CN103451688A - Method for preparing super-hydrophobic biomimetic surface on copper substrate - Google Patents
Method for preparing super-hydrophobic biomimetic surface on copper substrate Download PDFInfo
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- CN103451688A CN103451688A CN2013103983791A CN201310398379A CN103451688A CN 103451688 A CN103451688 A CN 103451688A CN 2013103983791 A CN2013103983791 A CN 2013103983791A CN 201310398379 A CN201310398379 A CN 201310398379A CN 103451688 A CN103451688 A CN 103451688A
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Abstract
The invention relates to a surface modification technology for metal materials, and in particular relates to a method for preparing a super-hydrophobic biomimetic surface on a copper substrate so as to improve the hydrophobic performance of a copper surface. The method comprises the following steps of: firstly, performing a pretreatment process of cleaning the copper substrate by using absolute ethyl alcohol; then immerging a sample in electroplate liquid to perform electro-deposition so as to ensure that the topographic characteristics of the surface of the sample are changed, the surface contain chemical elements different from the substrate, and a micro nano-scale double-layer graded structure is formed on the copper surface; finally, after reaction, forming a low-surface-energy film on the surface to ensure that the surface of the copper substrate with the micro nano-scale graded structure has super-hydrophobic properties and has adhesion of a 'petal effect' and self-cleaning property of a 'lotus leaf effect' respectively under different reaction conditions.
Description
Technical field:
The present invention relates to the metal surface properties modification technology, particularly relate to the preparation method of super-hydrophobic bionic surface on the copper matrix.
Background technology:
As everyone knows, the survival of the fittest in natural selection, nature was through the differentiation of 1 years, and every kind of biology all has its unique excellent properties, and many biological surfaces have formed natural super-hydrophobicity structure, as lotus leaf, Rose, Rice Leaf and water skipper leg etc.These natural biological surfaces have micro-nano double-deck hierarchy and chemical composition, demonstrate remarkable super-hydrophobicity, have possessed automatically cleaning effect and adhesivity simultaneously, namely famous " lotus leaf effect " and " petal effect ".Therefore, aspect the engineering materials Design and manufacture, these biological surface tissues usually are used as living prototype.
In recent years, the metallic substance hydrophobic film prepares increasing concern.Because copper has higher electric conductivity, heat conductivility, and the good excellent properties such as machinability, thus important structured material become, in industry and daily life, be used widely, as pipeline in thermal conductor, heat exchanger, electric power circuit and Seawater Desalination Project etc.Therefore, improve the copper surface property, the super hydrophobic surface that preparation has the double-deck hierarchy of micro-nano-scale will be a very promising technical study.
The preparation method of super-hydrophobic bionic surface is many, and electrodip process is generally arranged at present both at home and abroad, chemical method for etching, template, electrochemical process, photolithography, sol-gel method, self-assembly method etc. layer by layer.Electrodip process is to form the process of complex compound coating at material surface by the electrochemistry approach, easy, quick, the with low cost and easy realization of this method.For prepare the super hydrophobic surface with micro-nano hierarchy on the copper matrix, improve the surface property of copper substrate, to realize being changed between the high adhesion in surface and automatically cleaning, this is a kind of new trial, the development of effects on surface treatment technology is significant.
Technology contents:
The object of the invention is to improve surperficial hydrophobicity, the preparation method of super-hydrophobic bionic surface on a kind of copper matrix is provided.
The present invention is the feature of copying the animals and plants super-hydrophobicity microtextures such as lotus leaf, Rose, paddy rice and water skipper, adopt electro-deposition method, on copper base, preparation has the bionic super-hydrophobic surface of the double-deck hierarchy of micro-nano-scale on lotus leaf, Rose and Rice Leaf surface, improved surface property, make it there is super-hydrophobicity, high-adhesiveness and self-cleaning function, to being more widely used.
In order to achieve the above object, design bill of the present invention is:
The preparation method of super-hydrophobic bionic surface in a kind of copper substrate, step 1, pre-treating technology: at first with dehydrated alcohol, clean the copper substrate;
Step 2, electrolysis: will in the copper substrate sample immersion plating liquid after cleaning, carry out electrolysis, described electroplate liquid is comprised of Cerium II Chloride and tetradecanoic acid, Cerium II Chloride is 0.025-0.05mol, tetradecanoic acid is 0.05-0.16mol, Cerium II Chloride and tetradecanoic acid are stirred in dehydrated alcohol, form 100-300ml solution, electroplating time is selected any number between 5min～24h, after having reacted, surface forms low surface energy film, and this film is that the copper base surface with micro-nano double-deck hierarchy has the superhydrophobic characteristic of canonical biometric.
The quality of the shape characteristic of described specimen surface and generation novel substance is affected by the Cerium II Chloride of electroplate liquid and tetradecanoic acid mixed liquid concentration, the optimal concentration of electroplate liquid is: 0.038mol Cerium II Chloride and 0.1mol tetradecanoic acid stir in dehydrated alcohol, form 150ml solution.
The quality of the shape characteristic of described specimen surface and generation novel substance is affected by electroplating time also, and electroplating time selects 5min, 10min, 20min, 30min, 40min or 24h.
Said micro-nano double-deck hierarchy is that the chemical replacement reaction is occurred in electroplate liquid by the copper surface, at the copper specimen surface, forms pore space structure and mastoid process body, on the copper matrix, forms micro-nano multiple dimensioned double-deck hierarchy surface.
Said canonical biometric comprises the plants such as lotus leaf, roseleaf and Rice Leaf.
Beneficial effect: on this copper matrix, super-hydrophobic bionic surface has the double-deck hierarchy of micro-nano-scale, and its gained contact angle is greater than 150 °, reaches super-hydrophobic state.Under applying working condition, hydrophobic performance obviously strengthens, and can realize surperficial high-adhesiveness and the conversion between self-cleaning property, with simple galvanic deposit result, compares, and this invention has made marked progress.
The accompanying drawing explanation:
The SEM figure on Fig. 1 galvanic deposit surface, electroplating time is respectively:
(a)5min;(b)10min;(c)20min;(d)40min;(e)24h。
The water droplet state of the super hydrophobic surface that the different electrodeposition times of Fig. 2 are prepared, wherein:
(a) 10min; (b-d) 30min (water droplet respectively at 10ms, rolling condition when 60ms and 120ms).
Fig. 3 is different, and electrodeposition time makes surperficial contact angle, and galvanic deposit voltage is 20V, and electroplating time is respectively 5min, 10min, 20min, 30min, 40min, 1440min.
Embodiment:
The preparation method of super-hydrophobic bionic surface in a kind of copper substrate of the present invention, at first, carry out the design of copper matrix bionic surface:
With natural biologic material, for designing a model, on the copper matrix, design has the surface of the constitutional features of natural biological compounded material microtexture distribution.
Carry out the design of super-hydrophobicity bionic surface with the copper matrix:
Because copper has higher electric conductivity, heat conductivility, and the good excellent properties such as machinability, thereby become important structured material, in industry and daily life, be used widely, but because of its metallic surface hydrophobicity poor, thereby restricted to a great extent it in industrial application.The present invention can improve the copper surface hydrophobicity, realizes high-adhesiveness and automatically cleaning effect.
The preparation of super-hydrophobic bionic surface on the copper matrix: take copper as matrix, carry out surface treatment by electro-deposition method, pretreated copper sample directly is immersed in electroplate liquid, chief component is: 0.038mol Cerium II Chloride and 0.1mol tetradecanoic acid stir in dehydrated alcohol, form 150ml solution, its electroplating time is respectively 5min, 10min, 20min, 30min, 40min, 24h, carry out electrochemical reaction.After having reacted, form the tetradecanoic acid cerium film with low surface energy at the copper matrix surface.Observe surface topography, can find to have formed the double-deck hierarchy of biomimetic micro-nano yardstick, and because its surface has formed low surface energy film, make the copper surface there is typical biological super-hydrophobicity, and there is the adhesivity of typical petal effect and the self-cleaning property of lotus leaf effect under different experimental conditions.
Described electroplate liquid is: 0.038mol Cerium II Chloride and 0.1mol tetradecanoic acid stir in dehydrated alcohol, form 150ml solution.The difference of Cerium II Chloride and tetradecanoic acid mixed liquid concentration, can affect the shape characteristic of specimen surface and generate the quality of novel substance, the optimal concentration that this concentration is electroplating solution.
Described electroplating time selects 5min, 10min, 20min, 30min, 40min or 24h.The difference of copper sample electroplating time, can affect the shape characteristic of specimen surface and generate the quality of novel substance.
Said micro-nano double-deck hierarchy is that the chemical replacement reaction is occurred in electroplate liquid by the copper surface, at the copper specimen surface, forms pore space structure and mastoid process body, on the copper matrix, forms micro-nano multiple dimensioned double-deck hierarchy surface.
Said canonical biometric comprises the plants such as lotus leaf, roseleaf and Rice Leaf.
In the copper substrate, the preparation method of super-hydrophobic bionic surface carries out according to the following steps:
1, disclose canonical biometric its microtexture of hydrophobic surface and distribution characteristics rule.
2, the copper sample is carried out to pre-treatment: the copper sample of having polished is positioned in dehydrated alcohol and carries out ultrasonic cleaning 10min, remove the dirt of specimen surface.
3, galvanic deposit: will in the copper substrate immersion plating liquid after cleaning, carry out galvanic deposit, the electroplate liquid chief component is that 0.038mol Cerium II Chloride and 0.1mol tetradecanoic acid stir in dehydrated alcohol, forms 150ml solution.This experiment is at room temperature carried out, sample is carried out to the plating of different time, be respectively 5min, 10min, 20min, 30min, 40min and 24h, form the tetradecanoic acid cerium film with low surface energy at the copper specimen surface, surface microstructure is pore space structure and mastoid process body, that is, form the double-deck hierarchy of micro-nano-scale surface in the copper substrate, make the copper surface there is the superhydrophobic characteristic of canonical biometric.
Claims (5)
1. the preparation method of super-hydrophobic bionic surface in a copper substrate is characterized in that:
Step 1, pre-treating technology: at first with dehydrated alcohol, clean the copper substrate;
Step 2, electrolysis: will in the copper substrate sample immersion plating liquid after cleaning, carry out electrolysis, described electroplate liquid is comprised of Cerium II Chloride and tetradecanoic acid, Cerium II Chloride is 0.025-0.05mol, tetradecanoic acid is 0.05-0.16mol, Cerium II Chloride and tetradecanoic acid are stirred in dehydrated alcohol, form 100-300ml solution, electroplating time is selected any number between 5min～24h, after having reacted, surface forms low surface energy film, and this film is that the copper base surface with micro-nano double-deck hierarchy has the superhydrophobic characteristic of canonical biometric.
2. the preparation method of super-hydrophobic bionic surface on a kind of copper matrix according to claim 1 is characterized in that:
The quality of the shape characteristic of described specimen surface and generation novel substance is affected by the Cerium II Chloride of electroplate liquid and tetradecanoic acid mixed liquid concentration, the optimal concentration of electroplate liquid is: 0.038mol Cerium II Chloride and 0.1mol tetradecanoic acid stir in dehydrated alcohol, form 150ml solution.
3. the preparation method of super-hydrophobic bionic surface on a kind of copper matrix according to claim 1 is characterized in that:
The quality of the shape characteristic of described specimen surface and generation novel substance is affected by electroplating time also, and electroplating time selects 5min, 10min, 20min, 30min, 40min or 24h.
4. the preparation method of super-hydrophobic bionic surface on a kind of copper matrix according to claim 1 is characterized in that:
Said micro-nano double-deck hierarchy is that the chemical replacement reaction is occurred in electroplate liquid by the copper surface, at the copper specimen surface, forms pore space structure and mastoid process body, on the copper matrix, forms micro-nano multiple dimensioned double-deck hierarchy surface.
5. the preparation method of super-hydrophobic bionic surface on a kind of copper matrix according to claim 1 is characterized in that:
Said canonical biometric comprises lotus leaf, roseleaf and Rice Leaf plant.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104308369A (en) * | 2014-10-28 | 2015-01-28 | 吉林大学 | Method for manufacturing iridescent super-hydrophobic bionic surfaces on copper substrates |
| CN105237797A (en) * | 2015-09-17 | 2016-01-13 | 哈尔滨工程大学 | Super-lubricative surface material with groove-shaped substrate and preparation method thereof |
| CN105665855A (en) * | 2016-04-06 | 2016-06-15 | 吉林大学 | Preparation method of unmodified bionic super-hydrophobic and low-adhesion aluminum alloy surface |
| CN106048685A (en) * | 2016-06-30 | 2016-10-26 | 上海电力学院 | Preparation method of super-hydrophobic surface of aluminum alloy |
| CN106498458A (en) * | 2016-12-30 | 2017-03-15 | 福建钢泓金属科技股份有限公司 | A kind of automatically cleaning corrosion resistant plate and its production method |
| CN107191796A (en) * | 2017-06-15 | 2017-09-22 | 华南理工大学 | A kind of great power LED cooling lamp and a kind of preparation method of non-homogeneous wetability patterned surface |
| CN110644026A (en) * | 2019-10-30 | 2020-01-03 | 贵州民族大学 | Preparation method of super-hydrophobic aluminum alloy surface with self-repairing characteristic |
| CN110644027A (en) * | 2019-10-30 | 2020-01-03 | 贵州民族大学 | Preparation method of super-hydrophobic B10 copper-nickel alloy surface with self-repairing characteristic |
| CN111122198A (en) * | 2019-12-29 | 2020-05-08 | 北京理工大学 | Test device and method for measuring self-cleaning performance of bionic adhesion functional surface |
| CN113514800A (en) * | 2021-04-23 | 2021-10-19 | 吉林大学 | Water strider-imitated vibration sensing and positioning system and vibration sensing and positioning method |
| CN113956521A (en) * | 2021-10-21 | 2022-01-21 | 中国船舶重工集团公司第七二五研究所 | Preparation method of super-hydrophobic antifouling anti-drag material |
| CN114752990A (en) * | 2022-03-26 | 2022-07-15 | 四川轻化工大学 | Metal-based nest type micro-structure super-hydrophobic surface and preparation method and application thereof |
| CN114798384A (en) * | 2022-04-06 | 2022-07-29 | 漳州顺圆盛工艺品有限公司 | Method for spraying surface of copper handicraft |
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104308369A (en) * | 2014-10-28 | 2015-01-28 | 吉林大学 | Method for manufacturing iridescent super-hydrophobic bionic surfaces on copper substrates |
| CN104308369B (en) * | 2014-10-28 | 2016-08-24 | 吉林大学 | The preparation method of the super-hydrophobic bionic surface of iris at the bottom of a kind of cuprio |
| CN105237797A (en) * | 2015-09-17 | 2016-01-13 | 哈尔滨工程大学 | Super-lubricative surface material with groove-shaped substrate and preparation method thereof |
| CN105237797B (en) * | 2015-09-17 | 2018-12-07 | 哈尔滨工程大学 | With super lubricated surface material of groove-like substrate and preparation method thereof |
| CN105665855A (en) * | 2016-04-06 | 2016-06-15 | 吉林大学 | Preparation method of unmodified bionic super-hydrophobic and low-adhesion aluminum alloy surface |
| CN106048685A (en) * | 2016-06-30 | 2016-10-26 | 上海电力学院 | Preparation method of super-hydrophobic surface of aluminum alloy |
| CN106498458A (en) * | 2016-12-30 | 2017-03-15 | 福建钢泓金属科技股份有限公司 | A kind of automatically cleaning corrosion resistant plate and its production method |
| CN106498458B (en) * | 2016-12-30 | 2018-06-29 | 福建钢泓金属科技股份有限公司 | A kind of automatically cleaning stainless steel plate and its production method |
| CN107191796A (en) * | 2017-06-15 | 2017-09-22 | 华南理工大学 | A kind of great power LED cooling lamp and a kind of preparation method of non-homogeneous wetability patterned surface |
| CN107191796B (en) * | 2017-06-15 | 2023-09-19 | 华南理工大学 | High-power LED heat dissipation lamp and preparation method of non-uniform wettability patterned surface |
| CN110644027A (en) * | 2019-10-30 | 2020-01-03 | 贵州民族大学 | Preparation method of super-hydrophobic B10 copper-nickel alloy surface with self-repairing characteristic |
| CN110644026B (en) * | 2019-10-30 | 2020-09-18 | 贵州民族大学 | Preparation method of super-hydrophobic aluminum alloy surface with self-repairing characteristic |
| CN110644026A (en) * | 2019-10-30 | 2020-01-03 | 贵州民族大学 | Preparation method of super-hydrophobic aluminum alloy surface with self-repairing characteristic |
| CN111122198A (en) * | 2019-12-29 | 2020-05-08 | 北京理工大学 | Test device and method for measuring self-cleaning performance of bionic adhesion functional surface |
| CN113514800A (en) * | 2021-04-23 | 2021-10-19 | 吉林大学 | Water strider-imitated vibration sensing and positioning system and vibration sensing and positioning method |
| CN113514800B (en) * | 2021-04-23 | 2022-09-09 | 吉林大学 | Water strider-imitated vibration sensing and positioning system and vibration sensing and positioning method |
| CN113956521A (en) * | 2021-10-21 | 2022-01-21 | 中国船舶重工集团公司第七二五研究所 | Preparation method of super-hydrophobic antifouling anti-drag material |
| CN113956521B (en) * | 2021-10-21 | 2022-12-13 | 中国船舶重工集团公司第七二五研究所 | Preparation method of super-hydrophobic antifouling anti-drag material |
| CN114752990A (en) * | 2022-03-26 | 2022-07-15 | 四川轻化工大学 | Metal-based nest type micro-structure super-hydrophobic surface and preparation method and application thereof |
| CN114798384A (en) * | 2022-04-06 | 2022-07-29 | 漳州顺圆盛工艺品有限公司 | Method for spraying surface of copper handicraft |
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Application publication date: 20131218 |