CN103567456B - A kind of Metallic silver surface super-hydrophobicitymaterial material and preparation method thereof - Google Patents
A kind of Metallic silver surface super-hydrophobicitymaterial material and preparation method thereof Download PDFInfo
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- CN103567456B CN103567456B CN201310463063.6A CN201310463063A CN103567456B CN 103567456 B CN103567456 B CN 103567456B CN 201310463063 A CN201310463063 A CN 201310463063A CN 103567456 B CN103567456 B CN 103567456B
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Abstract
The invention discloses a kind of Metallic silver surface super-hydrophobicitymaterial material and preparation method thereof, the method comprises: metallic copper plate substrate clean for surface clean is put into the 0.01 ~ 0.1mol/L silver acetate solutions configured and carries out chemical reaction, and adjust its PH to 4 ~ 6 with acetic acid and ammoniacal liquor, reaction time is 1 ~ 60min, reaction temperature 10 ~ 90 DEG C; And then Metallic silver surface super-hydrophobicitymaterial material is obtained after water-repelling agent self-assembling reaction.The preparation method of Metallic silver surface super-hydrophobicitymaterial material provided by the invention in chemical reaction one step by metallic copper plate substrate directly and silver acetate solutions react, by adjusting pH value with acetic acid and ammoniacal liquor, temperature and concentration, form silver-colored micro nano structure on copper sheet surface, and acetate coordination ion controls reaction rate preferably; Simplify step compared to existing method, the silver ammino solution of new configuration and the reducing agent containing aldehyde radical need not be adopted.
Description
Technical field
Noble metal super hydrophobic surface that the present invention relates to a kind of technical field of metal and preparation method thereof, particularly a kind of Metallic silver surface super-hydrophobicitymaterial material and preparation method thereof.
Background technology
Super hydrophobic surface refers to that contact angle is greater than the surface of 150 °, and super hydrophobic surface is primarily of two because usually controlling, and one is surface topography, and another is the chemical state on surface.Because super hydrophobic surface has the features such as waterproof, antifog, automatically cleaning, significant in basic research and commercial Application at present, cause and paid close attention to widely.
Be that " 200810063478.3 " name is called in the application for a patent for invention of " method preparing super-hydrophobic high reflecting material " and Chinese application number be that " 200810034864.X " name is called the preparation method that all relate to the super hydrophobic surface of argent in the application for a patent for invention of " preparation method of hydrophobic silver surface " at Chinese application number, employ silver ammino solution in the method and contain the reducing agent of aldehyde radical.
Summary of the invention
The invention provides a kind of Metallic silver surface super-hydrophobicitymaterial material and preparation method thereof, this preparation method simplifies step for the preparation method of argent super hydrophobic surface conventional at present, namely need not adopt the silver ammino solution of new configuration and the reducing agent containing 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 solutions reacts, by by acetic acid and ammoniacal liquor adjusted to ph, temperature and concentration, silver-colored micro nano structure is formed on copper sheet surface, and acetate coordination ion controls reaction rate preferably, and then utilize Chemical self-assembly principle to assemble one deck organic sulfur alcohols hydrophobic substance at silver-colored micro-and nano-structural surface, thus obtain Metallic silver surface super-hydrophobicitymaterial material, reach the super-hydrophobicity of whole material.
Technical scheme of the present invention is as follows:
A kind of preparation method of Metallic silver surface super-hydrophobicitymaterial material, the method comprises: metallic copper plate substrate clean for surface clean is put into the 0.01 ~ 0.1mol/L silver acetate solutions configured and carries out chemical reaction, and adjust its pH to 4 ~ 6 with acetic acid and ammoniacal liquor, reaction time is 1 ~ 60min, reaction temperature 10 ~ 90 DEG C; And then Metallic silver surface super-hydrophobicitymaterial material is obtained after water-repelling agent self-assembling reaction.
Further, the more conventional temperature that described metallic copper plate substrate carries out chemical reaction in silver acetate solutions is 25 ~ 35 DEG C further, and pH value is 4 ~ 5.
Further preferably, the concentration of described silver acetate solutions is 0.02 ~ 0.1mol/L further.
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, dry obtained after chemical reaction, then immersing concentration is in the water-repelling agent of 0.01 ~ 0.05mol/L, and self-assembling reaction is carried out to its heating, reaction temperature is 30 ~ 120 DEG C, and the reaction time is 1 ~ 120min.Wherein, washing, drying can adopt any conventional means in the industry.
Preferred described water-repelling agent is selected from one or more in the chain alkyl mercaptan of C8-C22, fluorine-containing mercaptan above.
Because environment amenable floride-free water-repelling agent is current development trend, further preferred described water-repelling agent be selected from n-dodecyl mereaptan, positive tetradecanylthioalcohol, positive 16 mercaptan, positive stearylmercaptan or positive 20 mercaptan one or more.
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 process and pickling processes, and wherein surface degreasing process refers to the treatment process removed by the organic substances such as the greasy dirt of metallic copper plate substrate surface adhesion; Pickling processes refers to the operation oxide skin(coating) acid solution on metallic copper plate substrate surface removed.Surface degreasing and pickling processes do not limit sequencing, but first carry out surface degreasing process usually, then carry out pickling processes.
The present invention also provides a kind of Metallic silver surface super-hydrophobicitymaterial material 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-and nano-structural 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 Metallic silver surface super-hydrophobicitymaterial material provided by the invention in chemical reaction one step by metallic copper plate substrate directly and silver acetate solutions react, by by acetic acid and ammoniacal liquor adjusted to ph, temperature and concentration, form silver-colored micro nano structure on copper sheet surface, and acetate coordination ion controls reaction rate preferably; Simplify step compared to existing method, the silver ammino solution of new configuration and the reducing agent containing aldehyde radical need not be adopted.
Detailed description of the invention
Below in conjunction with specific embodiment, set forth the present invention further.Should be appreciated that, these embodiments only for illustration of the present invention, and are not intended to limit the scope of the invention.The improvement made according to the present invention of those skilled in the art and adjustment, still belong to protection scope of the present invention in actual applications.
Embodiment 1
The present embodiment adopts following methods to prepare Metallic silver surface super-hydrophobicitymaterial material:
(1) choose metallic copper plate substrate, oil removing, pickling processes are carried out successively in its surface;
(2) the metallic copper plate substrate after (1) step being cleaned is placed in 0.02mol/L silver acetate chemical solution and carries out chemical reaction, and adjust pH to 5 with ammoniacal liquor and acetic acid, chemical reaction temperature is 35 DEG C, and chemical time is 15min;
(3) it is clean that the metal copper sheet obtained after chemical reaction in (2) step spends deionized water, dry afterwards, then be placed in positive 16 thiol solutions of 0.015mol/L, be placed in 100 DEG C of baking ovens and react 30min, obtain Metallic silver surface super-hydrophobicitymaterial material.
SEM observation is carried out on the Metallic silver surface super-hydrophobicitymaterial material surface of above-mentioned preparation, and result shows that metal silver surface is the Silver Clusters of 1 ~ 1.5 μm, and Silver Clusters is made up of the silver particles of 20-60nm; Produce contact angle instrument OCA20 with Germany, 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 Metallic silver surface super-hydrophobicitymaterial material:
(1) choose metallic copper plate substrate, oil removing, pickling processes are carried out successively in its surface;
(2) the metallic copper plate substrate after (1) step being cleaned is placed in 0.10mol/L silver acetate chemical solution and carries out chemical reaction, and this adjusts pH to 4 with ammoniacal liquor and acetic acid, and chemical reaction temperature is 25 DEG C, and chemical time is 1min;
(3) it is clean that the metal copper sheet obtained after chemical reaction in (2) step spends deionized water, dry afterwards, then be placed in positive 16 thiol solutions of 0.05mol/L, be placed in 100 DEG C of baking ovens and react 30min, then obtain Metallic silver surface super-hydrophobicitymaterial material.
SEM observation is carried out on the Metallic silver surface super-hydrophobicitymaterial material surface of above-mentioned preparation, and result shows that metal silver surface is the bladed structure of 300 ~ 700nm size; Produce contact angle instrument OCA20 with Germany, 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 Metallic silver surface super-hydrophobicitymaterial material:
(1) choose metallic copper plate substrate, oil removing, pickling processes are carried out successively in its surface;
(2) the metallic copper plate substrate after (1) step being cleaned is placed in 0.02mol/L silver acetate chemical solution and carries out chemical reaction, and adjust pH to 4 with ammoniacal liquor and acetic acid, chemical reaction temperature is 25 DEG C, and chemical time is 1h;
(3) it is clean that the metal copper sheet obtained after chemical reaction in (2) step spends deionized water, dry afterwards, is then placed in positive 20 thiol solutions of 0.03mol/L, is placed in 100 DEG C of baking ovens and reacts 30min, obtain Metallic silver surface super-hydrophobicitymaterial material.
SEM observation is carried out on above-mentioned preparation Metallic silver surface super-hydrophobicitymaterial material surface, and result shows that metal silver surface is the chondritic of 300 ~ 400nm size; Produce contact angle instrument OCA20 with Germany, 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 cited by the present invention and method can realize the present invention, and the bound value of each raw material and technique, interval value can realize the present invention, do not enumerate embodiment at this.
Claims (9)
1. the preparation method of a Metallic silver surface super-hydrophobicitymaterial material, it is characterized in that, the method comprises: metallic copper plate substrate clean for surface clean is put into the 0.01 ~ 0.1mol/L silver acetate solutions configured and carries out chemical reaction, and adjust its pH to 4 ~ 6 with acetic acid and ammoniacal liquor, reaction time is 1 ~ 60min, reaction temperature 10 ~ 90 DEG C; And then Metallic silver surface super-hydrophobicitymaterial material is obtained after water-repelling agent self-assembling reaction.
2. the preparation method of Metallic silver surface super-hydrophobicitymaterial material according to claim 1, is characterized in that, the temperature that described metallic copper plate substrate carries out chemical reaction in silver acetate solutions is 25 ~ 35 DEG C, and pH value is 4 ~ 5.
3. the preparation method of Metallic silver surface super-hydrophobicitymaterial material according to claim 1, is characterized in that, the concentration of described silver acetate solutions is 0.02 ~ 0.1mol/L.
4. the preparation method of Metallic silver surface super-hydrophobicitymaterial material according to claim 1, it is characterized in that, described water-repelling agent self-assembling reaction is: by the metal copper sheet washing, dry obtained after chemical reaction, then immersing concentration is in the water-repelling agent of 0.01 ~ 0.05mol/L, and self-assembling reaction is carried out to its heating, reaction temperature is 30 ~ 120 DEG C, and the reaction time is 1 ~ 120min.
5. the preparation method of the Metallic silver surface super-hydrophobicitymaterial material according to claim 1 or 4, is characterized in that, described water-repelling agent be selected from the chain alkyl mercaptan of C8-C22, fluorine-containing mercaptan one or more.
6. the preparation method of Metallic silver surface super-hydrophobicitymaterial material according to claim 5, is characterized in that, described water-repelling agent be selected from n-dodecyl mereaptan, positive tetradecanylthioalcohol, positive 16 mercaptan, positive stearylmercaptan or positive 20 mercaptan one or more.
7. the preparation method of Metallic silver surface super-hydrophobicitymaterial material according to claim 1, is characterized in that, the surface clean of described metallic copper plate substrate is for carry out surface degreasing process and pickling processes successively.
8. the Metallic silver surface super-hydrophobicitymaterial material prepared by described preparation method arbitrary in claim 1-7, 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 silver-colored micro-and nano-structural surface.
9. a kind of Metallic silver surface super-hydrophobicitymaterial material according to claim 8, is characterized in that, described hydrophobic film thickness is 4 ~ 20nm.
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| CN103785826B (en) * | 2014-02-19 | 2016-03-30 | 南京林业大学 | A kind of preparation method of modified Nano nickel powder |
| CN105110288B (en) * | 2015-08-27 | 2017-01-25 | 陕西科技大学 | Method for preparing patterned Ag nano-particles |
| US10241238B2 (en) * | 2015-10-19 | 2019-03-26 | Materion Corporation | Corrosion resistant optical device |
| 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 |
| CN110684968B (en) * | 2019-10-31 | 2021-09-24 | 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 |
| 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 |
| 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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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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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