阅读说明：本技术 一步法绿色制备铜基超疏水涂层 (One-step green preparation of copper-based super-hydrophobic coating ) 是由 江凡 匡一龙 张书博 朱天麒 刘战辉 吴红艳 杨欣烨 于 2021-07-20 设计创作，主要内容包括：本发明公开了一步法绿色制备铜基超疏水涂层,包括以下步骤：S1、电极前处理；S2、配置电解液；S3、配置连接改性电解液；S4、电沉积；S5、电沉积后,将样品进行超声清洗、吹干得到铜基超疏水涂层；本发明通过采用绿色电沉积的手段来制备超疏水铜涂层,也就是采用氯化胆碱-乙二醇离子液体作为电沉积过程中的基础电解液。相比于其他制备超疏水涂层的工艺方法,在离子液体中一次性的电沉积超疏水涂层的技术具有更加绿色、节能的优点,工艺重复性更高,参数更易调节,本发明绿色、环保和相对较低的能耗,并且体系稳定,工艺参数易控制,这些优点符合当前社会发展和绿色制造的需要,具有更好的市场化运用的前景。(The invention discloses a one-step green preparation method of a copper-based super-hydrophobic coating, which comprises the following steps: s1, electrode pretreatment; s2, preparing electrolyte; s3, preparing connection modified electrolyte; s4, electrodeposition; s5, after electrodeposition, carrying out ultrasonic cleaning and blow-drying on the sample to obtain the copper-based super-hydrophobic coating; the invention adopts a green electrodeposition method to prepare the super-hydrophobic copper coating, namely choline chloride-ethylene glycol ionic liquid is adopted as basic electrolyte in the electrodeposition process. Compared with other process methods for preparing the super-hydrophobic coating, the technology for electrodepositing the super-hydrophobic coating in the ionic liquid at one time has the advantages of greenness and energy conservation, higher process repeatability and easier parameter adjustment.)

1. The one-step method for preparing the copper-based super-hydrophobic coating in a green manner is characterized by comprising the following steps of:

s1, electrode pretreatment: firstly, polishing a copper sheet and a copper block by using sand paper, then carrying out ultrasonic cleaning on the copper sheet and the copper block, then washing the copper sheet and the copper block by using deionized water for one time, then putting the washed copper sheet and the copper block into a 10 wt% hydrochloric acid solution for acid cleaning, and finally washing and drying the copper sheet and the copper block for the second time by using the deionized water;

s2, preparing electrolyte: mixing choline chloride and ethylene glycol according to a molar ratio of 1:2 to form ionic liquid, continuously magnetically stirring at 70 ℃ until colorless transparent liquid is formed, then adding copper chloride into a mixed solution of ethylene glycol and choline chloride, and continuously stirring at the temperature until yellow transparent liquid is obtained;

s3, preparing connection modified electrolyte: preparing a stearic acid-ethanol solution according to 2 wt%, uniformly mixing, measuring a certain amount of the stearic acid-ethanol solution, adding the stearic acid-ethanol solution into the yellow transparent liquid in S2, and continuously stirring at 70 ℃ until the stearic acid-ethanol solution and the yellow transparent liquid are uniformly mixed; then adding salicylic acid, and stirring at 70 ℃ until a uniform mixed liquid is formed;

s4, electrodeposition: immersing an electrode into the electrolyte, connecting the electrode with a power supply, and carrying out constant current electrodeposition, wherein a copper sheet is used as a soluble anode, a copper block is used as a working electrode, and the working electrode is parallel and opposite to a counter electrode;

and S5, after electrodeposition, carrying out ultrasonic cleaning and blow-drying on the sample to obtain the copper-based super-hydrophobic coating.

2. The one-step green preparation copper-based super-hydrophobic coating according to claim 1, characterized in that: in the step S1, when the sand paper is used for polishing, 1000#, 1500# and 2000# SiC sand paper are used for polishing in sequence, wherein the polishing time is 1-2min each time;

the ultrasonic cleaning solution is acetone, the cleaning time is 10-20min, the height of the inner tank of the ultrasonic cleaning equipment is 35-40cm, the power of the single vibrating plate at the bottom is kept at 0.3-0.5W/cm²；

Pickling in 10 wt% hydrochloric acid solution for 8-12 min.

3. The one-step green preparation copper-based super-hydrophobic coating according to claim 1, characterized in that: in the S2, the concentration of the copper chloride is 0.1mol/L-0.2 mol/L.

4. The one-step green preparation copper-based super-hydrophobic coating according to claim 1, characterized in that: in the S3, the addition amount of the stearic acid-ethanol solution is 20ml-70 ml.

5. The one-step green preparation copper-based super-hydrophobic coating according to claim 4, characterized in that: the addition amount of the salicylic acid is 0.01-0.02 mol/L.

6. The one-step process of claim 1The green preparation copper-based super-hydrophobic coating is characterized in that: in the S4, the constant current density is 3-9mA/cm²。

7. The one-step green preparation copper-based super-hydrophobic coating according to claim 6, characterized in that: the electrodeposition temperature is 70 ℃, and the electrodeposition time is 5-20 minutes.

8. The one-step green preparation copper-based super-hydrophobic coating according to claim 1, characterized in that: in the step S5, the ultrasonic cleaning time is 10-20min, the height of the inner tank of the ultrasonic cleaning equipment is 35-40cm, the power of the single vibrating plate at the bottom is kept at 0.3-0.5W/cm²。

Technical Field

The invention relates to the technical field of surface treatment, in particular to a one-step method for green preparation of a copper-based super-hydrophobic coating.

Background

In recent years, due to the demands of scientific development and engineering applications, superhydrophobic coatings have gained widespread attention. In nature, many animals and plants are observed to have superhydrophobic phenomena, for example, the surface of lotus leaves has good superhydrophobic and self-cleaning capabilities, so that 'sludge-free' is achieved. Compared with a hydrophilic coating and a hydrophobic coating, the super-hydrophobic coating has the obvious characteristic that the contact angle is larger than 150 degrees, and meanwhile, the super-hydrophobic coating also has the obvious functions of self-cleaning, corrosion protection, fog resistance, ice prevention, fluid drag reduction, biomedicine and the like.

In the development process of scientific research, methods for preparing super-hydrophobic coatings are increasing, such as anodic oxidation, solution soaking, electrostatic spinning, spraying, magnetron sputtering, sol-gel method, chemical etching, electrodeposition and the like. The electrodeposition technology is a mature and cheap technology, and the electrodeposition is that metal ions are reduced into a metal coating on the surface of a cathode in electrolyte under the action of current, so that the preparation method has the advantages of simple preparation process, low cost, uniform coating and the like. For the electrodeposition of the super-hydrophobic coating, the method is divided into a one-step method and a two-step method, wherein the one-step method means that the super-hydrophobic coating is directly electrodeposited in the electrolyte, and compared with the two-step method, the one-step method has the advantages of being simpler and more convenient and cheaper.

The core of the electrodeposition technology lies in the selection of electrolyte, and most people electrodeposit the super-hydrophobic coating in aqueous solution, and although the electrodeposition of the super-hydrophobic coating in aqueous solution has many advantages, such as mature technology, convenient operation, low price and the like, the disadvantages are obvious, such as the possibility of water electrolysis, hydrogen embrittlement of the coating and the generation of hydrogen gas. Also, electrodeposition of superhydrophobic coatings in aqueous solutions often uses H₂SO₄Isochoric acid to adjust pH, and H₂SO₄Etc. can seriously pollute the environment, which is contrary to the green manufacturing promoted by the state today. Therefore, the one-step green preparation of the copper-based super-hydrophobic coating is provided.

Disclosure of Invention

The invention aims to provide a one-step green preparation method of a copper-based super-hydrophobic coating, so as to solve the problems in the background technology.

In order to achieve the purpose, the invention provides the following technical scheme: the one-step method for green preparation of the copper-based super-hydrophobic coating comprises the following steps:

s1, electrode pretreatment: firstly, polishing a copper sheet and a copper block by using sand paper, then carrying out ultrasonic cleaning on the copper sheet and the copper block, then washing the copper sheet and the copper block by using deionized water for one time, then putting the washed copper sheet and the copper block into a 10 wt% hydrochloric acid solution for acid cleaning, and finally washing and drying the copper sheet and the copper block for the second time by using the deionized water;

s2, preparing electrolyte: mixing choline chloride and ethylene glycol according to a molar ratio of 1:2 to form ionic liquid, continuously magnetically stirring at 70 ℃ until colorless transparent liquid is formed, then adding copper chloride into a mixed solution of ethylene glycol and choline chloride, and continuously stirring at the temperature until yellow transparent liquid is obtained;

s3, preparing connection modified electrolyte: preparing a stearic acid-ethanol solution according to 2 wt%, uniformly mixing, measuring a certain amount of the stearic acid-ethanol solution, adding the stearic acid-ethanol solution into the yellow transparent liquid in S2, and continuously stirring at 70 ℃ until the stearic acid-ethanol solution and the yellow transparent liquid are uniformly mixed; then adding salicylic acid, and stirring at 70 ℃ until a uniform mixed liquid is formed;

s4, electrodeposition: immersing an electrode into the electrolyte, connecting the electrode with a power supply, and carrying out constant current electrodeposition, wherein a copper sheet is used as a soluble anode, a copper block is used as a working electrode, and the working electrode is parallel and opposite to a counter electrode;

and S5, after electrodeposition, carrying out ultrasonic cleaning and blow-drying on the sample to obtain the copper-based super-hydrophobic coating.

Preferably: in the step S1, when the sand paper is used for polishing, 1000#, 1500# and 2000# SiC sand paper are used for polishing in sequence, wherein the polishing time is 1-2min each time;

the ultrasonic cleaning solution is acetone, the cleaning time is 10-20min, the height of the inner tank of the ultrasonic cleaning equipment is 35-40cm, the power of the single vibrating plate at the bottom is kept at 0.3-0.5W/cm²；

Pickling in 10 wt% hydrochloric acid solution for 8-12 min.

Preferably: in the S2, the concentration of the copper chloride is 0.1mol/L-0.2 mol/L.

Preferably: in the S3, the addition amount of the stearic acid-ethanol solution is 20ml-70 ml.

Preferably: the addition amount of the salicylic acid is 0.01-0.02 mol/L.

Preferably: in the S4, the constant current density is 3-9mA/cm²。

Preferably: the electrodeposition temperature is 70 ℃, and the electrodeposition time is 5-20 minutes.

Preferably: in the step S5, the ultrasonic cleaning time is 10-20min, the height of the inner tank of the ultrasonic cleaning equipment is 35-40cm, the power of the single vibrating plate at the bottom is kept at 0.3-0.5W/cm²。

Compared with the prior art, the invention has the beneficial effects that: the invention adopts a green electrodeposition method to prepare the super-hydrophobic copper coating, namely choline chloride-ethylene glycol ionic liquid is adopted as basic electrolyte in the electrodeposition process. Compared with other process methods for preparing the super-hydrophobic coating, the technology for electrodepositing the super-hydrophobic coating in the ionic liquid at one time has the advantages of greenness and energy conservation, higher process repeatability and easier parameter adjustment.

Drawings

FIG. 1 is a graph showing the rolling angle of a copper-based superhydrophobic coating prepared in Experimental example 1 of the present invention;

FIG. 2 is a rolling angle diagram of a copper-based superhydrophobic coating prepared in Experimental example 2 of the present invention;

FIG. 3 is a graph showing the rolling angle of a copper-based superhydrophobic coating prepared in Experimental example 3 of the present invention;

FIG. 4 is a flow chart of the preparation method of the present invention.

Detailed Description

The technical solutions in the experimental examples of the present invention will be clearly and completely described below with reference to the drawings in the experimental examples of the present invention, and it is obvious that the described experimental examples are only a part of the experimental examples of the present invention, and not all of the experimental examples. Based on the experimental examples in the present invention, all other experimental examples obtained by a person of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

Example 1

Referring to fig. 1-4, the present invention provides a technical solution: the one-step method for green preparation of the copper-based super-hydrophobic coating comprises the following steps:

s1, electrode pretreatment: firstly, polishing a copper sheet and a copper block by using sand paper, then carrying out ultrasonic cleaning on the copper sheet and the copper block, then washing the copper sheet and the copper block by using deionized water for one time, then putting the washed copper sheet and the copper block into a 10 wt% hydrochloric acid solution for acid cleaning, and finally washing and drying the copper sheet and the copper block for the second time by using the deionized water;

s2, preparing electrolyte: mixing choline chloride and ethylene glycol according to a molar ratio of 1:2 to form ionic liquid, continuously magnetically stirring at 70 ℃ until colorless transparent liquid is formed, then adding copper chloride into a mixed solution of ethylene glycol and choline chloride, and continuously stirring at the temperature until yellow transparent liquid is obtained;

s3, preparing connection modified electrolyte: preparing a stearic acid-ethanol solution according to 2 wt%, uniformly mixing, measuring a certain amount of the stearic acid-ethanol solution, adding the stearic acid-ethanol solution into the yellow transparent liquid in S2, and continuously stirring at 70 ℃ until the stearic acid-ethanol solution and the yellow transparent liquid are uniformly mixed; then adding salicylic acid, and stirring at 70 ℃ until a uniform mixed liquid is formed;

s4, electrodeposition: immersing an electrode into the electrolyte, connecting the electrode with a power supply, and carrying out constant current electrodeposition, wherein a copper sheet is used as a soluble anode, a copper block is used as a working electrode, and the working electrode is parallel and opposite to a counter electrode;

and S5, after electrodeposition, carrying out ultrasonic cleaning and blow-drying on the sample to obtain the copper-based super-hydrophobic coating.

In this experimental example, the following are specific: in the step S1, when the sand paper is used for polishing, 1000#, 1500# and 2000# SiC sand paper are used for polishing in sequence, wherein the polishing time is 1-2min each time;

the ultrasonic cleaning solution is acetone, the cleaning time is 10-20min, the height of the inner tank of the ultrasonic cleaning equipment is 35-40cm, the power of the single vibrating plate at the bottom is kept at 0.3-0.5W/cm²；

Pickling in 10 wt% hydrochloric acid solution for 8-12 min.

In this experimental example, the following are specific: in the S2, the concentration of the copper chloride is 0.1mol/L-0.2 mol/L.

In this experimental example, the following are specific: in the S3, the addition amount of the stearic acid-ethanol solution is 20ml-70 ml.

In this experimental example, the following are specific: the addition amount of the salicylic acid is 0.01-0.02 mol/L.

In this experimental example, the following are specific: in the S4, the constant current density is 3-9mA/cm²。

In this experimental example, the following are specific: the electrodeposition temperature is 70 ℃, and the electrodeposition time is 5-20 minutes.

In this experimental example, the following are specific: in the step S5, the ultrasonic cleaning time is 10-20min, the height of the inner tank of the ultrasonic cleaning equipment is 35-40cm, the power of the single vibrating plate at the bottom is kept at 0.3-0.5W/cm²。

Experimental data:

the invention also provides experimental data for preparing the copper-based super-hydrophobic coating based on the method, as shown in experimental examples 1-3:

experimental example 1

1) The copper sheet and the copper block are grinded and polished by 1000#, 1500# and 2000# SiC sand paper, then are ultrasonically cleaned in acetone, are washed by deionized water and are then put into 10 wt% hydrochloric acid solution for acid cleaning so as to remove pollutants and oxides on the metal surface. Then washing with deionized water and drying.

2) Choline chloride (ChCl) and Ethylene Glycol (EG) are proportioned according to a molar ratio of 1:2 to form ionic liquid, and continuous magnetic stirring is carried out at 70 ℃ until colorless transparent liquid is formed. Then 0.2mol/L of copper chloride was added to the mixture of ethylene glycol and choline chloride, and stirring was continued at that temperature until a yellow transparent liquid was obtained.

3) Preparing stearic acid-ethanol solution according to 2 wt%, uniformly mixing, measuring 70ml of stearic acid-ethanol solution, adding into the yellow transparent liquid, and continuously stirring at 70 ℃ until uniform mixing; then 0.02mol/L salicylic acid (C7H6O3) was added and stirred at 70 ℃ until a homogeneous mixed liquid was formed.

4) And (3) immersing the electrode in the electrolyte, connecting the electrode with a power supply, taking a copper sheet as a soluble anode, namely a counter electrode, taking a copper block as a working electrode, wherein the working electrode is opposite to the counter electrode in parallel, and starting electrodeposition under the conditions that the electrodeposition temperature is 70 ℃, the electrodeposition time is 5min, the power supply is a direct current power supply, and the current density is 9mA/cm 2.

5) After electrodeposition, the sample was taken out and ultrasonically cleaned with deionized water, and blow-dried.

The rolling angle of the resulting copper-based superhydrophobic coating is shown in fig. 1, and it can be found that the contact angle of the resulting coating is greater than 150 °, showing superhydrophobicity.

Experimental example 2

1) The copper sheet and the copper block are grinded and polished by 1000#, 1500# and 2000# SiC sand paper, then are ultrasonically cleaned in acetone, are washed by deionized water and are then put into 10 wt% hydrochloric acid solution for acid cleaning so as to remove pollutants and oxides on the metal surface. Then washing with deionized water and drying.

2) Choline chloride (ChCl) and Ethylene Glycol (EG) are proportioned according to a molar ratio of 1:2 to form ionic liquid, and continuous magnetic stirring is carried out at 70 ℃ until colorless transparent liquid is formed. Then 0.15mol/L of copper chloride was added to the mixture of ethylene glycol and choline chloride, and stirring was continued at that temperature until a yellow transparent liquid was obtained.

3) Preparing a stearic acid-ethanol solution according to 2 wt%, uniformly mixing, measuring 45ml of the stearic acid-ethanol solution, adding the stearic acid-ethanol solution into the yellow transparent liquid, and continuously stirring at 70 ℃ until the stearic acid-ethanol solution and the yellow transparent liquid are uniformly mixed; then, 0.015mol/L salicylic acid (C7H6O3) was added thereto, and stirred at 70 ℃ until a homogeneous mixed liquid was formed.

4) And (3) immersing the electrode in the electrolyte, connecting the electrode with a power supply, taking a copper sheet as a soluble anode, namely a counter electrode, taking a copper block as a working electrode, wherein the working electrode is opposite to the counter electrode in parallel, and starting electrodeposition under the conditions that the electrodeposition temperature is 70 ℃, the electrodeposition time is 12min, the power supply is a direct current power supply, and the current density is 6mA/cm 2.

5) After electrodeposition, the sample was taken out and ultrasonically cleaned with deionized water, and blow-dried.

The rolling angle of the resulting copper-based superhydrophobic coating is shown in fig. 2, and it can be found that the contact angle of the resulting coating is greater than 150 °, showing superhydrophobicity.

Experimental example 3

1) The copper sheet and the copper block are grinded and polished by 1000#, 1500# and 2000# SiC sand paper, then are ultrasonically cleaned in acetone, are washed by deionized water and are then put into 10 wt% hydrochloric acid solution for acid cleaning so as to remove pollutants and oxides on the metal surface. Then washing with deionized water and drying.

2) Choline chloride (ChCl) and Ethylene Glycol (EG) are proportioned according to a molar ratio of 1:2 to form ionic liquid, and continuous magnetic stirring is carried out at 70 ℃ until colorless transparent liquid is formed. Then 0.1mol/L of copper chloride was added to the mixture of ethylene glycol and choline chloride, and stirring was continued at that temperature until a yellow transparent liquid was obtained.

3) Preparing a stearic acid-ethanol solution according to 2 wt%, uniformly mixing, measuring 20ml of the stearic acid-ethanol solution, adding the stearic acid-ethanol solution into the yellow transparent liquid, and continuously stirring at 70 ℃ until the stearic acid-ethanol solution and the yellow transparent liquid are uniformly mixed; then 0.01mol/L salicylic acid (C7H6O3) was added and stirred at 70 ℃ until a homogeneous mixed liquid was formed.

4) And (3) immersing the electrode in the electrolyte, connecting the electrode with a power supply, taking a copper sheet as a soluble anode, namely a counter electrode, taking a copper block as a working electrode, wherein the working electrode is opposite to the counter electrode in parallel, and starting electrodeposition under the conditions that the electrodeposition temperature is 70 ℃, the electrodeposition time is 20min, the power supply is a direct current power supply, and the current density is 3mA/cm 2.

5) After electrodeposition, the sample was taken out and ultrasonically cleaned with deionized water, and blow-dried.

The rolling angle of the resulting copper-based superhydrophobic coating is shown in fig. 3, and it can be found that the contact angle of the resulting coating is greater than 150 °, showing superhydrophobicity.

Working principle or structural principle: the invention adopts a green electrodeposition method to prepare the super-hydrophobic copper coating, namely choline chloride-ethylene glycol ionic liquid is adopted as basic electrolyte in the electrodeposition process. Compared with other process methods for preparing the super-hydrophobic coating, the technology for electrodepositing the super-hydrophobic coating in the ionic liquid at one time has the advantages of greenness and energy conservation, higher process repeatability and easier parameter adjustment.

Although experimental examples of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and alterations can be made herein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.