CN105239066A - Preparation method of self-cleaning coating on copper surface - Google Patents
Preparation method of self-cleaning coating on copper surface Download PDFInfo
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- CN105239066A CN105239066A CN201510778652.2A CN201510778652A CN105239066A CN 105239066 A CN105239066 A CN 105239066A CN 201510778652 A CN201510778652 A CN 201510778652A CN 105239066 A CN105239066 A CN 105239066A
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Abstract
The invention provides a preparation method of a self-cleaning coating on a copper surface. The method comprises the following steps: 1, a copper base is ultrasonically cleaned through absolute ethyl alcohol and deionized water respectively for 5-10 min and then soaked in a mixed solution with the concentration of caustic alkali of 1.0-15 mol.L<-1> and the concentration of ammonium peroxydisulfate ions of 0.05-0.5 mol.L<-1>, and the reaction is carried out at the room temperature for 40-80 min; 2, the copper base in step 1 is taken out and fully cleaned with deionized water, blown dry with nitrogen and soaked into an ethanol solution with the concentration of aluminum stearate of 0.001-0.004 mol.L<-1>, and the reaction is carried out at the room temperature for 20-28 h; and 3, the copper base in the step 2 is taken out and cleaned with absolute ethyl alcohol, residual and unreacted stearic acid is removed, and the copper base is blown dry with nitrogen, so that the copper base with a self-cleaning coating on the surface is obtained. The preparation method of the bionic structure is simple; large devices are not required in the operation process; reagents are cheap; besides, the bionic structure prepared with the method can keep super-hydrophobicity within a wide temperature range and after long-time storage; and the bionic structure has a broad industrial application prospect.
Description
Technical field
The invention belongs to automatic cleaning coating field, metallic surface, be specifically related to a kind of preparation method of automatic cleaning coating of copper surface.
Background technology
Current people have worked out the method for many structured surface microtextures, and technique used has anodic metal oxide, electrochemical deposition, plasma etching, electron beam evaporation, sol-gel method, chemical vapour deposition etc.But in these methods, some preparation process are complicated, consuming time takes a lot of work, the expensive reagent of some needs.Although people's utilization in recent years has the silicon fluoride of low surface energy, hydrophobic polymkeric substance etc. has prepared a series of super hydrophobic surface, but the super-hydrophobicity problem of metallic surface is effectively solved always.Explore and set up simple and effective and quick, the inexpensive method being applicable to big area and preparing class lotus leaf biomimetic features, and be applied to suitability for industrialized production, remain people institute facing challenges.
Summary of the invention
The present invention is for solving the problem and carrying out.One of them object is to provide a kind of metallic copper and the super-hydrophobic coating of copper alloy surface; Another object is the preparation method providing this coating a kind of, adopt a kind of surface oxidation technology utilizing alkali auxiliary, copper substrate is prepared the method for nano bionic CuO structure, can show superhydrophobic property after treatment, coating has self-cleaning function.
The technical solution adopted in the present invention is as follows:
The invention provides a kind of preparation method of copper self-cleaning surface coating, have following steps: step 1, by copper substrate respectively after dehydrated alcohol and deionized water ultrasonic cleaning 5 ~ 10min, being immersed in containing concentration is 1.0 ~ 15molL
-1caustic alkali and concentration be 0.05 ~ 0.5molL
-1peroxydisulfate mixing solutions in, under room temperature react 40 ~ 80min; Step 2, fully cleaned by the copper substrate taking-up deionized water in step 1, immersing concentration after nitrogen dries up again is 0.001 ~ 0.004molL
-1stearic ethanolic soln in, under room temperature react 20 ~ 28h; Step 3, rinses the copper substrate taking-up dehydrated alcohol in step 2, and remove residual unreacted stearic acid, nitrogen dries up, and obtains the steel structure of surface with automatic cleaning coating.
Further, in step 1, caustic alkali is NaOH or KOH, preferred NaOH; Peroxydisulfate is (NH preferably
4)
2s
2o
8.Causticity paper mill wastewater is preferably 5 ~ 11molL
-1, most preferably 8molL
-1; The concentration of peroxydisulfate is preferably 0.2 ~ 0.4molL
-1, most preferably 0.3molL
-1.The reaction times of copper substrate in the mixing solutions containing caustic alkali and peroxydisulfate preferred 60min.
Further, in step 2, containing the preferably 0.002 ~ 0.003molL of stearic concentration described in stearic ethanolic soln
-1, most preferably 0.003molL
-1.Copper substrate contains the reaction times preferred 24h in stearic ethanolic soln at this.
Invention effect and effect
According to the preparation method of copper self-cleaning surface coating provided by the invention, first the copper substrate after cleaning is reacted in the mixing solutions containing caustic alkali and peroxydisulfate, then it is processed through the ethanolic soln containing aluminum stearate, show superhydrophobic property, even there will be super-hydrophobic and hydrophilic conversion.The preparation method of this biomimetic features is simple, operating process does not need main equipment, and reagent is cheap, and can keep ultra-hydrophobicity according to biomimetic features prepared by the method in wide temperature range He after long-time storage, has wide industrial applications prospect.
Embodiment
Embodiment one
The preparation method of the copper self-cleaning surface coating that the present embodiment provides, has following steps:
Step 1, by copper substrate respectively after dehydrated alcohol and deionized water ultrasonic cleaning 5min, being immersed in containing concentration is 1.0molL
-1naOH and concentration be 0.05molL
-1(NH
4)
2s
2o
8mixing solutions in, react 80min under room temperature;
Step 2, fully cleaned by the copper substrate taking-up deionized water in step 1, immersing concentration after nitrogen dries up again is 0.004molL
-1aluminum stearate ethanolic soln in, react 20h under room temperature;
Step 3, rinses the described copper substrate taking-up dehydrated alcohol in step 2, and remove residual unreacted stearic acid, nitrogen dries up, and obtains the steel structure of surface with automatic cleaning coating.
The effect of embodiment one and effect
According to the CuO biomimetic features that the method for the present embodiment one obtains, copper surface is 161.0 ° to the static contact angle of water, and contact angle hysteresis is 11.5 °.
Embodiment two
The preparation method of the copper self-cleaning surface coating that the present embodiment provides, has following steps:
Step 1, by copper substrate respectively after dehydrated alcohol and deionized water ultrasonic cleaning 10min, being immersed in containing concentration is 15molL
-1kOH and concentration be 0.5molL
-1(NH
4)
2s
2o
8mixing solutions in, react 40min under room temperature;
Step 2, fully cleaned by the copper substrate taking-up deionized water in step 1, immersing concentration after nitrogen dries up again is 0.001molL
-1aluminum stearate ethanolic soln in, react 28h under room temperature;
Step 3, rinses the described copper substrate taking-up dehydrated alcohol in step 2, and remove residual unreacted stearic acid, nitrogen dries up, and obtains the steel structure of surface with automatic cleaning coating.
The effect of embodiment two and effect
According to the CuO biomimetic features that the method for the present embodiment one obtains, copper surface is 158.5 ° to the static contact angle of water, and contact angle hysteresis is 11.2 °.
Embodiment three
The preparation method of the copper self-cleaning surface coating that the present embodiment provides, has following steps:
Step 1, by copper substrate respectively after dehydrated alcohol and deionized water ultrasonic cleaning 10min, being immersed in containing concentration is 8molL
-1naOH and concentration be 0.3molL
-1(NH
4)
2s
2o
8mixing solutions in, react 60min under room temperature;
Step 2, fully cleaned by the copper substrate taking-up deionized water in step 1, immersing concentration after nitrogen dries up again is 0.002molL
-1aluminum stearate ethanolic soln in, react 24h under room temperature;
Step 3, rinses the described copper substrate taking-up dehydrated alcohol in step 2, and remove residual unreacted stearic acid, nitrogen dries up, and obtains the steel structure of surface with automatic cleaning coating.
The effect of embodiment three and effect
According to the CuO biomimetic features that the method for the present embodiment one obtains, copper surface is 159.5 ° to the static contact angle of water, and contact angle hysteresis is 11.4 °.
In above-mentioned three embodiments, have employed concrete numerical value and the preparation method of automatic cleaning coating in the present invention is illustrated.Present inventor confirms by experiment, when the concentration of NaOH or KOH is 1.0 ~ 15molL
-1in any one numerical value, (NH
4)
2s
2o
8concentration be 0.05 ~ 0.5molL
-1in any one numerical value, be 0.001 ~ 0.004molL containing the concentration of aluminum stearate in the ethanolic soln of aluminum stearate
-1in any one numerical value time, all can realize object of the present invention, namely copper surface is about 160 ° to the static contact angle of water, and contact angle hysteresis is about 11.7 °.
Claims (8)
1. a preparation method for copper self-cleaning surface coating, is characterized in that, has following steps:
Step 1, by copper substrate respectively after dehydrated alcohol and deionized water ultrasonic cleaning 5 ~ 10min, being immersed in containing concentration is 1.0 ~ 15molL
-1caustic alkali and concentration be 0.05 ~ 0.5molL
-1peroxydisulfate mixing solutions in, under room temperature react 40 ~ 80min;
Step 2, fully cleaned by the copper substrate taking-up deionized water in step 1, immersing concentration after nitrogen dries up again is 0.001 ~ 0.004molL
-1stearic ethanolic soln in, under room temperature react 20 ~ 28h;
Step 3, rinses the described copper substrate taking-up dehydrated alcohol in step 2, and remove residual unreacted stearic acid, nitrogen dries up, and obtains the steel structure of surface with automatic cleaning coating.
2. the preparation method of copper self-cleaning surface coating according to claim 1, is characterized in that:
Wherein, in described step 1, described caustic alkali is NaOH or KOH.
3. the preparation method of copper self-cleaning surface coating according to claim 1 and 2, is characterized in that:
Wherein, in described step 1, be (NH containing peroxydisulfate
4)
2s
2o
8.
4. the preparation method of copper self-cleaning surface coating according to claim 1, is characterized in that:
Wherein, in described step 1, described causticity paper mill wastewater is 5 ~ 11molL
-1, the concentration of described peroxydisulfate is 0.2 ~ 0.4molL
-1.
5. the preparation method of copper self-cleaning surface coating according to claim 1, is characterized in that:
Wherein, in described step 1, described causticity paper mill wastewater is 8molL
-1, the concentration of described peroxydisulfate is 0.3molL
-1.
6. the preparation method of copper self-cleaning surface coating according to claim 1, is characterized in that:
Wherein, in described step 1, the reaction times of described copper substrate in the mixing solutions containing described caustic alkali and peroxydisulfate is 60min.
7. the preparation method of copper self-cleaning surface coating according to claim 1, is characterized in that:
Wherein, in described step 2, be 0.002 ~ 0.003molL containing stearic concentration described in stearic ethanolic soln
-1.
8. the preparation method of copper self-cleaning surface coating according to claim 1, is characterized in that:
Wherein, in described step 2, described copper substrate is being 24h containing the reaction times in stearic ethanolic soln.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107502885A (en) * | 2017-07-24 | 2017-12-22 | 湖北大学 | It is a kind of can automatically cleaning, the preparation method of erosion-resisting super-amphiphobic copper sheet |
| CN109023319A (en) * | 2018-09-18 | 2018-12-18 | 中国石油大学(华东) | A method of preparing dendroid micro nano structure copper oxide super-hydrophobic coat |
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| US20030233960A1 (en) * | 2002-06-23 | 2003-12-25 | John Grunwald | Method for electroless plating without precious metal sensitization |
| 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 |
| CN103406248A (en) * | 2013-08-26 | 2013-11-27 | 武汉理工大学 | Manufacturing method for copper-based super-hydrophobic surface structure |
| CN103469215A (en) * | 2013-09-06 | 2013-12-25 | 许昌学院 | Copper based super-hydrophobic surface with low friction coefficient and preparation method thereof |
| CN103640278A (en) * | 2013-11-29 | 2014-03-19 | 江苏大学 | Copper sheet with super-hydrophobic surface and preparation method thereof |
| CN104846376A (en) * | 2015-05-29 | 2015-08-19 | 清华大学 | Preparation method of metal-based super-hydrophobic surface |
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2015
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030233960A1 (en) * | 2002-06-23 | 2003-12-25 | John Grunwald | Method for electroless plating without precious metal sensitization |
| 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 |
| CN103406248A (en) * | 2013-08-26 | 2013-11-27 | 武汉理工大学 | Manufacturing method for copper-based super-hydrophobic surface structure |
| CN103469215A (en) * | 2013-09-06 | 2013-12-25 | 许昌学院 | Copper based super-hydrophobic surface with low friction coefficient and preparation method thereof |
| CN103640278A (en) * | 2013-11-29 | 2014-03-19 | 江苏大学 | Copper sheet with super-hydrophobic surface and preparation method thereof |
| CN104846376A (en) * | 2015-05-29 | 2015-08-19 | 清华大学 | Preparation method of metal-based super-hydrophobic surface |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107502885A (en) * | 2017-07-24 | 2017-12-22 | 湖北大学 | It is a kind of can automatically cleaning, the preparation method of erosion-resisting super-amphiphobic copper sheet |
| CN109023319A (en) * | 2018-09-18 | 2018-12-18 | 中国石油大学(华东) | A method of preparing dendroid micro nano structure copper oxide super-hydrophobic coat |
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