent that concentration is 0.01～0.05mol/L, and its heating is carried out to self-assembling reaction, reaction temperature is 30～120 ℃, and the reaction time is 1～120 min.Wherein, washing, dry can adopt any conventional means in the industry.
Preferred described water-repelling agent is selected from the chain alkyl mercaptan of C8-C22, one or more in fluorine-containing mercaptan above.
Because environment amenable floride-free water-repelling agent is current development trend, further preferred described water-repelling agent is selected from one or more in positive lauryl mercaptan, positive tetradecanylthioalcohol, positive 16 mercaptan, positive stearylmercaptan or positive 20 mercaptan.
The surface clean of metallic copper plate substrate can adopt any conventional means in the industry at present, the surface clean of the preferred described metallic copper plate substrate of the present invention is for carrying out surface degreasing processing and pickling processes, and wherein surface degreasing is processed and referred to the treatment process that the organic substances such as the greasy dirt of metallic copper plate substrate surface adhesion are removed; Pickling processes refers to the operation that the oxide skin(coating) on metallic copper plate substrate surface is removed by acid solution.Surface degreasing and pickling processes do not limit sequencing, but conventionally first carry out surface degreasing processing, then carry out pickling processes.
The present invention also provides a kind of metal silver surface super-hydrophobicity material of being prepared by above-mentioned preparation method, this material is formed at metallic copper substrate surface, it comprises silver-colored micro-nano surface coarse structure and hydrophobic film, and wherein, hydrophobic film is self-assembled to described silver-colored micro nano structure surface.
Preferred described hydrophobic film thickness is 4～20nm, makes it still can keep original micro nano structure pattern.
Compared with prior art, beneficial effect of the present invention is as follows:
The preparation method of metal silver surface super-hydrophobicity material provided by the invention in chemical reaction one step by metallic copper plate substrate directly and silver acetate solution reaction, by adjusting pH value with acetic acid and ammoniacal liquor, temperature and concentration, on copper sheet surface, form silver-colored micro nano structure, and acetate coordination ion has been controlled reaction rate preferably; Than existing method, simplify step, needn't adopt the silver ammino solution of new configuration and containing the reducing agent of aldehyde radical.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be appreciated that, these embodiment are only for the present invention is described, and are not intended to limit the scope of the invention.Those skilled in the art make according to the present invention in actual applications improvement and adjustment, still belong to protection scope of the present invention.
Embodiment 1
The present embodiment adopts following methods to prepare metal silver surface super-hydrophobicity material:
(1) choose metallic copper plate substrate, its surface is carried out to oil removing, pickling processes successively;
(2) the metallic copper plate substrate after the cleaning of (1) step is placed in to 0.02 mol/L silver acetate chemical solution and carries out chemical reaction, with ammoniacal liquor and acetic acid, adjust PH to 5, chemical reaction temperature is 35 ℃, and chemical time is 15min;
(3) the metal copper sheet obtaining after chemical reaction in (2) step spends ionized water washes clean, dry afterwards, then be placed in positive 16 thiol solutions of 0.015mol/L, be placed in 100 ℃ of baking ovens and react 30min, obtain metal silver surface super-hydrophobicity material.
The metal silver surface super-hydrophobicity material surface of above-mentioned preparation is carried out to SEM observation, and result shows that metal silver surface is the Silver Clusters of 1～1.5 μ m, and Silver Clusters consists of the silver particles of 20-60nm; With Germany, produce contact angle instrument OCA20,4 μ L water droplets carry out hydrophobic experiment, and result shows that its contact angle is 160 °.
Embodiment 2
The present embodiment adopts following methods to prepare metal silver surface super-hydrophobicity material:
(1) choose metallic copper plate substrate, its surface is carried out to oil removing, pickling processes successively;
(2) the metallic copper plate substrate after the cleaning of (1) step is placed in to 0.10 mol/L silver acetate chemical solution and carries out chemical reaction, this adjusts PH to 4 with ammoniacal liquor and acetic acid, and chemical reaction temperature is 25 ℃, and chemical time is 1min;
(3) the metal copper sheet obtaining after chemical reaction in (2) step spends ionized water washes clean, dry afterwards, then be placed in positive 16 thiol solutions of 0.05mol/L, be placed in 100 ℃ of baking ovens and react 30min, then obtain metal silver surface super-hydrophobicity material.
The metal silver surface super-hydrophobicity material surface of above-mentioned preparation is carried out to SEM observation, and result shows that metal silver surface is the bladed structure of 300～700nm size; With Germany, produce contact angle instrument OCA20,4 μ L water droplets carry out hydrophobic experiment, and result shows that its contact angle is greater than 150 °.
Embodiment 3
The present embodiment adopts following methods to prepare metal silver surface super-hydrophobicity material:
(1) choose metallic copper plate substrate, its surface is carried out to oil removing, pickling processes successively;
(2) the metallic copper plate substrate after the cleaning of (1) step is placed in to 0.02 mol/L silver acetate chemical solution and carries out chemical reaction, with ammoniacal liquor and acetic acid, adjust PH to 4, chemical reaction temperature is 25 ℃, and chemical time is 1h;
(3) the metal copper sheet obtaining after chemical reaction in (2) step spends ionized water washes clean, dry afterwards, then be placed in positive 20 thiol solutions of 0.03mol/L, be placed in 100 ℃ of baking ovens and react 30min, obtain metal silver surface super-hydrophobicity material.
Above-mentioned preparation metal silver surface super-hydrophobicity material surface is carried out to SEM observation, and result shows that metal silver surface is the chondritic of 300～400nm size; With Germany, produce contact angle instrument OCA20,4 μ L water droplets carry out hydrophobic experiment, and result shows that its contact angle is greater than 150 °.
Through instruction of the present invention, those skilled in the art will appreciate that each raw material and method that the present invention is cited can realize the present invention, and the bound value of each raw material and technique, interval value can realize the present invention, at this, do not enumerate embodiment.
Claims (9)
1. the preparation method of a metal silver surface super-hydrophobicity material, it is characterized in that, the method comprises: the clean metallic copper plate substrate of surface clean is put into the 0.01～0.1mol/L silver acetate solution configuring and carry out chemical reaction, and adjust its PH to 4～6 with acetic acid and ammoniacal liquor, reaction time is 1～60min, 10～90 ℃ of reaction temperatures; And then after water-repelling agent self-assembling reaction, obtain metal silver surface super-hydrophobicity material.
2. the preparation method of metal silver surface super-hydrophobicity material according to claim 1, is characterized in that, the temperature that described metallic copper plate substrate carries out chemical reaction in silver acetate solution is further 25～35 ℃, and pH value is 4～5.
3. the preparation method of metal silver surface super-hydrophobicity material according to claim 1, is characterized in that, the concentration of described silver acetate solution is further 0.02～0.1mol/L.
4. the preparation method of metal silver surface super-hydrophobicity material according to claim 1, it is characterized in that, described water-repelling agent self-assembling reaction is: by the metal copper sheet washing obtaining after chemical reaction, dry, then immerse in the water-repelling agent that concentration is 0.01～0.05mol/L, and its heating is carried out to self-assembling reaction, reaction temperature is 30～120 ℃, and the reaction time is 1～120 min.
5. according to the preparation method of the metal silver surface super-hydrophobicity material described in claim 1 or 4, it is characterized in that, described water-repelling agent is selected from the chain alkyl mercaptan of C8-C22, one or more in fluorine-containing mercaptan.
6. the preparation method of metal silver surface super-hydrophobicity material according to claim 5, is characterized in that, described water-repelling agent is selected from one or more in positive lauryl mercaptan, positive tetradecanylthioalcohol, positive 16 mercaptan, positive stearylmercaptan or positive 20 mercaptan.
7. the preparation method of metal silver surface super-hydrophobicity material according to claim 1, is characterized in that, the surface clean of described metallic copper plate substrate is for carrying out successively surface degreasing processing and pickling processes.
8. the metal silver surface super-hydrophobicity material that in claim 1-7 prepared by arbitrary described preparation method, it is characterized in that, this material is formed at metallic copper substrate surface, it comprises silver-colored micro-nano surface coarse structure and hydrophobic film, wherein, hydrophobic film is self-assembled to described silver-colored micro nano structure surface.
9. a kind of metal silver surface super-hydrophobicity material according to claim 8, is characterized in that, described hydrophobic film thickness is 4～20nm.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103785826A (en) * | 2014-02-19 | 2014-05-14 | 南京林业大学 | Method for preparing modified nanometer nickel powder |
| CN105110288A (en) * | 2015-08-27 | 2015-12-02 | 陕西科技大学 | Method for preparing patterned Ag nano-particles |
| CN107523817A (en) * | 2017-08-25 | 2017-12-29 | 华南理工大学 | A kind of preparation method of the controllable super-hydrophobic film layer of surface wettability |
| CN109371354A (en) * | 2018-12-20 | 2019-02-22 | 曾任坚 | A kind of preparation method of metal-base superhydrophobic material |
| CN109690365A (en) * | 2015-10-19 | 2019-04-26 | 美题隆公司 | Anti-corrosion Optical devices |
| CN109848436A (en) * | 2019-03-01 | 2019-06-07 | 淮海工学院 | A method of preparing silver nanoparticle band |
| CN110684968A (en) * | 2019-10-31 | 2020-01-14 | 济南大学 | Surface modification method for preventing white eggs in fish breeding earthen pot |
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| CN101270475A (en) * | 2008-03-20 | 2008-09-24 | 上海交通大学 | Method for preparing hydrophobic silver surface |
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| CN102230169A (en) * | 2011-06-13 | 2011-11-02 | 哈尔滨工业大学 | Method for constructing super-hydrophobic membrane on surface of copper matrix |
| CN102703886A (en) * | 2012-06-20 | 2012-10-03 | 太原理工大学 | Method for preparing magnesium alloy super-hydrophobic surface |
| CN103085380A (en) * | 2013-01-29 | 2013-05-08 | 上海交通大学 | Copper super-hydrophobic surface with decay resistance and preparation method thereof |
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| CN101270475A (en) * | 2008-03-20 | 2008-09-24 | 上海交通大学 | Method for preparing hydrophobic silver surface |
| CN101603187A (en) * | 2009-07-16 | 2009-12-16 | 上海交通大学 | Based on high-hydrophobic material of surface nano array structure and preparation method thereof |
| CN102230169A (en) * | 2011-06-13 | 2011-11-02 | 哈尔滨工业大学 | Method for constructing super-hydrophobic membrane on surface of copper matrix |
| CN102703886A (en) * | 2012-06-20 | 2012-10-03 | 太原理工大学 | Method for preparing magnesium alloy super-hydrophobic surface |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103785826A (en) * | 2014-02-19 | 2014-05-14 | 南京林业大学 | Method for preparing modified nanometer nickel powder |
| CN103785826B (en) * | 2014-02-19 | 2016-03-30 | 南京林业大学 | A kind of preparation method of modified Nano nickel powder |
| CN105110288A (en) * | 2015-08-27 | 2015-12-02 | 陕西科技大学 | Method for preparing patterned Ag nano-particles |
| CN109690365A (en) * | 2015-10-19 | 2019-04-26 | 美题隆公司 | Anti-corrosion Optical devices |
| CN107523817A (en) * | 2017-08-25 | 2017-12-29 | 华南理工大学 | A kind of preparation method of the controllable super-hydrophobic film layer of surface wettability |
| CN107523817B (en) * | 2017-08-25 | 2019-08-20 | 华南理工大学 | A kind of preparation method for the super-hydrophobic film layer that surface wettability is controllable |
| CN109371354A (en) * | 2018-12-20 | 2019-02-22 | 曾任坚 | A kind of preparation method of metal-base superhydrophobic material |
| CN109848436A (en) * | 2019-03-01 | 2019-06-07 | 淮海工学院 | A method of preparing silver nanoparticle band |
| CN110684968A (en) * | 2019-10-31 | 2020-01-14 | 济南大学 | Surface modification method for preventing white eggs in fish breeding earthen pot |
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| CN103567456B (en) | 2016-04-13 |
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