CN113817203A - Method for preparing Cu-CNTs super-hydrophobic coating on plastic surface - Google Patents
Method for preparing Cu-CNTs super-hydrophobic coating on plastic surface Download PDFInfo
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- 239000004332 silver Substances 0.000 claims abstract description 8
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims abstract description 7
- 230000009466 transformation Effects 0.000 claims abstract description 6
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- 239000000243 solution Substances 0.000 claims description 78
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- 239000006087 Silane Coupling Agent Substances 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 230000001235 sensitizing effect Effects 0.000 claims description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
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- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 7
- 206010070834 Sensitisation Diseases 0.000 claims description 7
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
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- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
- C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention discloses a method for preparing a Cu-CNTs super-hydrophobic coating on the surface of plastic, belonging to the field of hydrophobic coatings. The method comprises the steps of placing pretreated plastics in chemical silver plating solution for chemical silver plating, then carrying out electroplating treatment in composite plating solution prepared from blue vitriol, sulfuric acid, carbon nano tubes and deionized water, and finally placing in air or drying, wherein the coating is subjected to wettability transformation to obtain the Cu-CNTs super-hydrophobic coating with super-hydrophobic performance. The invention adopts a one-step method to prepare the Cu-CNTs composite coating with good conductivity and super hydrophobicity on the surface of the pre-silvered ABS plastic, has simple preparation process and can widen the application field of the conductive super-hydrophobic material.
Description
Technical Field
The invention belongs to the field of hydrophobic coatings, and particularly relates to a method for preparing a Cu-CNTs super-hydrophobic coating on a plastic surface.
Background
Plastics are widely used in aerospace, automobiles, communication equipment and daily necessities due to their light weight, good chemical stability and excellent processability. The plastic surface metallization process can combine the advantages of plastics and metals, so that the material obtains excellent comprehensive performance, maintains the low density of the plastics, and simultaneously endows the plastics with the metal characteristics, such as conductivity, wear resistance, electromagnetic shielding property, decoration property and the like.
In the industries of microelectronics, automobiles and the like, an electroplating method is the most common plastic surface metallization method, and the surface of a material can obtain the characteristics of metal by electroplating copper on the surface, so that various performances such as conductivity, friction resistance and the like are realized, but the surface of a pure copper coating is easy to adsorb corrosive media to cause chemical corrosion and electrochemical corrosion. The super-hydrophobic surface is a surface with a contact angle of water drops on the surface being more than or equal to 150 degrees and a rolling angle being less than or equal to 10 degrees, the super-hydrophobic surface shows hydrophobicity, the water drops can roll off when the surface has a certain inclination angle, and the super-hydrophobic surface can effectively reduce the contact area between the material and the water drops, so that the occurrence of corrosion behavior is inhibited.
In general, the preparation of superhydrophobic surfaces requires two steps: firstly, constructing a micro-nano coarse structure on the surface of a material by a physical or chemical method; secondly, the rough surface is modified by low surface energy substances such as fluorine and the like, so that the surface energy of the material is reduced. However, the current process often requires complicated and expensive equipment and fluorine-containing harmful substances, thereby limiting the industrial application of the superhydrophobic surface.
In conclusion, aiming at the defects of the prior art, the development of the preparation method of the super-hydrophobic surface, which has the advantages of simple process, low cost and short manufacturing period, is beneficial to the industrial application of the super-hydrophobic surface.
Disclosure of Invention
In order to solve the problems of long manufacturing period and complex production process of the existing super-hydrophobic surface, the invention provides a method for preparing a Cu-CNTs super-hydrophobic coating on a plastic surface. The treatment process is easy to realize, short in manufacturing period, low in production cost and suitable for industrial mass production.
The purpose of the invention is realized by the following technical scheme.
A method for preparing a Cu-CNTs super-hydrophobic coating on a plastic surface comprises the following steps:
(1) electroplating a Cu-CNTs composite coating: placing the plastic subjected to the pre-silvering treatment in a composite plating solution, and preparing a Cu-CNTs composite plating layer by an electroplating method; the composite plating solution consists of Carbon Nano Tubes (CNTs), sodium dodecyl sulfate, copper sulfate pentahydrate, sulfuric acid and water;
(2) wettability transformation of the Cu-CNTs composite coating: and (2) cleaning the Cu-CNTs composite coating obtained in the step (1), and then placing the Cu-CNTs composite coating in air or drying the Cu-CNTs composite coating to convert the Cu-CNTs composite coating from a hydrophilic state to a super-hydrophobic state.
Preferably, the composite plating solution in the step (1) comprises the following components: 1-2.5 g/L carbon nanotube, 0.5-1.5 g/L sodium dodecyl sulfate, 180-240 g/L blue vitriol, 20-40 ml/L sulfuric acid.
Preferably, the electroplating temperature in the step (1) is 20-30 ℃, and the current density is 0.5-2.5A/dm2The electroplating time is 3-10 minutes. The current density is more preferably 1 to 2.5A/dm2。
Preferably, the electroplating process is carried out with the addition of 500r/min of magnetic stirring.
Preferably, in the step (2), the drying temperature is 70-90 ℃ and the drying time is 48-72 hours; the time of placing in the air is more than or equal to 11 days.
Preferably, the carbon nanotubes in the step (1) are carboxylated multi-wall carbon nanotubes, the diameter of the carbon nanotubes is less than 8nm, and the length of the carbon nanotubes is 10-30 μm.
Preferably, the composite plating solution in step (1) is prepared by the following method:
dissolving blue vitriol in deionized water, and adding sulfuric acid to obtain electroplating solution; and (2) taking the carbon nano tube and the sodium dodecyl sulfate to be uniformly dispersed in deionized water by ultrasonic, adding the carbon nano tube and the sodium dodecyl sulfate into the electroplating solution, and uniformly mixing under the ultrasonic action to obtain the Cu-CNTs composite plating solution.
Preferably, the plastic in step (1) is acrylonitrile-butadiene-styrene (ABS) plastic.
Preferably, the pre-silvering treatment in the step (1) comprises the following steps:
cleaning ABS plastic, sequentially placing the cleaned ABS plastic in silane coupling agent solution and sensitizing solution for surface modification treatment and sensitizing treatment, and then placing the cleaned ABS plastic in chemical silver plating solution for pre-silver plating treatment; after each step of treatment, the water is washed by deionized water and absolute ethyl alcohol;
the silane coupling agent solution is an alcohol solution of 3-Mercaptopropyltriethoxysilane (MPTES), wherein the concentration of the 3-mercaptopropyltriethoxysilane is 10-30 ml/L, and the alcohol solution consists of deionized water and absolute ethyl alcohol with the volume fraction of 1: 9; the surface modification treatment is to soak the workpiece in a silane coupling agent solution for 50-70 minutes;
the sensitizing solution is an aqueous solution of stannous chloride and hydrochloric acid, wherein the concentration of the stannous chloride is 15-25 g/L, the concentration of the hydrochloric acid is 30-50 ml/L, and the hydrochloric acid is a 37 wt% hydrochloric acid solution; the sensitization condition is that the workpiece is soaked in sensitization liquid at normal temperature for 5-15 minutes;
the pre-silver plating treatment is to place a workpiece in a silver ammonia solution at 40-50 ℃, add a reducing agent solution with the same volume for plating for 5-15 minutes, wherein the silver ammonia solution is prepared by dripping 15-20 g/L silver nitrate solution into ammonia water until the solution is clear, and the reducing agent is 7.5-10 g/L glucose aqueous solution.
A Cu-CNTs super-hydrophobic coating prepared by any one of the methods; the Cu-CNTs super-hydrophobic coating has good conductivity and super-hydrophobic performance (the water contact angle is more than 150 degrees, and the rolling angle is less than 10 degrees).
Compared with the prior art, the invention has the following advantages and effects:
(1) the method for preparing the Cu-CNTs super-hydrophobic coating on the surface of the ABS plastic can prepare the super-hydrophobic film layer on the conductive surface in 3 minutes at the fastest speed, has short preparation period and low production cost, and is suitable for industrial mass production;
(2) the preparation method of the super-hydrophobic membrane layer can complete the wettability conversion from hydrophilicity to hydrophobicity by the adsorption of the coating layer on low surface energy substances in the air, and does not need to further modify the low surface energy substances;
(3) the method for preparing the Cu-CNTs super-hydrophobic coating does not need special equipment, is simple in preparation method, easy to control the treatment process, and capable of avoiding the use of fluorine-containing harmful substances, and the composite plating solution is simple in components, easy to treat and less in harm to the environment.
Drawings
FIG. 1 is a scanning electron microscope image and a contact angle test result image of a Cu-CNTs super-hydrophobic coating prepared in example 1;
FIG. 2 is a scanning electron microscope image and a contact angle test result image of the Cu-CNTs super-hydrophobic coating prepared in example 2;
FIG. 3 is a scanning electron microscope image and a contact angle test result image of the Cu-CNTs super-hydrophobic coating prepared in example 3.
Fig. 4 is a contact angle test result graph of the copper-graphene composite plating layer prepared in comparative example 1.
FIG. 5 is a graph showing the results of the Cu-CNTs composite coating wettability transition test prepared in example 2.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
A method for preparing a Cu-CNTs super-hydrophobic coating on the surface of ABS plastic comprises the following specific operation steps:
the method comprises the following steps: modification treatment of ABS plastic silane coupling agent
Placing the cleaned ABS plastic with the size of 30 multiplied by 40 multiplied by 1(mm) into 100mL of silane coupling agent solution to be soaked for 50 minutes; taking out, washing with deionized water and absolute ethyl alcohol, and blow-drying for later use; wherein the concentration of the silane coupling agent (MPTES) is 10 ml/L.
Step two: ABS plastic sensitization
Placing the ABS plastic obtained in the step one into 100mL of sensitizing solution to be soaked for 5 minutes at room temperature; taking out, washing with deionized water and absolute ethyl alcohol, and blow-drying for later use; the sensitizing solution is a mixed solution of 15g/L stannous chloride and 30ml/L hydrochloric acid (37 wt%).
Step three: chemical silvering of ABS plastics
Soaking the ABS plastic obtained in the step two into 100mL of silver ammonia solution, adding reducing agent solution with the same volume, uniformly mixing for 5 minutes at 40 ℃, taking out, washing with deionized water and absolute ethyl alcohol, and drying for later use; the silver-ammonia solution is prepared by dripping ammonia water into 15g/L silver nitrate solution until the solution is clear, and the reducing agent solution is 7.5g/L glucose solution.
Step four: preparation of Cu-CNTs composite plating solution
Dissolving 180g of blue vitriod in 1L of deionized water, and adding 20mL of concentrated sulfuric acid (98%) to obtain electroplating solution; adding 50mL of deionized water into 1g of carbon nano tube and 0.5g of sodium dodecyl sulfate, performing ultrasonic dispersion uniformly, adding into 950mL of electroplating solution, and mixing uniformly under the ultrasonic action to obtain the Cu-CNTs composite plating solution.
Step five: Cu-CNTs super-hydrophobic coating plated on ABS plastic
Electroplating the ABS plastic with silver-plated surface obtained in the third step in the composite plating solution obtained in the fourth step, wherein the electroplating temperature is 20 ℃, and the current density is 1A/dm2The electroplating time is 3 minutes, and the magnetic stirring of 500r/min is additionally needed in the electroplating process.
Step six: drying treatment
And washing and drying the sample obtained in the fifth step by using deionized water and absolute ethyl alcohol, and then placing the sample in a drying oven at 70 ℃ for drying treatment for 48 hours to obtain the Cu-CNTs super-hydrophobic coating on the ABS surface.
The prepared Cu-CNTs super-hydrophobic coating on the ABS surface is detected and characterized as follows:
(1) and (3) morphology analysis: the scanning electron microscope image of the Cu-CNTs composite coating prepared in this example is shown in fig. 1 (a), the surface of the composite coating is rough, copper grains are deposited on the ABS surface in a lamellar form, and a large amount of air remains between lamellae, which is a special microstructure that imparts superhydrophobic properties to the Cu-CNTs composite coating.
(2) And (3) wettability testing: the contact angle test result of the Cu-CNTs composite coating prepared in the example is shown in (b) in FIG. 1, and the water contact angle reaches 151.4 degrees.
(3) And (3) testing the conductivity: the conductivity of the Cu-CNTs composite plating layer prepared by the embodiment is characterized by a four-probe sheet resistance meter, and the sheet resistance is 0.236 omega/sq.
Example 2
A method for preparing a Cu-CNTs super-hydrophobic coating on the surface of ABS plastic comprises the following specific operation steps:
the method comprises the following steps: modification treatment of ABS plastic silane coupling agent
Placing the cleaned ABS plastic with the size of 30 multiplied by 40 multiplied by 1(mm) into 100mL of silane coupling agent solution for soaking for 60 minutes; taking out, washing with deionized water and absolute ethyl alcohol, and blow-drying for later use; wherein the concentration of the silane coupling agent (MPTES) is 20 ml/L.
Step two: ABS plastic sensitization
Placing the ABS plastic obtained in the step one into 100mL of sensitizing solution to be soaked for 5 minutes at room temperature; taking out, washing with deionized water and absolute ethyl alcohol, and blow-drying for later use; the sensitizing solution is a mixed solution of stannous chloride of 20g/L and hydrochloric acid of 40ml/L (37 wt%).
Step three: chemical silvering of ABS plastics
Soaking the ABS plastic obtained in the step two into 100mL of silver ammonia solution, adding reducing agent solution with the same volume, uniformly mixing for 10 minutes at 45 ℃, taking out, washing with deionized water and absolute ethyl alcohol, and drying for later use; the silver-ammonia solution is prepared by dripping 17g/L of silver nitrate solution into ammonia water until the solution is clear, and the reducing agent solution is 8.5g/L of glucose solution.
Step four: preparation of Cu-CNTs composite plating solution
Dissolving 220g of blue vitriod in 1L of deionized water, and adding 30mL of concentrated sulfuric acid (98%) to obtain electroplating solution; adding 50mL of deionized water into 1.5g of carbon nano tube and 1g of sodium dodecyl sulfate, performing ultrasonic dispersion uniformly, adding into 950mL of electroplating solution, and mixing uniformly under the ultrasonic action to obtain the Cu-CNTs composite plating solution.
Step five: Cu-CNTs super-hydrophobic coating plated on ABS plastic
Electroplating the ABS plastic with silver-plated surface obtained in the third step in the composite plating solution obtained in the fourth step, wherein the electroplating temperature is 25 ℃, and the current density is 1A/dm2The electroplating time is 5 minutes, and the magnetic stirring of 500r/min is additionally needed in the electroplating process.
Step six: drying treatment
And washing and drying the sample obtained in the fifth step by using deionized water and absolute ethyl alcohol, and then placing the sample in a drying oven at 80 ℃ for drying treatment for 60 hours to obtain the Cu-CNTs super-hydrophobic coating on the ABS surface.
The prepared Cu-CNTs super-hydrophobic coating on the ABS surface is detected and characterized as follows:
(1) and (3) morphology analysis: the scanning electron microscope image of the Cu-CNTs composite coating prepared in this example is shown in fig. 2 (a), and the surface of the composite coating is rough, so that the lamellar structures on the surface can be clearly seen to overlap, and a large amount of air is captured.
(2) Wettability transition test: the workpiece prepared in the fifth step of this example is exposed to air for wettability transformation test, and the prepared Cu-CNTs composite coating is in a super-hydrophilic state (contact angle is about 0 °) when it is prepared, and the wettability transformation into a super-hydrophobic state (contact angle is about 158.7 °) occurs when it is left in air, and the transformation process is shown in fig. 5. The contact angle test is carried out after the surface moisture is removed, and the result shows that the special micro-morphology of the composite coating can oxidize and adsorb air pollutants when the composite coating is placed in the air, so that an organic pollutant film is formed on the surface, and the nonpolar air pollutants have hydrophobicity and can reduce the free energy of the surface of the material, so that the material is endowed with super-hydrophobic performance.
(3) And (3) wettability testing: the contact angle test result of the Cu-CNTs composite plating layer prepared in this example is shown in fig. 2 (b), and the water contact angle thereof reaches 158.7 °.
(4) And (3) testing the conductivity: the conductivity of the Cu-CNTs composite coating prepared by the embodiment is characterized by a four-probe sheet resistance meter, and the sheet resistance is 0.126 omega/sq.
Example 3
A method for preparing a Cu-CNTs super-hydrophobic coating on the surface of ABS plastic comprises the following specific operation steps:
the method comprises the following steps: modification treatment of ABS plastic silane coupling agent
Placing the cleaned ABS plastic with the size of 30 multiplied by 40 multiplied by 1(mm) into 100mL of silane coupling agent solution for soaking for 70 minutes; taking out, washing with deionized water and absolute ethyl alcohol, and blow-drying for later use; wherein the concentration of the silane coupling agent (MPTES) is 30 ml/L.
Step two: ABS plastic sensitization
Placing the ABS plastic obtained in the step one into 100mL of sensitizing solution to be soaked for 15 minutes at room temperature; taking out, washing with deionized water and absolute ethyl alcohol, and blow-drying for later use; the sensitizing solution is a mixed solution of 25g/L stannous chloride and 40ml/L hydrochloric acid (37 wt%).
Step three: chemical silvering of ABS plastics
Soaking the ABS plastic obtained in the step two into 100mL of silver ammonia solution, adding reducing agent solution with the same volume, uniformly mixing for 15 minutes at 50 ℃, taking out, washing with deionized water and absolute ethyl alcohol, and drying for later use; the silver-ammonia solution is prepared by dripping ammonia water into 20g/L silver nitrate solution until the solution is clear, and the reducing agent solution is 10g/L glucose solution.
Step four: preparation of Cu-CNTs composite plating solution
Dissolving 240g of blue vitriod in 1L of deionized water, and adding 40mL of concentrated sulfuric acid (98%) to obtain electroplating solution; adding 50mL of deionized water into 2.5g of carbon nano tube and 1.5g of sodium dodecyl sulfate, performing ultrasonic dispersion uniformly, adding into 950mL of electroplating solution, and mixing uniformly under the ultrasonic action to obtain the Cu-CNTs composite plating solution.
Step five: Cu-CNTs super-hydrophobic coating plated on ABS plastic
Electroplating the ABS plastic with silver-plated surface obtained in the third step in the composite plating solution obtained in the fourth step, wherein the electroplating temperature is 30 ℃, and the current density is 2.5A/dm2The electroplating time is 5 minutes, and the magnetic stirring of 500r/min is additionally needed in the electroplating process.
Step six: drying treatment
And washing and drying the sample obtained in the fifth step by using deionized water and absolute ethyl alcohol, and then placing the sample in a drying oven at 90 ℃ for drying treatment for 72 hours to obtain the Cu-CNTs super-hydrophobic coating on the ABS surface.
The prepared Cu-CNTs super-hydrophobic coating on the ABS surface is detected and characterized as follows:
(1) and (3) morphology analysis: the scanning electron microscope image of the Cu-CNTs composite coating prepared in this example is shown in fig. 3 (a), and the lamellar Cu on the surface of the composite coating continuously grows and overlaps to form a micro-roughness structure.
(2) And (3) wettability testing: the contact angle test result of the Cu-CNTs composite plating layer prepared in this example is shown in fig. 3 (b), and the water contact angle thereof reaches 153.4 °.
(3) And (3) testing the conductivity: the conductivity of the Cu-CNTs composite plating layer prepared by the embodiment is characterized by a four-probe sheet resistance meter, and the sheet resistance is 0.031 omega/sq.
Example 4
On the basis of the embodiment 2, other conditions are controlled to be unchanged, and the current densities in the electroplating process are respectively changed as follows: 0.5A/dm2、1A/dm2、1.5A/dm2、2A/dm2、2.5A/dm2. The change of the conductivity and the super-hydrophobicity is shown in table 1:
TABLE 1
As can be seen from table 1, the sheet resistance of the composite plating layer continuously decreased as the current density increased. Under the condition that other conditions are not changed, the thickness of the plating layer can be increased by increasing the current density, so that the conductivity of the plating layer is improved.
In addition, the super-hydrophobic property of the coating is observed to increase and then decrease with the increase of the current density. When the current density is low, the flaky copper particles of the coating are mutually dispersed, and an air film layer with enough air can not be trapped, so that a stable super-hydrophobic model is difficult to form. When the current density is high, the flaky copper particles are easy to aggregate, and the super-hydrophobic property is reduced. Therefore, when the current density is 1A/dm2And meanwhile, the super-hydrophobic property of the coating is optimal, the flaky copper particles are overlapped in a staggered mode to form a stable Cassie-Baxter model, a large amount of air is trapped between the particles, and the hydrophobicity of the particles is improved.
Comparative example 1
On the basis of the embodiment 2, other conditions are controlled to be unchanged, the carbon nano tube is replaced by the graphene material, the copper-graphene composite coating is prepared on the surface of the ABS plastic, and the following characteristics are performed:
(1) and (3) wettability testing: the contact angle test result of the copper-graphene composite plating layer prepared in the comparative example is shown in fig. 4, and the water contact angle is 112.9 °. It can be seen that the copper-graphene composite coating cannot form super-hydrophobic performance similar to that of the Cu-CNTs composite coating.
(2) And (3) testing the conductivity: the conductivity of the copper-graphene composite plating layer prepared by the embodiment is characterized by a four-probe sheet resistance meter, and the sheet resistance is 0.016 omega/sq.
Claims (10)
1. A method for preparing a Cu-CNTs super-hydrophobic coating on a plastic surface is characterized by comprising the following steps:
(1) electroplating a Cu-CNTs composite coating: placing the plastic subjected to the pre-silvering treatment in a composite plating solution, and preparing a Cu-CNTs composite plating layer by an electroplating method; the composite plating solution consists of carbon nano tubes, sodium dodecyl sulfate, copper sulfate pentahydrate, sulfuric acid and water;
(2) wettability transformation of the Cu-CNTs composite coating: and (2) cleaning the Cu-CNTs composite coating obtained in the step (1), and then placing the Cu-CNTs composite coating in air or drying the Cu-CNTs composite coating to convert the Cu-CNTs composite coating from a hydrophilic state to a super-hydrophobic state.
2. The method according to claim 1, wherein the composite plating solution of step (1) comprises the following components: 1-2.5 g/L carbon nanotube, 0.5-1.5 g/L sodium dodecyl sulfate, 180-240 g/L blue vitriol, 20-40 ml/L sulfuric acid.
3. The method according to claim 1, wherein the temperature of the electroplating in the step (1) is 20 to 30 ℃ and the current density is 0.5 to 2.5A/dm2The electroplating time is 3-10 minutes.
4. The method of claim 3, wherein the electroplating is performed with an additional 500r/min magnetic stirring.
5. The method according to claim 1, wherein in the step (2), the drying temperature is 70-90 ℃ and the drying time is 48-72 hours; the time of placing in the air is more than or equal to 11 days.
6. The method of claim 1, wherein the carbon nanotubes of step (1) are carboxylated multi-walled carbon nanotubes, and have a diameter of less than 8nm and a length of 10 to 30 μm.
7. The method according to claim 1, wherein the composite plating solution of step (1) is prepared by:
dissolving blue vitriol in deionized water, and adding sulfuric acid to obtain electroplating solution; and (2) taking the carbon nano tube and the lauryl sodium sulfate to be dispersed uniformly in deionized water by ultrasonic, adding the mixture into the electroplating solution, and uniformly mixing under the ultrasonic action to obtain the composite electroplating solution.
8. The method of claim 1, wherein the plastic of step (1) is an ABS plastic.
9. The method according to claim 8, wherein the pre-silvering treatment of step (1) comprises the steps of:
cleaning ABS plastic, sequentially placing the cleaned ABS plastic in silane coupling agent solution and sensitizing solution for surface modification treatment and sensitizing treatment, and then placing the cleaned ABS plastic in chemical silver plating solution for pre-silver plating treatment; after each step of treatment, the water is washed by deionized water and absolute ethyl alcohol;
the silane coupling agent solution is an alcohol solution of 3-mercaptopropyltriethoxysilane, wherein the concentration of the 3-mercaptopropyltriethoxysilane is 10-30 ml/L, and the alcohol solution consists of deionized water and absolute ethyl alcohol with the volume fraction of 1: 9; the surface modification treatment is to soak the workpiece in a silane coupling agent solution for 50-70 minutes;
the sensitizing solution is an aqueous solution of stannous chloride and hydrochloric acid, wherein the concentration of the stannous chloride is 15-25 g/L, the concentration of the hydrochloric acid is 30-50 ml/L, and the hydrochloric acid is a 37 wt% hydrochloric acid solution; the sensitization condition is that the workpiece is soaked in sensitization liquid at normal temperature for 5-15 minutes;
the pre-silver plating treatment is to place a workpiece in a silver ammonia solution at 40-50 ℃, add a reducing agent solution with the same volume for plating for 5-15 minutes, wherein the silver ammonia solution is prepared by dripping 15-20 g/L silver nitrate solution into ammonia water until the solution is clear, and the reducing agent is 7.5-10 g/L glucose aqueous solution.
10. A Cu-CNTs superhydrophobic coating prepared by the method of any of claims 1-9.
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