阅读说明：本技术 一种可改善表面光洁度的低共熔离子液体电沉积铜涂层的制备方法 (Preparation method of eutectic ionic liquid electrodeposited copper coating capable of improving surface finish ) 是由 江凡 匡一龙 朱天麒 吴红艳 杨欣烨 刘战辉 于 2021-07-14 设计创作，主要内容包括：本发明提供一种可改善表面光洁度的低共熔离子液体电沉积铜涂层的制备方法,包括：将氯化胆碱、乙二醇和氯化铜混合均匀并加热,恒温搅拌直到固体全部溶解,生成棕色粘稠的液体,得到电解液,向电解液中加入一定量的水杨酸；铜片作为可溶性阳极,铜块作为阴极,浸入电解液后与电源连接,进行恒电流电沉积；电沉积后,取出样品并清洗、吹干,即得到铜涂层。本发明在电解液中加入水杨酸,可对低共熔离子液体电沉积铜涂层技术进行改进,以获得更加致密平整的铜涂层,从而有效地提高了铜涂层的表面光洁度。本发明采用的原料廉价,绿色环保,安全无毒,电解液后期处理简单,且实验结果的重复性强。(The invention provides a preparation method of a eutectic ionic liquid electrodeposited copper coating capable of improving surface finish, which comprises the following steps: uniformly mixing choline chloride, ethylene glycol and copper chloride, heating, stirring at constant temperature until the solid is completely dissolved to generate brown viscous liquid to obtain electrolyte, and adding a certain amount of salicylic acid into the electrolyte; the copper sheet is used as a soluble anode, the copper block is used as a cathode, and the copper sheet is immersed in the electrolyte and then connected with a power supply to carry out constant current electrodeposition; and after electrodeposition, taking out the sample, cleaning and drying to obtain the copper coating. The salicylic acid is added into the electrolyte, so that the technology of the eutectic ionic liquid electrodeposition copper coating can be improved to obtain a more compact and smooth copper coating, and the surface finish of the copper coating is effectively improved. The electrolyte is cheap in raw materials, green, environment-friendly, safe and non-toxic, simple in post-treatment of the electrolyte and strong in repeatability of experimental results.)

1. A preparation method of eutectic ionic liquid electrodeposited copper coating capable of improving surface finish is characterized by comprising the following steps:

s1, preparation of electrolyte: uniformly mixing choline chloride, ethylene glycol and copper chloride, heating to 70-80 ℃, stirring at constant temperature until the solid is completely dissolved to generate brown viscous liquid to obtain electrolyte, and adding a certain amount of salicylic acid into the electrolyte;

s2, connecting electrode: in the electrolyte prepared in S1, the copper sheet is used as a soluble anode, the copper block is used as a cathode, and the distance between the anode and the cathode is 4 cm;

s3, electrodeposition: immersing an electrode into the salicylic acid-added electrolyte, and then connecting the electrode with a power supply to perform constant-current electrodeposition;

s4, taking out a sample: and after electrodeposition, taking out the sample, cleaning the sample and drying the sample by blowing.

2. The method for preparing the copper-based super-hydrophobic coating without adding the low surface energy substance, according to claim 1, wherein the mixing molar ratio of the choline chloride, the ethylene glycol and the copper chloride in S1 is 20:40: 1.

3. The method for preparing the copper-based super-hydrophobic coating without adding the low surface energy substance, as recited in claim 1, wherein the concentration of the salicylic acid in the electrolyte is 0.01-0.03mol/L after the salicylic acid is added in S1.

4. The method for preparing the copper-based super-hydrophobic coating without the addition of the low surface energy substances according to claim 1, wherein in S2, the anode and the cathode are subjected to electrode pretreatment before connection, specifically, after the copper sheet and the copper block are mechanically polished by SiC sand paper of No. 1000, No. 1500 and No. 2000, the copper sheet and the copper block are ultrasonically cleaned by ethanol for 30 minutes and then are washed by water, and then the copper sheet and the copper block are washed by 10% hydrochloric acid solution for 30 seconds and then are dried for later use.

5. The method for preparing copper-based super-hydrophobic coating without adding low surface energy substance as claimed in claim 1, wherein in S3, the constant current density is 5-10mA/cm²The electrodeposition temperature is 60-70 ℃, and the electrodeposition time is 6-10 minutes.

6. The method for preparing copper-based super-hydrophobic coating without adding low surface energy substance as claimed in claim 1, wherein in S3, the constant current density is 5mA/cm²The electrodeposition temperature was 70 ℃ and the electrodeposition time was 10 minutes.

7. The method for preparing the copper-based super-hydrophobic coating without adding the low surface energy substances according to claim 1, wherein in S4, the electrodeposited sample is sequentially subjected to ultrasonic cleaning in alcohol and deionized water for 10min and then dried.

The technical field is as follows:

the invention belongs to the technical field of surface treatment, and particularly relates to a preparation method of a eutectic ionic liquid electrodeposited copper coating capable of improving surface finish.

Background art:

nowadays, electrodeposition technology is widely used due to its advantages of low cost, high benefit and suitability for large-scale production. Related researchers (Rahul Jain, Ranga pitchumani. surface contamination of Durable coppers Based Superhydrophic Surfaces Via Electrodeposition [ J ]. Langmuir,2018,34(10): 3159-. As described in the r.jain experiment, sulfuric acid is generally used to adjust the pH of an electrolyte in an aqueous electrodeposition system, the waste liquid generated after the experiment causes serious environmental pollution and high recovery cost, and hydrogen gas is evolved during electrodeposition, which affects the performance of a sample. Compared with the electrodeposition in aqueous solution, the widely used eutectic ionic liquid electrodeposition in the field of electrodeposition has the advantages of no need of adjusting pH value, no hydrogen evolution, greenness and low energy consumption. However, for the eutectic ionic liquid electrodeposited copper coating, there are some problems, especially the problems of poor surface smoothness and uneven texture of the electrodeposited copper coating, which seriously affect the usability of the copper coating, and also greatly limit the subsequent further processing of the copper coating, and finally affect the development of the eutectic ionic liquid electrodeposited copper coating technology.

Based on the above, the invention provides a preparation method of eutectic ionic liquid electrodeposited copper coating capable of improving surface smoothness so as to solve the above problems.

The invention content is as follows:

the invention aims to solve the problem of surface smoothness of an electrodeposited copper coating in a eutectic ionic liquid, and provides a preparation method of the electrodeposited copper coating of the eutectic ionic liquid, which can improve the surface smoothness.

The invention adopts the following technical scheme:

a preparation method of eutectic ionic liquid electrodeposited copper coating capable of improving surface finish degree comprises the following steps:

s1, preparation of electrolyte: uniformly mixing choline chloride, ethylene glycol and copper chloride, heating to 70-80 ℃, stirring at constant temperature until the solid is completely dissolved to generate brown viscous liquid to obtain electrolyte, and adding a certain amount of salicylic acid into the electrolyte;

s2, connecting electrode: in the electrolyte prepared in S1, the copper sheet is used as a soluble anode, the copper block is used as a cathode, and the distance between the anode and the cathode is 4 cm;

s3, electrodeposition: immersing an electrode into the salicylic acid-added electrolyte, and then connecting the electrode with a power supply to perform constant-current electrodeposition;

s4, taking out a sample: and after electrodeposition, taking out the sample, cleaning the sample and drying the sample by blowing.

Further, in S1, the mixing molar ratio of choline chloride, ethylene glycol and copper chloride is 20:40: 1.

Furthermore, in S1, after salicylic acid is added, the concentration of the salicylic acid in the electrolyte is 0.01-0.03 mol/L.

Further, in S2, the anode and the cathode are subjected to electrode pretreatment before connection, specifically, after mechanically polishing the copper sheet and the copper block with 1000#, 1500# and 2000# SiC abrasive paper, ultrasonically cleaning with ethanol for 30 minutes, then washing with water after pickling with 10% hydrochloric acid solution for 30 seconds, and drying for later use.

Further, in S3, the constant current density is 5-10mA/cm²The electrodeposition temperature is 60-70 ℃, and the electrodeposition time is 6-10 minutes.

Further, in S3, the constant current density was 5mA/cm²The electrodeposition temperature was 70 ℃ and the electrodeposition time was 10 minutes.

Further, in S4, the sample after electrodeposition is sequentially ultrasonically cleaned in alcohol and deionized water for 10min, and then dried.

The invention has the beneficial effects that:

the salicylic acid is added into the electrolyte, so that the technology of the eutectic ionic liquid electrodeposition copper coating can be improved to obtain a more compact and smooth copper coating, and the surface finish of the copper coating is effectively improved. Salicylic acid can react with the precipitate on the surface of the coating to generate a complex, and the salicylic acid is fat-soluble organic acid, can be well dissolved with the eutectic ionic liquid, and has stable and uniform plating solution system and better environmental protection. The electrolyte is cheap in raw materials, green, environment-friendly, safe and non-toxic, simple in post-treatment of the electrolyte and strong in repeatability of experimental results.

Description of the drawings:

FIG. 1 is a macroscopic view (b-c) of a copper coating after electrodeposition and a macroscopic view (d) of a copper coating after cleaning, obtained from an electrolyte (a) according to example 1 of the present invention;

FIG. 2 is a macroscopic view (b-c) of a copper coating after electrodeposition in an electrolyte (a) and a macroscopic view (d) of a copper coating after cleaning, obtained in example 2 of the present invention;

FIG. 3 is a macroscopic view (b-c) of the copper coating after electrodeposition in the electrolyte (a) and a macroscopic view (d) of the copper coating after cleaning obtained in the comparative example of the present invention.

The specific implementation mode is as follows:

in order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.

Example 1

The embodiment provides a preparation method of a eutectic ionic liquid electrodeposited copper coating capable of improving surface finish, which comprises the following steps:

s1, preparation of electrolyte: uniformly mixing choline chloride, ethylene glycol and copper chloride (the mixing molar ratio is 20:40:1), heating to 70 ℃, stirring at constant temperature until all solids are dissolved to generate brown viscous liquid to obtain electrolyte, adding salicylic acid into the electrolyte, and uniformly stirring at constant temperature, wherein the concentration of the salicylic acid in the electrolyte is 0.02 mol/L.

S2, connecting electrode: mechanically polishing copper sheets and copper blocks by using 1000#, 1500# and 2000# SiC abrasive paper, ultrasonically cleaning the copper sheets and the copper blocks by using ethanol for 30 minutes, then washing the copper sheets and the copper blocks by using water, and then washing the copper sheets and the copper blocks by using 10% hydrochloric acid solution for 30 seconds and blow-drying the copper sheets and the copper blocks by using water; in the electrolyte prepared in S1, the copper sheet is used as a soluble anode, the copper block is used as a cathode, and the distance between the anode and the cathode is 4 cm;

s3, electrodeposition: immersing the electrode in the said electrolyte, connecting with power supply, and performing constant current electrodeposition with constant current density of 5mA/cm²The electrodeposition temperature is 70 ℃, and the electrodeposition time is 10 minutes;

s4, taking out a sample: and ultrasonically cleaning the electrodeposited sample in alcohol and deionized water for 10min in sequence, and drying to obtain the copper coating.

The macroscopic view of the copper coating prepared by the embodiment is shown in FIG. 1, and the obtained coating has uniform surface texture, no pollutant adhesion and high surface smoothness.

Example 2

The embodiment provides a preparation method of a eutectic ionic liquid electrodeposited copper coating capable of improving surface finish, which comprises the following steps:

s1, preparation of electrolyte: uniformly mixing choline chloride, ethylene glycol and copper chloride (the mixing molar ratio is 20:40:1), heating to 80 ℃, stirring at constant temperature until all solids are dissolved to generate brown viscous liquid to obtain electrolyte, adding salicylic acid into the electrolyte, and uniformly stirring at constant temperature, wherein the concentration of the salicylic acid in the electrolyte is 0.03 mol/L.

S2, connecting electrode: mechanically polishing copper sheets and copper blocks by using 1000#, 1500# and 2000# SiC abrasive paper, ultrasonically cleaning the copper sheets and the copper blocks by using ethanol for 30 minutes, then washing the copper sheets and the copper blocks by using water, and then washing the copper sheets and the copper blocks by using 10% hydrochloric acid solution for 30 seconds and blow-drying the copper sheets and the copper blocks by using water; in the electrolyte prepared in S1, the copper sheet is used as a soluble anode, the copper block is used as a cathode, and the distance between the anode and the cathode is 4 cm;

s3, electrodeposition: immersing the electrode in the said electrolyte, connecting with power supply, and performing constant current electrodeposition with constant current density of 5mA/cm²The electrodeposition temperature is 70 ℃, and the electrodeposition time is 10 minutes;

s4, taking out a sample: and ultrasonically cleaning the electrodeposited sample in alcohol and deionized water for 10min in sequence, and drying to obtain the copper coating.

The macroscopic view of the copper coating prepared by the embodiment is shown in FIG. 2, and the obtained coating has uniform surface texture, no pollutant adhesion and high surface smoothness.

Comparative example

The preparation method of the eutectic ionic liquid electrodeposited copper coating comprises the following steps:

s1, preparation of electrolyte: the method comprises the steps of uniformly mixing choline chloride, ethylene glycol and copper chloride (the mixing molar ratio is 20:40:1), heating to 70-80 ℃, and stirring at a constant temperature until solids are completely dissolved to generate brown viscous liquid, so as to obtain the electrolyte.

S2, connecting electrode: mechanically polishing copper sheets and copper blocks by using 1000#, 1500# and 2000# SiC abrasive paper, ultrasonically cleaning the copper sheets and the copper blocks by using ethanol for 30 minutes, then washing the copper sheets and the copper blocks by using water, and then washing the copper sheets and the copper blocks by using 10% hydrochloric acid solution for 30 seconds and blow-drying the copper sheets and the copper blocks by using water; in the electrolyte prepared in S1, the copper sheet is used as a soluble anode, the copper block is used as a cathode, and the distance between the anode and the cathode is 4 cm;

s3, electrodeposition: immersing the electrode in the electrolyte, connecting with a power supply, and performing constant current electrodeposition with a constant current density of 5mA/cm²The electrodeposition temperature is 70 ℃, and the electrodeposition time is 10 minutes;

s4, taking out a sample: and ultrasonically cleaning the electrodeposited sample in alcohol and deionized water for 10min in sequence, and drying to obtain the copper coating.

The macroscopic view of the obtained copper coating is shown in FIG. 3, and it can be found that the surface of the obtained coating has irregularities and complex adheres.

The salicylic acid is added into the electrolyte, so that the technology of the eutectic ionic liquid electrodeposition copper coating can be improved to obtain a more compact and smooth copper coating, and the surface finish of the copper coating is effectively improved. Salicylic acid can react with the precipitate on the surface of the coating to generate a complex, and the salicylic acid is fat-soluble organic acid, can be well dissolved with the eutectic ionic liquid, and has stable and uniform plating solution system and better environmental protection. The electrolyte is cheap in raw materials, green, environment-friendly, safe and non-toxic, simple in post-treatment of the electrolyte and strong in repeatability of experimental results.

The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention, it should be noted that, for those skilled in the art, several modifications and decorations without departing from the principle of the present invention should be regarded as the protection scope of the present invention.