CN115161640B - Copper-based super-hydrophobic coating and batch production process method and application thereof - Google Patents
Copper-based super-hydrophobic coating and batch production process method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/103—Other heavy metals copper or alloys of copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/40—Metallic substrate based on other transition elements
- B05D2202/45—Metallic substrate based on other transition elements based on Cu
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Abstract
The invention relates to a copper-based superhydrophobic coating and a process method and application of batch production thereof, wherein the process method comprises the steps of firstly immersing a polished copper substrate with preset roughness into 9-11 wt% of hydrochloric acid solution for activation reaction, then immersing the copper substrate into 14-16 wt% of nitric acid solution for etching reaction, and finally immersing the copper substrate into stearic acid ethanol solution for modification reaction to obtain the copper-based superhydrophobic coating. The method can be used for preparing the copper-based superhydrophobic coating after the copper substrate is treated by the low-surface active substances only by combining hydrochloric acid activation with nitric acid etching, and compared with the prior art, the method has the advantages of simple raw materials, no toxic organic matters, simplicity and convenience in operation, no post-treatment process requirement, simplicity in equipment requirement and no limitation on the size of the copper substrate, and can be suitable for batch industrial production of large-size superhydrophobic coatings.
Description
Technical Field
The invention belongs to the field of surface treatment, and relates to a copper-based superhydrophobic coating, a process method for mass production of the copper-based superhydrophobic coating and application of the copper-based superhydrophobic coating.
Background
The super-hydrophobic coating is a material with a contact angle of more than 150 degrees and a rolling angle of less than 10 degrees, and has good self-cleaning, corrosion resistance, ice coating resistance and other performances. At present, the super-hydrophobic coating is applied to the fields of self-cleaning, pollution resistance, ice coating resistance, corrosion resistance, oil-water separation and the like. Currently, electrochemical, thermal cracking, chemical deposition, sol-gel, self-assembly, and the like methods can be used to prepare the superhydrophobic coating.
Compared with other technologies, the wet chemical etching method is easy to control and is suitable for large-scale production of the super-hydrophobic surface. Related researchers have reported that etching agents such as hydrogen peroxide and hydrochloric acid are firstly used for chemical etching, then heat treatment is carried out on an etched substrate, and then stearic acid is used for modification to obtain a super-hydrophobic coating (Surface and Coatings Technology,2019, 362:62-71.), and also have researcher use hydrochloric acid solution for etching, and then AgNO is used for etching 3 The solution was displaced and stearic acid was used to modify the surface of the prepared superhydrophobic iron (Applied Surface Science,2015, 346:458-463.). However, the method needs to add an additional post-treatment process after chemical etching and before immersing stearic acid modification, so that an ideal super-hydrophobic coating can be obtained, and the steps and the complexity of the process method are increased. CN101812680B discloses a preparation method of superhydrophobic copper base, in which the cleaned and dried metallic copper is immersed in a methanol solution of 12-hydroxystearic acid with concentration of 0.005-0.015M, and a rough surface structure is formed on the surface of the metallic copper by immersing at room temperature, so that the superhydrophobic surface is formed without modification of low surface energy, but the method can only be limited to preparation in the methanol solution, and the film prepared by using ethanol as a solvent has no superhydrophobic property, so that the method has great toxicity to environment and human body, increases difficulty degree of preparation, and needs to be immersed in the methanol solution of 12-hydroxystearic acid for a very long time (60-80 h), so that the method cannot be successfully applied to preparation of large-size superhydrophobic coating and large-scale industrial production thereof.
Therefore, there is still a need to develop a simple and convenient process for preparing the superhydrophobic coating, so that the process is suitable for mass production of large-size superhydrophobic coatings.
Disclosure of Invention
In view of the problems existing in the prior art, the invention aims to provide a copper-based superhydrophobic coating and a batch production process method and application thereof. Compared with the prior art, the process method has the advantages of simple raw materials, simple and convenient operation, no toxic organic matters, no post-treatment process requirement, simple equipment requirement and no limitation on the size of the copper matrix, and can be suitable for batch industrial production of large-size superhydrophobic coatings.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a process method for batch production of copper-based superhydrophobic coatings, the process method comprising the following steps:
(1) Polishing the copper matrix to enable the surface roughness of the copper matrix to reach 1.5+/-0.03 mu m, and then immersing the copper matrix into hydrochloric acid solution with the concentration of 9-11 wt% for activation reaction to obtain an activated copper matrix;
(2) Immersing the activated copper matrix in the step (1) into a nitric acid solution with the concentration of 14-16 wt% for etching reaction to obtain an etched copper matrix;
(3) Immersing the etched copper matrix in the step (2) into ethanol solution of stearic acid for modification reaction to obtain the copper-based superhydrophobic coating.
The invention needs to polish the surface of the copper matrix and reach the preset roughness, namely the surface roughness of the matrix reaches 1.5+/-0.03 mu m, and the subsequent steps can be carried out; on one hand, polishing can effectively remove impurities on the surface of the copper matrix, and on the other hand, the polished copper matrix is more beneficial to the follow-up hydrochloric acid activation reaction.
The operation of using hydrochloric acid to perform the activation reaction cannot be omitted, the oxidation film layer on the surface of the copper matrix can be removed by hydrochloric acid activation treatment, so that the fresh pure copper matrix in the copper matrix is exposed, and when the copper matrix is immersed in hydrochloric acid solution for treatment and taken out, the surface of the copper matrix is covered with a layer of liquid film, so that the copper matrix can be effectively prevented from being oxidized again, and the etching reaction in the step (2) is facilitated; other acid solutions cannot be used for replacing the effect of the hydrochloric acid solution, the concentration of the hydrochloric acid solution used in the method is required to be within a certain range, the substrate is passivated due to the fact that the concentration is too high, and the oxide film layer cannot be completely removed due to the fact that the concentration is too low.
The operation of etching reaction by using the nitric acid solution cannot be omitted, the step is needed to be carried out after hydrochloric acid activation, and the exposed copper substrate surface is etched into a micro-nano structure by using the nitric acid solution, so that the micro-nano structure is favorable for forming a super-hydrophobic structure of a copper coating in the later stage; other acid solutions cannot be used for replacing the effect of the nitric acid solution, the concentration of the nitric acid solution used in the method needs to be within a certain range, the excessive etching of the substrate can be caused by the excessive concentration, and the incomplete etching can be caused by the insufficient concentration.
The invention is suitable for preparing copper-based superhydrophobic coatings, and can be applied to substrates made of other materials, such as metal substrates of stainless steel and the like, so that the final product obtains a certain hydrophobic effect, but the hydrophobic capacity of the copper-based superhydrophobic coating is poorer than that of the copper substrate, and even the superhydrophobic effect cannot be achieved.
Compared with the prior art, the process method has the advantages of simple raw materials, simple and convenient operation, no toxic organic matters, no post-treatment process requirements, simple equipment requirements and no limitation on the size of the copper matrix, and can be suitable for batch industrial production of large-size superhydrophobic coatings.
The activation reaction in the step (2) of the present invention is carried out by immersing in a hydrochloric acid solution having a concentration of 9 to 11wt%, for example, 9wt%, 9.2wt%, 9.4wt%, 9.6wt%, 9.8wt%, 10wt%, 10.2wt%, 10.4wt%, 10.6wt%, 10.8wt% or 11wt%, etc., but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned numerical ranges are equally applicable.
The etching reaction in the step (3) of the present invention is performed in a nitric acid solution having a concentration of 14 to 16wt%, for example, 14wt%, 14.2wt%, 14.4wt%, 14.6wt%, 14.8wt%, 15wt%, 15.2wt%, 15.4wt%, 15.6wt%, 15.8wt% or 16wt%, etc., but the etching reaction is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned range are applicable.
The following technical scheme is a preferred technical scheme of the invention, but is not a limitation of the technical scheme provided by the invention, and the technical purpose and beneficial effects of the invention can be better achieved and realized through the following technical scheme.
As a preferable technical scheme of the invention, the method for polishing the copper matrix in the step (1) comprises the step of sequentially polishing by using SiC sand paper with the model number of 500#, 800# and 1000 #.
As a preferable technical scheme of the invention, after the copper matrix is polished in the step (1), the copper matrix is further cleaned and dried before the activation reaction.
The activation reaction is preceded by immersing in a hydrochloric acid solution with a concentration of 9-11 wt% for activation reaction.
Preferably, the washed detergent comprises ethanol.
Preferably, the cleaning comprises ultrasonic cleaning.
Preferably, the washing time is 3 to 8min, for example, 3min, 3.5min, 4min, 4.5min, 5min, 5.5min, 6min, 6.5min, 7min, 7.5min, or 8min, but not limited to the recited values, and other non-recited values within the above range are equally applicable.
In a preferred embodiment of the present invention, the activation reaction time in the step (1) is 25 to 35s, for example, 25s, 26s, 27s, 28s, 29s, 30s, 31s, 32s, 33s, 34s or 35s, etc., but the present invention is not limited to the above-mentioned values, and other values not shown in the above-mentioned value ranges are equally applicable.
In a preferred embodiment of the present invention, the etching reaction time in the step (2) is 2 to 6min, for example, 2min, 2.5min, 3min, 3.5min, 4min, 4.5min, 5min, 5.5min or 6min, but not limited to the above-mentioned values, and other values not listed in the above-mentioned value ranges are equally applicable.
In a preferred embodiment of the present invention, the concentration of stearic acid in the ethanol solution of stearic acid in step (3) is 0.03 to 0.06M, for example, 0.03M, 0.035M, 0.04M, 0.045M, 0.05M, 0.055M or 0.03M, etc., but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned numerical ranges are equally applicable.
The thickness of the stearic acid with low surface energy, which is used in the invention, covered on the copper-based surface has less influence on the superhydrophobic performance, but the time of the modification reaction matched with the stearic acid can be adjusted by changing the concentration of the stearic acid in the ethanol water solution, and when the concentration is increased within a preferred range, the time of the modification reaction can be properly shortened, so that the total time consumption of the working procedure is saved.
In a preferred embodiment of the present invention, the temperature of the modification reaction in the step (3) is 25 to 50 ℃, for example, 25 ℃, 27 ℃, 29 ℃, 31 ℃, 33 ℃, 35 ℃, 37 ℃, 39 ℃, 41 ℃, 43 ℃, 45 ℃, 47 ℃, 49 ℃, 50 ℃ or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned numerical ranges are equally applicable.
Preferably, the time of the modification reaction in the step (3) is 12 to 36 hours, for example, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours, 26 hours, 28 hours, 30 hours, 32 hours, 34 hours or 36 hours, etc., but the present invention is not limited to the listed values, and other non-listed values within the above-mentioned range are equally applicable.
In the step (3) of the invention, the temperature of the modification reaction is related to time, and when the modification temperature is higher, the time can be properly reduced, otherwise, when the modification temperature is lower, the modification time should be properly prolonged, so that the copper coating and the stearic acid are combined to form copper stearate, and a specific micro-nano structure is formed.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) Sequentially polishing a copper matrix by using SiC sand paper with the model number of 500#, 800# and 1000# to ensure that the surface roughness of the copper matrix reaches 1.5+/-0.03 mu m, then carrying out ultrasonic cleaning for 3-8 min in ethanol solution, drying, and then immersing in hydrochloric acid solution with the concentration of 9-11 wt% for 25-35 s to obtain an activated copper matrix;
(2) Immersing the activated copper matrix in the step (1) into a nitric acid solution with the concentration of 14-16 wt% for 2-6 min to obtain an etched copper matrix;
(3) Immersing the etched copper matrix in the step (2) into an ethanol solution of stearic acid with the concentration of 0.03-0.06M, and carrying out modification reaction for 12-36 h at the temperature of 25-50 ℃ to obtain the copper-based superhydrophobic coating.
In a second aspect, the present invention provides a copper-based superhydrophobic coating prepared according to the process of the first aspect.
In a third aspect, the invention provides the use of a copper-based superhydrophobic coating according to the second aspect in the field of corrosion protection.
Compared with the prior art, the invention has at least the following beneficial effects:
according to the method, the copper substrate can be treated by the low-surface-activity substances only through the combination of hydrochloric acid activation and nitric acid etching, and the superhydrophobic copper coating is obtained.
Drawings
FIG. 1 is a macroscopic photograph of a copper-based superhydrophobic coating according to example 1 of the invention;
FIG. 2 is a graph showing the contact angle test results of the copper-based superhydrophobic coating according to example 2 of the invention;
FIG. 3 is a rolling angle test result of the copper-based superhydrophobic coating of example 3 of the invention.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a process method for batch production of copper-based superhydrophobic coatings, which comprises the following steps:
(1) Sequentially polishing copper matrixes with the size specification of 15mm by using SiC sand paper with the model number of 500#, 800# and 1000# to enable the surface roughness of the copper matrixes to reach 1.5+/-0.03 mu m, then carrying out ultrasonic cleaning in ethanol solution for 5min, drying, and immersing the copper matrixes into hydrochloric acid solution with the concentration of 10wt% for 30s of activation reaction to obtain activated copper matrixes;
(2) Immersing the activated copper matrix in the step (1) into a nitric acid solution with the concentration of 15wt% for 2min of etching reaction to obtain an etched copper matrix;
(3) Immersing the etched copper matrix in the step (2) into an ethanol solution of stearic acid with the concentration of 0.03M, and carrying out a modification reaction at 40 ℃ for 12 hours to obtain the copper-based superhydrophobic coating.
Example 2
The embodiment provides a process method for batch production of copper-based superhydrophobic coatings, which comprises the following steps:
(1) Sequentially polishing copper matrixes with the size specification of 100mm by using SiC sand paper with the model number of 500#, 800# and 1000# to ensure that the surface roughness of the copper matrixes reaches 1.5+/-0.03 mu m, then carrying out ultrasonic cleaning in ethanol solution for 5min, drying, and immersing the copper matrixes in hydrochloric acid solution with the concentration of 10wt% for 30s to obtain activated copper matrixes;
(2) Immersing the activated copper matrix in the step (1) into a nitric acid solution with the concentration of 15wt% for 4min of etching reaction to obtain an etched copper matrix;
(3) Immersing the etched copper matrix in the step (2) into an ethanol solution of stearic acid with the concentration of 0.04M, and carrying out modification reaction at 25 ℃ for 18 hours to obtain the copper-based superhydrophobic coating.
Example 3
The embodiment provides a process method for batch production of copper-based superhydrophobic coatings, which comprises the following steps:
(1) Sequentially polishing copper matrixes with the size specification of 300mm by using SiC sand paper with the model number of 500#, 800# and 1000# to ensure that the surface roughness of the copper matrixes reaches 1.5+/-0.03 mu m, then carrying out ultrasonic cleaning in ethanol solution for 5min, drying, and immersing the copper matrixes in hydrochloric acid solution with the concentration of 10wt% for 30s to obtain activated copper matrixes;
(2) Immersing the activated copper matrix in the step (1) into a nitric acid solution with the concentration of 15wt% for 6min of etching reaction to obtain an etched copper matrix;
(3) Immersing the etched copper matrix in the step (2) into an ethanol solution of stearic acid with the concentration of 0.06M, and carrying out a modification reaction at 50 ℃ for 24 hours to obtain the copper-based superhydrophobic coating.
Example 4
The embodiment provides a process method for batch production of copper-based superhydrophobic coatings, which comprises the following steps:
(1) Sequentially polishing copper matrixes with the size specification of 200mm by using SiC sand paper with the model number of 500#, 800# and 1000# to ensure that the surface roughness of the copper matrixes reaches 1.5+/-0.03 mu m, then carrying out ultrasonic cleaning in ethanol solution for 8min, drying, and then immersing the copper matrixes in 11wt% hydrochloric acid solution for 35s of activation reaction to obtain activated copper matrixes;
(2) Immersing the activated copper matrix in the step (1) into a nitric acid solution with the concentration of 16wt% for 5min of etching reaction to obtain an etched copper matrix;
(3) Immersing the etched copper matrix in the step (2) into an ethanol solution of stearic acid with the concentration of 0.05M, and carrying out a modification reaction for 30 hours at 35 ℃ to obtain the copper-based superhydrophobic coating.
Example 5
The embodiment provides a process method for batch production of copper-based superhydrophobic coatings, which comprises the following steps:
(1) Sequentially polishing 50 mm-sized copper substrates by using 500#, 800# and 1000# SiC sand paper to enable the surface roughness of the copper substrates to reach 1.5+/-0.03 mu m, then carrying out ultrasonic cleaning in ethanol solution for 3min, drying, and immersing in 9wt% hydrochloric acid solution for 25s of activation reaction to obtain activated copper substrates;
(2) Immersing the activated copper matrix in the step (1) into a nitric acid solution with the concentration of 14wt% for 3min of etching reaction to obtain an etched copper matrix;
(3) Immersing the etched copper matrix in the step (2) into an ethanol solution of stearic acid with the concentration of 0.02M, and carrying out a modification reaction at 25 ℃ for 36 hours to obtain the copper-based superhydrophobic coating.
Example 6
This example provides a process for the mass production of copper-based hydrophobic coatings, which is identical to example 1 except that the activation reaction for 30s described in step (1) is adjusted to 15 s.
Example 7
This example provides a process for the mass production of copper-based hydrophobic coatings, which is identical to example 1 except that the activation reaction for 30s described in step (1) is adjusted to 45 s.
Example 8
The present embodiment provides a process method for batch production of copper-based hydrophobic coating, and the process method is identical to that of embodiment 1 except that the etching reaction performed for 2min in step (2) is adjusted to 1 min.
Example 9
The present embodiment provides a process method for batch production of copper-based hydrophobic coating, and the process method is identical to that of embodiment 1 except that the etching reaction performed for 2min in step (2) is adjusted to 7 min.
Example 10
The present example provides a process for mass production of copper-based hydrophobic coating, which is identical to that of example 1 except that the modification reaction performed for 12 hours in step (3) is adjusted to 10 hours.
Example 11
The present example provides a process for mass production of copper-based superhydrophobic coatings, which is identical to that of example 1 except that the modification reaction performed for 12 hours in step (3) is adjusted to 38 hours.
Example 12
This example provides a process for the mass production of copper-based hydrophobic coatings, which is identical to example 1 except that in step (3), the etched copper substrate of step (2) is immersed in an ethanol solution of stearic acid having a concentration of 0.01M.
Example 13
The present example provides a process for mass production of copper-based superhydrophobic coatings, which is identical to example 1 except that in step (3), the etched copper substrate of step (2) is immersed in an ethanol solution of stearic acid having a concentration of 0.08M.
Comparative example 1
The comparative example provides a process method for batch production of copper-based hydrophobic coatings, wherein in the process method, a copper substrate is not polished in the step (1), namely, in the step (1), the copper substrate with the size specification of 15mm is immersed in ethanol solution for ultrasonic cleaning for 5min and drying, and then immersed in hydrochloric acid solution with the concentration of 10wt% for 30s for activation reaction, so as to obtain an activated copper substrate; except for this, the steps (2) and (3) of this example are identical to those of example 1.
Comparative example 2
The comparative example provides a process method for batch production of copper-based hydrophobic coatings, wherein the step (1) of the process method comprises the steps of sequentially polishing a copper substrate with the size specification of 15mm by using SiC abrasive paper with the model number of 500# and 800# to ensure that the surface roughness of the copper substrate reaches 2.2+/-0.03 mu m, then carrying out ultrasonic cleaning in ethanol solution for 5min and drying, and then immersing the copper substrate in hydrochloric acid solution with the concentration of 10wt% for 30s for activation reaction to obtain an activated copper substrate; the comparative example was identical to example 1 in step (2) and step (3).
Comparative example 3
The comparative example provides a process method for batch production of copper-based hydrophobic coatings, wherein the step (1) of the process method comprises the steps of sequentially polishing a copper substrate with the size specification of 15mm by using SiC sand paper with the model number of 500#, 800#, 1000# and 1200# to ensure that the surface roughness of the copper substrate reaches 1.2+/0.03 mu m, then carrying out ultrasonic cleaning in ethanol solution for 5min, drying, and then immersing in hydrochloric acid solution with the concentration of 10wt% for 30s for activation reaction to obtain an activated copper substrate; the comparative example was identical to example 1 in step (2) and step (3).
Comparative example 4
The comparative example provides a process method for batch production of copper-based hydrophobic coatings, wherein hydrochloric acid solution is not used for carrying out an activation reaction in the step (1), namely, step (1) is to sequentially polish copper matrixes with the size specification of 15mm by using SiC sand paper with the model number of 500#, 800# and 1000# so that the surface roughness of the copper matrixes reaches 1.5+/-0.03 mu m, and then ultrasonic cleaning is carried out in ethanol solution for 5min and drying is carried out to obtain the copper matrixes; the comparative example was identical to example 1 in step (2) and step (3).
Comparative example 5
This comparative example provides a process for mass production of copper-based hydrophobic coating, which is exactly the same as example 1 except that the activation reaction is performed for 30 seconds by immersing in a hydrochloric acid solution having a concentration of 7wt% in step (1).
Comparative example 6
This comparative example provides a process for mass production of copper-based hydrophobic coating, which is exactly the same as example 1 except that the activation reaction is performed for 30 seconds by immersing in a 13wt% hydrochloric acid solution in step (1).
Comparative example 7
The present comparative example provides a process for mass production of copper-based hydrophobic coating, which does not use nitric acid solution for etching reaction, i.e. omits step (2), and only sequentially performs step (1) and step (3), and the steps (1) and (3) are identical to those of example 1.
Comparative example 8
This comparative example provides a process for mass production of copper-based hydrophobic coating, which is exactly the same as example 1 except that the etching reaction is performed in step (2) by immersing in a nitric acid solution having a concentration of 12wt% for 2 minutes.
Comparative example 9
This comparative example provides a process for mass production of copper-based hydrophobic coating, which is exactly the same as example 1 except that the etching reaction is performed in step (2) by immersing in a nitric acid solution having a concentration of 18wt% for 2 minutes.
Comparative example 10
The comparative example provides a process method for mass production of stainless steel-based hydrophobic coatings, which comprises the following steps:
(1) Sequentially polishing stainless steel matrixes with the size specification of 15mm by using SiC sand paper with the model number of 500#, 800# and 1000# to enable the surface roughness of the stainless steel matrixes to reach 1.5+/-0.03 mu m, then carrying out ultrasonic cleaning in ethanol solution for 5min, drying, and then immersing the stainless steel matrixes in hydrochloric acid solution with the concentration of 10wt% for 30s to obtain activated stainless steel matrixes;
(2) Immersing the activated stainless steel substrate in the step (1) into a nitric acid solution with the concentration of 15wt% for 2min of etching reaction to obtain an etched stainless steel substrate;
(3) Immersing the etched stainless steel substrate in the step (2) into an ethanol solution of stearic acid with the concentration of 0.03M, and carrying out a modification reaction at 40 ℃ for 12 hours to obtain the stainless steel-based hydrophobic coating.
Uniformly testing the super-hydrophobic coatings or the hydrophobic coatings obtained in the examples and the comparative examples to obtain contact angle and rolling angle test results; fig. 1 and 2 are macroscopic images and contact angle test results of the copper-based superhydrophobic coatings according to the embodiments 1 and 2, respectively, and it can be seen from the figures that the contact angles are 154.2 ° and 155.3 °, respectively; FIG. 3 is a graph showing the results of the rolling angle test of the copper-based superhydrophobic coating according to example 3 of the invention, wherein the rolling angle is 6.5 degrees; the test results for other examples and comparative examples are also recorded in table 1.
TABLE 1
Note that: "-" means that the roll angle test cannot be performed and that no effective measurement results can be obtained.
As can be seen from table 1:
(1) The process methods in the embodiments 1 to 5 can be adopted to obtain the copper-based superhydrophobic coating with the contact angle larger than 150 degrees and the rolling angle smaller than 10 degrees, and the process method disclosed by the invention can be suitable for the treatment of copper matrixes with smaller specifications (15 mm is 15 mm) and the treatment of copper matrixes with larger specifications (300 mm is 300 mm), and the method disclosed by the invention is not limited to the specific copper matrix size, has good adaptability and can be reasonably adjusted according to actual production requirements in combination with cost control;
(2) Comparing example 1 with comparative examples 1-3, it was found that comparative example 1 was not sanded and the resulting coating had poor water repellency with a contact angle of only 120.2 °; while the polishing roughness of the copper matrix in step (1) in comparative example 2 was insufficient to achieve a predetermined roughness of 1.5.+ -. 0.03. Mu.m, the surface of the copper matrix in comparative example 3 was excessively polished, and the water repellency of the coating obtained by both was reduced as compared with that of example 1, but it was still excellent in water repellency, and it was seen that further obtaining a superhydrophobic structure required the matrix to achieve a specific roughness in the early stage;
(3) Comparing example 1 with examples 6-7 and comparative examples 4-6, it was found that under a suitable hydrochloric acid concentration, insufficient (example 6) or too long (example 7) activation time of hydrochloric acid had an effect on the hydrophobic ability of the coating, and the resulting coating had good hydrophobic effect although the contact angle was reduced and the rolling angle was increased compared to the coating obtained in example 1; in comparative example 4, no hydrochloric acid activation was used, the contact angle of the resulting coating was significantly reduced, only 138.2 °, and the hydrophobic ability was severely lost; the hydrochloric acid concentration used in comparative example 5 was 7wt% less than the preferred range, and the oxide scale of the substrate could not be completely removed, and the hydrochloric acid concentration used in comparative example 6 was 13wt% more than the preferred range, and the substrate could be passivated to some extent, so that the hydrophobic ability of both was inferior to that of the coating obtained in example 1; it can be seen that when the surface oxide skin can be completely removed by controlling the activation of hydrochloric acid but no further passivation is caused, the formation of the coating with the super-hydrophobic structure is more facilitated;
(4) Comparing example 1 with examples 8-9 and comparative examples 7-9, it was found that under a suitable nitric acid concentration, the insufficient etching reaction time (example 8) or too long etching reaction time (example 9) has an effect on the hydrophobic ability of the coating, and the coating obtained in example 8 has a good hydrophobic effect although the contact angle and the rolling angle of the coating obtained in example 1 are reduced; in example 9, too long etching time makes the surface damage of the substrate serious, the contact angle of the obtained coating is only 128.9 degrees, and the effective rolling angle cannot be measured; in comparative example 7, no nitric acid was used for etching, the contact angle of the obtained coating was significantly reduced, only 122.4 °, and the hydrophobic ability was severely lost; the nitric acid concentration used in comparative example 8 was 12wt% less than the preferred range, and was not able to give a completely etched structure to the activated copper substrate, resulting in a coating having a lower water repellency than the coating obtained in example 1; comparative example 9 uses a nitric acid concentration of 18wt%, above the preferred range, which would result in excessive etching of the substrate, resulting in a coating with a contact angle of only 138.9; it can be seen that the etching of nitric acid is a necessary condition for generating a specific structure, and the control of the etching of nitric acid can enable the activated substrate to reach a proper etching degree, which is more beneficial to the formation of the coating of the superhydrophobic structure;
(5) Comparing example 1 with examples 10-11, it was found that when the concentration of stearic acid is proper, example 10 adjusts the modification time to less than 10 hours in the preferred range, which results in less than optimal reaction of stearic acid with copper, thus slightly decreasing the degree of hydrophobicity, and example 11 adjusts the modification time to 38 hours above the preferred range, which results in a superhydrophobic coating, but the process takes longer; therefore, in the proper modification time, stearic acid and copper react sufficiently to generate proper micro-nano structure, the reaction degree is proper and the time can be saved;
(6) Comparing example 1 with examples 12-13, it was found that the concentration of stearic acid used in example 12 is lower than the preferred range, resulting in insufficient reaction of stearic acid with copper, reduced hydrophobic ability compared to example 1, and the concentration of stearic acid used in example 13 is higher than the preferred range, and a superhydrophobic coating can be obtained, but the contact angle and rolling angle are less different from those of example 1, and the amount of stearic acid exceeding the preferred range does not further effectively increase hydrophobic ability, but additionally increases production cost;
(7) Comparing example 1 with comparative example 10, it is found that the comparative example 10 cannot obtain a superhydrophobic coating by using stainless steel as a substrate, the obtained coating has poor hydrophobicity, the contact angle of the coating is only 100.5 degrees, and the rolling angle cannot be measured, and the process method is only applicable to the production of the superhydrophobic coating of a copper substrate;
in conclusion, the copper substrate coating can obtain good super-hydrophobic performance under proper parameters through simple activation and erosion actions and then through the reaction of stearic acid and copper to generate copper stearate to form a specific micro-nano structure.
The detailed structural features of the present invention are described in the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (10)
1. The process method for batch production of the copper-based superhydrophobic coating is characterized by comprising the following steps of:
(1) Polishing the copper matrix to enable the surface roughness of the copper matrix to reach 1.5+/-0.03 mu m, and then immersing the copper matrix into hydrochloric acid solution with the concentration of 9-11 wt% for an activation reaction for 25-35 s to obtain an activated copper matrix;
(2) Immersing the activated copper matrix in the step (1) into a nitric acid solution with the concentration of 14-16 wt% for etching reaction for 2-6 min to obtain an etched copper matrix;
(3) Immersing the etched copper matrix in the step (2) into ethanol solution of stearic acid for modification reaction for 12-36 h, wherein the concentration of stearic acid in the ethanol solution of stearic acid is 0.03-0.06M, and obtaining the copper-based superhydrophobic coating.
2. The process of claim 1, wherein the method of polishing the copper substrate of step (1) comprises polishing sequentially using SiC sandpaper of model 500#, 800# and 1000 #.
3. The process of claim 1, further comprising washing and drying after the polishing of the copper substrate in step (1) and before the activation reaction.
4. A process according to claim 3, wherein the cleaned detergent comprises ethanol.
5. A process according to claim 3, wherein the cleaning comprises ultrasonic cleaning.
6. A process according to claim 3, wherein the washing is for a period of 3 to 8 minutes.
7. The process according to claim 1, wherein the temperature of the modification reaction in step (3) is 25 to 50 ℃.
8. A process according to claim 1, characterized in that it comprises the steps of:
(1) Sequentially polishing a copper matrix by using SiC sand paper with the model number of 500#, 800# and 1000# to ensure that the surface roughness of the copper matrix reaches 1.5+/-0.03 mu m, then carrying out ultrasonic cleaning for 3-8 min in ethanol solution, drying, and then immersing in hydrochloric acid solution with the concentration of 9-11 wt% for 25-35 s to obtain an activated copper matrix;
(2) Immersing the activated copper matrix in the step (1) into a nitric acid solution with the concentration of 14-16 wt% for 2-6 min to obtain an etched copper matrix;
(3) Immersing the etched copper matrix in the step (2) into an ethanol solution of stearic acid with the concentration of 0.03-0.06M, and carrying out modification reaction for 12-36 h at the temperature of 25-50 ℃ to obtain the copper-based superhydrophobic coating.
9. A copper-based superhydrophobic coating prepared according to the process of any one of claims 1-8.
10. Use of the copper-based superhydrophobic coating according to claim 9 in the field of corrosion protection.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103074629A (en) * | 2012-12-19 | 2013-05-01 | 上海电力学院 | Cupronickel B30 having super-hydrophobic surface and preparation method thereof |
| CN103469215A (en) * | 2013-09-06 | 2013-12-25 | 许昌学院 | Copper based super-hydrophobic surface with low friction coefficient and preparation method thereof |
| CN104888498A (en) * | 2015-06-12 | 2015-09-09 | 东南大学 | Preparation method of durable super-hydrophobic super-oleophylic foamy copper for oil and water separation |
| CN106367756A (en) * | 2016-12-02 | 2017-02-01 | 江苏理工学院 | Preparation method of hydrophobic micro-nano structure aluminum surface |
| KR101837309B1 (en) * | 2016-12-07 | 2018-03-12 | 동국대학교 산학협력단 | A method for creating a superhydrophobic coating on a copper substrate |
| CN109127328A (en) * | 2018-07-13 | 2019-01-04 | 西安交通大学 | A kind of method of metal surface building super-hydrophobic coat |
| CN109518175A (en) * | 2018-11-29 | 2019-03-26 | 鲁东大学 | A kind of super-hydrophobic coating for metal surfaces and preparation method thereof |
| CN113680625A (en) * | 2021-08-16 | 2021-11-23 | 四川工程职业技术学院 | Method for constructing super-hydrophobic modified layer on surface of aluminum-copper alloy |
| CN114517055A (en) * | 2020-11-18 | 2022-05-20 | 中国石油化工股份有限公司 | Super-hydrophobic compound modified metal surface hydrophobic layer and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150124540A (en) * | 2014-04-28 | 2015-11-06 | 삼성디스플레이 주식회사 | Echtant and method for manufacturing display device using the same |
-
2022
- 2022-06-29 CN CN202210757487.2A patent/CN115161640B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103074629A (en) * | 2012-12-19 | 2013-05-01 | 上海电力学院 | Cupronickel B30 having super-hydrophobic surface and preparation method thereof |
| CN103469215A (en) * | 2013-09-06 | 2013-12-25 | 许昌学院 | Copper based super-hydrophobic surface with low friction coefficient and preparation method thereof |
| CN104888498A (en) * | 2015-06-12 | 2015-09-09 | 东南大学 | Preparation method of durable super-hydrophobic super-oleophylic foamy copper for oil and water separation |
| CN106367756A (en) * | 2016-12-02 | 2017-02-01 | 江苏理工学院 | Preparation method of hydrophobic micro-nano structure aluminum surface |
| KR101837309B1 (en) * | 2016-12-07 | 2018-03-12 | 동국대학교 산학협력단 | A method for creating a superhydrophobic coating on a copper substrate |
| CN109127328A (en) * | 2018-07-13 | 2019-01-04 | 西安交通大学 | A kind of method of metal surface building super-hydrophobic coat |
| CN109518175A (en) * | 2018-11-29 | 2019-03-26 | 鲁东大学 | A kind of super-hydrophobic coating for metal surfaces and preparation method thereof |
| CN114517055A (en) * | 2020-11-18 | 2022-05-20 | 中国石油化工股份有限公司 | Super-hydrophobic compound modified metal surface hydrophobic layer and preparation method thereof |
| CN113680625A (en) * | 2021-08-16 | 2021-11-23 | 四川工程职业技术学院 | Method for constructing super-hydrophobic modified layer on surface of aluminum-copper alloy |
Non-Patent Citations (1)
| Title |
|---|
| Varshney, P.Durable and regenerable superhydrophobic coatings for brass surfaces with excellent self-cleaning and anti-fogging properties prepared by immersion technique.Tribology International.2018,第123卷17-25. * |
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