CN112795965A - Graphene oxide electroplating solution and preparation method and application thereof - Google Patents
Graphene oxide electroplating solution and preparation method and application thereof Download PDFInfo
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25D3/00—Electroplating: Baths therefor
Abstract
The invention provides a graphene oxide electroplating solution and a preparation method and application thereof. The graphene oxide electroplating solution includes a combination of graphene oxide, a surfactant, a stabilizer, and a conductive agent. The preparation method comprises the following steps: and mixing and dispersing graphene oxide, a surfactant, a stabilizer and a conductive agent to obtain the graphene oxide electroplating solution. The preparation method of the graphene oxide electroplating solution provided by the invention is simple, mild in process conditions, environment-friendly, pollution-free and suitable for industrial production. Meanwhile, the graphene coating prepared from the graphene oxide electroplating solution provided by the invention has good compactness and high adhesive force on the metal surface, and is suitable for being used as a metal anticorrosive coating.
Description
Technical Field
The invention belongs to the technical field of graphene, and particularly relates to a graphene oxide electroplating solution and a preparation method and application thereof.
Background
The metal material is damaged by the action of surrounding medium, which is called metal corrosion, and the marine environment is a complex corrosion environment, in which seawater itself is a strong corrosion medium, and at the same time, waves, tides, currents and the like generate low-frequency reciprocating stress and impact on metal components, and in addition, marine microorganisms, attached organisms and metabolites thereof and the like generate direct or indirect acceleration effect on the corrosion process. Thus, marine corrosion is one of the major causes of failure of marine equipment and is also a global metal corrosion problem. The graphene has a single atomic layer structure and is impermeable to molecules, and has excellent properties of high temperature and high humidity resistance, salt mist corrosion resistance, mold resistance and the like. The appearance of the graphene material provides a new idea for developing an anticorrosive coating of metal.
However, graphene coatings prepared in the prior art are poor in compactness and small in adhesion on metal surfaces, and therefore, the graphene coatings are not suitable for being used as metal anticorrosion coatings and are often used as textile coatings. For example, CN109457499A discloses a graphene coated fabric and a preparation process thereof. The preparation process comprises the following steps: uniformly mixing the graphene powder with an adhesive to obtain a mixture a, transferring the mixture a to prepare a membrane, and coating the membrane on a fabric substrate to obtain the graphene coating fabric. The method is suitable for preparing the coating on the surface of the flexible textile, has insufficient adhesion strength on the surface of the metal material, and is easy to fall off.
CN106283609A discloses a preparation process of a graphene coating fabric. The preparation process comprises 5 steps of plate making, solution preparation, coating, drying and shaping and curing, and finally the fabric with high conductivity and antistatic performance is obtained. In the process, the conductive performance and the antistatic performance are provided by doping copper powder or silver powder with the weight ratio of 3-5%, so that the cost is high, the metal powder has certain sensitization on skin contacting with the fabric, and the safety performance is low; in addition, volatile organic solvents such as acetone or butanone are added in the solution preparation step of the process, so that the process is not friendly to human bodies and environment.
CN103469555A discloses a preparation method of an ultraviolet-proof antistatic graphene coating textile fabric. The method is characterized in that: vibrating and dispersing the graphene solution, adding the graphene solution into a water-soluble polyurethane solution, and fully stirring the mixed solution; placing the graphene masking agent solution in a soaking tank of a padding machine, and padding the graphene masking agent on the fabric by a fabric base cloth through a two-soaking and two-rolling process at room temperature; and drying in a high-temperature oven. Although the textile fabric prepared by the process has excellent ultraviolet-proof and antistatic functions, the process requires two-dipping and two-rolling procedures in the preparation process, has complicated process steps, higher cost and lower efficiency, and is not suitable for being used as a metal anticorrosive coating.
Therefore, how to provide a graphene coating which has good compactness, large adhesive force on the metal surface, good corrosion resistance, simple preparation method, mild process conditions, environmental friendliness and suitability for metal corrosion prevention becomes a technical problem to be solved at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a graphene oxide electroplating solution and a preparation method and application thereof. The technical problems of poor uniformity and stability of the graphene oxide electroplating solution are solved through component design of the graphene oxide electroplating solution, and the preparation method of the graphene oxide electroplating solution provided by the invention is simple, mild in process conditions, environment-friendly and suitable for industrial production. Meanwhile, the graphene coating prepared from the graphene oxide electroplating solution provided by the invention has good compactness and high adhesive force on the metal surface, and is suitable for being used as a metal anticorrosive coating.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a graphene oxide electroplating solution comprising a combination of graphene oxide, a surfactant, a stabilizer, and a conductive agent.
According to the invention, the graphene oxide electroplating solution compounded by specific components has good uniformity and stability, and simultaneously has higher conductivity, the preparation method of the graphene oxide electroplating solution provided by the invention is simple, the process condition is mild, the graphene oxide electroplating solution is environment-friendly and is suitable for industrial production, and meanwhile, the graphene coating prepared by the graphene oxide electroplating solution provided by the invention has good compactness, has higher adhesive force on the metal surface, and is suitable for being used as a metal anticorrosive coating.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the object and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
In a preferred embodiment of the present invention, the concentration of graphene oxide in the graphene oxide plating solution is 0.1 to 1g/L (for example, 0.1g/L, 0.2g/L, 0.3g/L, 0.4g/L, 0.5g/L, 0.6g/L, 0.7g/L, 0.8g/L, 0.9g/L, or 1 g/L), and more preferably 0.2 to 0.5 g/L.
Preferably, the surfactant is selected from a nonionic surfactant and/or an anionic surfactant.
Preferably, the nonionic surfactant is selected from any one of emulsifier OP-10, fluorosurfactant, polyethylene oxide polypropylene oxide monobutyl ether, C8-C10 alcohol polyoxyethylene ether or castor oil polyoxyethylene ether or a combination of at least two of the above.
Preferably, the anionic surfactant is selected from any one of sodium dodecyl sulfate, sodium methylene dinaphthalene sulfonate, polyacrylamide, sodium alkyl benzene sulfonate, sodium alpha-olefin sulfonate, sodium alkyl sulfonate, sodium succinate sulfonate, sodium alkyl naphthalene sulfonate or sodium lignin sulfonate or a combination of at least two of the above.
Preferably, the concentration of the surfactant in the graphene oxide electroplating solution is 0.01 to 0.2g/L (for example, 0.01g/L, 0.02g/L, 0.04g/L, 0.06g/L, 0.08g/L, 0.1g/L, 0.12g/L, 0.14g/L, 0.16g/L, 0.18g/L, or 0.2 g/L), and more preferably 0.05 to 0.1 g/L.
In a preferred embodiment of the present invention, the stabilizer is selected from one or a combination of at least two of polyvinylpyrrolidone, sodium cholate, sodium polystyrene sulfonate, and polyvinyl alcohol.
Preferably, the concentration of the stabilizer in the graphene oxide electroplating solution is 0.03 to 0.2g/L (for example, 0.03g/L, 0.04g/L, 0.06g/L, 0.08g/L, 0.1g/L, 0.12g/L, 0.14g/L, 0.16g/L, 0.18g/L, or 0.2 g/L), and more preferably 0.05 to 0.1 g/L.
Preferably, the conductive agent is a soluble sulfate and/or a soluble chloride.
Preferably, the soluble sulfate is selected from any one of potassium sulfate, sodium sulfate or ammonium sulfate or a combination of at least two thereof.
Preferably, the soluble chloride is selected from any one of sodium chloride, potassium chloride or ammonium chloride or a combination of at least two thereof.
Preferably, the concentration of the conductive agent in the graphene oxide electroplating solution is 1 to 100g/L (for example, 1g/L, 5g/L, 10g/L, 20g/L, 30g/L, 40g/L, 50g/L, 60g/L, 70g/L, 80g/L, 90g/L or 100g/L, etc.), and more preferably 5 to 50 g/L.
In a preferred embodiment of the present invention, the graphene oxide plating solution further includes a buffer.
Preferably, the buffer is an acetate buffer and/or a phosphate buffer.
Preferably, the solute in the acetate buffer comprises a combination of acetic acid and sodium acetate.
Preferably, the solute in the phosphate buffer comprises a combination of sodium monohydrogen phosphate and sodium dihydrogen phosphate.
Preferably, the concentration of the buffer in the graphene oxide electroplating solution is 0.2 to 1mol/L (for example, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, or 1 mol/L), and more preferably 0.4 to 0.6 mol/L.
It should be noted that the concentration of the buffer in the graphene oxide plating solution is the sum of the concentrations of the solutes in the buffer, and for the convenience of testing, the pH of the buffer in the present invention can be qualitatively determined as the pH of the graphene plating solution.
In a preferred embodiment of the present invention, the graphene oxide electroplating solution further includes an anodic depolarizer.
Preferably, the anode depolarizer is selected from any one of hydroxylamine hydrochloride, hydrazine sulfate or potassium sodium tartrate or a combination of at least two of them.
Preferably, the concentration of the anode depolarizer in the graphene oxide electroplating solution is 0.05 to 0.5g/L (for example, 0.05g/L, 0.1g/L, 0.15g/L, 0.2g/L, 0.25g/L, 0.3g/L, 0.35g/L, 0.4g/L, 0.45g/L, or 0.5 g/L), and more preferably 0.1 to 0.3 g/L.
In a preferred embodiment of the present invention, the graphene oxide plating solution further includes other additives.
Preferably, the other additive is selected from any one of fluorophenol, fluoroaniline or fluorophenylacetic acid or a combination of at least two of them.
Preferably, the concentration of the other additive in the graphene oxide plating solution is 0.01 to 0.2g/L (for example, 0.01g/L, 0.02g/L, 0.04g/L, 0.06g/L, 0.08g/L, 0.1g/L, 0.12g/L, 0.14g/L, 0.16g/L, 0.18g/L, or 0.2 g/L), and more preferably 0.03 to 0.05 g/L.
Preferably, the solvent of the graphene oxide electroplating solution is deionized water.
The graphene oxide plating solution preferably has a pH of 5 to 8 (for example, 5, 5.2, 5.5, 5.8, 6, 6.3, 6.5, 6.7, 7, 7.2, 7.5, 7.8, 8, or the like), and more preferably 6 to 7.
In a second aspect, the present invention provides a method for preparing a graphene oxide electroplating solution as described in the first aspect, including the following steps:
and mixing and dispersing graphene oxide, a surfactant, a stabilizer and a conductive agent to obtain the graphene oxide electroplating solution.
In a preferred embodiment of the present invention, the temperature of the mixing and dispersing is 0 to 30 ℃ and may be, for example, 0 ℃, 3 ℃, 6 ℃, 9 ℃, 12 ℃, 15 ℃, 18 ℃, 21 ℃, 24 ℃, 27 ℃ or 30 ℃.
Preferably, the mixing and dispersing time is 10-360 min, for example, 10min, 20min, 50min, 70min, 100min, 120min, 150min, 170min, 200min, 230min, 250min, 280min, 300min, 330min or 360 min.
Preferably, the mixing and dispersing method is grinding and/or ultrasonic dispersing.
Preferably, the power of ultrasonic dispersion is 400-1000 kW, for example, 400kW, 450kW, 500kW, 550kW, 600kW, 650kW, 700kW, 750kW, 800kW, 850kW, 900kW, 950kW, 1000kW, or the like can be obtained.
As a preferred technical scheme of the invention, the preparation method specifically comprises the following steps:
under the condition of 0-30 ℃, carrying out grinding dispersion and/or ultrasonic dispersion on graphene oxide, a surfactant, a stabilizer, a conductive agent, an optional buffering agent, an optional anode depolarizer, optional other additives and deionized water for 10-360 min to obtain the graphene oxide electroplating solution;
in the graphene oxide electroplating solution, the concentration of graphene oxide is 0.1-1 g/L, the concentration of a surfactant is 0.01-0.2 g/L, the concentration of a stabilizer is 0.03-0.2 g/L, the concentration of a conductive agent is 1-100 g/L, the concentration of an optional buffering agent is 0.2-1 mol/L, the concentration of an optional anode depolarizer is 0.05-0.5 g/L, and the concentration of optional other additives is 0.01-0.2 g/L; the pH value of the graphene oxide electroplating solution is 5-8.
In a third aspect, the present invention provides the use of a graphene oxide electroplating solution as described in the first aspect for preparing a graphene coating.
Preferably, the graphene coating is used as a metal anticorrosion coating.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, through the interaction among the components in the graphene oxide electroplating solution, the concentration of the surfactant and the concentration of the stabilizer are further controlled within a specific range, the prepared graphene oxide electroplating solution has good uniformity and stability, the Zeta potential of the graphene oxide electroplating solution is 25-42 mV, and the technical problem that the uniformity and stability of the graphene oxide electroplating solution are poor is solved.
(2) According to the invention, the compactness of the prepared graphene coating is good, the adhesion and the compactness on the metal surface are high by controlling the concentrations of the surfactant and the stabilizer within a specific range, the adhesion is 0.1-0.32 MPa, the pressing depth is 3.1-4.3 mu m, the penetration of oxygen, water molecules and other small molecules can be effectively prevented, and after the metal sample plated with the graphene coating is put into 3% hydrochloric acid spray for 24 hours, the graphene coating on the surface layer of the metal sample is complete and is difficult to scrape and has no obvious corrosion phenomenon, so that the prepared graphene coating has good corrosion resistance and is suitable for being used as a metal corrosion-resistant coating.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The sources of some of the components in the examples and comparative examples are as follows:
and (3) graphene oxide: qingdao rock-ocean carbon materials, Inc., HGP-3A;
emulsifier OP-10: OP-10, the science and technology company of Leishu Lingfei, Jiangsu;
fluorine surfactant: DuPont corporation, FS-81;
polyethylene oxide polypropylene oxide monobutyl ether: shanghai Cramar reagent, UCON Lubricant 50-HB-260;
polyvinylpyrrolidone: jiafeng chemical ltd, jia, jiang, K30;
fluorophenol: 206-736-0 of Kaiser chemical Co.Ltd of Shanghai;
fluoroaniline: 206-735-5, Kyoto Kaiser chemical Co.
Example 1
The present embodiment provides a graphene oxide electroplating solution (pH 7) and a preparation method thereof, where the graphene oxide electroplating solution includes the following components:
the preparation method of the graphene oxide electroplating solution comprises the following steps:
and grinding and dispersing the graphene oxide, an emulsifier OP-10, polyvinylpyrrolidone, potassium sulfate and deionized water for 60min at the temperature of 10 ℃ to obtain the graphene oxide electroplating solution.
Example 2
The present embodiment provides a graphene oxide electroplating solution (pH 6) and a preparation method thereof, where the graphene oxide electroplating solution includes the following components:
the preparation method of the graphene oxide electroplating solution comprises the following steps:
and (2) carrying out ultrasonic dispersion on graphene oxide, a fluorine surfactant, sodium cholate, sodium sulfate, sodium monohydrogen phosphate, sodium dihydrogen phosphate, hydroxylamine hydrochloride, fluorophenol and deionized water at the temperature of 18 ℃, wherein the ultrasonic power is 600kW, and the ultrasonic time is 30min, so as to obtain the graphene oxide electroplating solution.
Example 3
The present embodiment provides a graphene oxide electroplating solution (pH 8) and a preparation method thereof, where the graphene oxide electroplating solution includes the following components:
the preparation method of the graphene oxide electroplating solution comprises the following steps:
and (2) grinding and dispersing graphene oxide, sodium dodecyl sulfate, polyvinylpyrrolidone and deionized water for 240min by using a high-speed grinder (the model is German Silusson SCX-7) at the temperature of 20 ℃, then adding sodium chloride, sodium monohydrogen phosphate, sodium dihydrogen phosphate, hydrazine sulfate and fluoroaniline, and performing ultrasonic dispersion for 10min at the temperature of 20 ℃ with the ultrasonic power of 400kW to obtain the graphene oxide electroplating solution.
Example 4
The present embodiment provides a graphene oxide electroplating solution (pH 5) and a preparation method thereof, where the graphene oxide electroplating solution includes the following components:
the preparation method of the graphene oxide electroplating solution comprises the following steps:
and carrying out ultrasonic dispersion on graphene oxide, sodium bismethylenedinaphthalene sulfonate, sodium cholate, ammonium sulfate, acetic acid, sodium acetate, hydrazine sulfate, fluorophenol and deionized water for 10min at the temperature of 30 ℃, wherein the ultrasonic power is 1000kW, so as to obtain the graphene oxide electroplating solution.
Example 5
The present embodiment provides a graphene oxide electroplating solution (pH 6.4) and a preparation method thereof, wherein the graphene oxide electroplating solution includes the following components in concentration:
the preparation method of the graphene oxide electroplating solution comprises the following steps:
and (2) grinding and dispersing graphene oxide, polyethylene oxide polypropylene oxide monobutyl ether, polyvinylpyrrolidone and deionized water for 120min by using a high-speed grinding machine (the model is German Silusson SCX-7) at the temperature of 0 ℃, then adding potassium chloride, sodium dihydrogen phosphate, hydroxylamine hydrochloride and fluorophenol, and performing ultrasonic dispersion for 240min at the temperature of 0 ℃ with the ultrasonic power of 700kW to obtain the graphene oxide electroplating solution.
Example 6
This example provides a graphene oxide plating solution (pH 6) and a method for preparing the same, which are different from example 2 only in that the fluorine surfactant concentration is 0.01g/L, and other conditions are the same as example 2.
Example 7
This example provides a graphene oxide plating solution (pH 6) and a method for preparing the same, which are different from example 2 only in that the fluorine surfactant concentration is 0.2g/L, and other conditions are the same as example 2.
Example 8
This example provides a graphene oxide plating solution (pH 6) and a method for preparing the same, which are different from example 2 only in that the fluorine surfactant concentration is 0.005g/L, and other conditions are the same as example 2.
Example 9
This example provides a graphene oxide plating solution (pH 6) and a method for preparing the same, which are different from example 2 only in that the fluorine surfactant concentration is 0.25g/L, and other conditions are the same as example 2.
Example 10
This example provides a graphene oxide plating solution (pH 6) and a method for preparing the same, which are different from example 2 only in that the concentration of sodium cholate is 0.01g/L, and the other conditions are the same as example 2.
Example 11
This example provides a graphene oxide plating solution (pH 6) and a method for preparing the same, which are different from example 2 only in that the concentration of sodium cholate is 0.2g/L, and the other conditions are the same as example 2.
Example 12
This example provides a graphene oxide plating solution (pH 6) and a method for preparing the same, which are different from example 2 only in that the concentration of sodium cholate is 0.005g/L, and the other conditions are the same as example 2.
Example 13
This example provides a graphene oxide plating solution (pH 6) and a method for preparing the same, which are different from example 2 only in that the concentration of sodium cholate is 0.25g/L, and the other conditions are the same as example 2.
Comparative example 1
This comparative example provides a graphene oxide plating solution (pH 6) and a method for preparing the same, differing from example 2 only in that the graphene oxide plating solution does not contain a fluorine surfactant, and the other conditions are the same as example 2.
Comparative example 2
This comparative example provides a graphene oxide plating solution (pH 6) and a method for preparing the same, which are different from example 2 only in that sodium cholate is not contained in the graphene oxide plating solution, and the other conditions are the same as example 2.
The graphene oxide electroplating solution provided by examples 1 to 13 and comparative examples 1 to 2 is subjected to an electrodeposition in-situ electro-reduction method to prepare a graphene coating on a metal surface. The specific electrodeposition method is as follows: respectively taking a 201-type stainless steel metal substrate plate as a cathode plate and an anode plate, and connecting a water-cooling high-frequency power supply to carry out electroplating to obtain a graphene coating with the thickness of 30 mu m; the distance between the cathode plate and the anode plate is 2mm, the voltage between the cathode plate and the anode plate is set to be 15V, the current is 0.1A, and the frequency of the water-cooling high-frequency power supply is 1000 Hz.
The performance of the graphene oxide electroplating solution and the performance of the prepared graphene coating provided by the above examples and comparative examples are tested, and the test standards are as follows:
zeta potential: the Zeta potential of the graphene oxide electroplating solution was measured using a Nanotrac wave type II Zeta potential tester from Microtrac.
Degree of corrosion: and (3) putting the metal sample plated with the graphene coating into 3% hydrochloric acid spray for 24h, and observing whether the surface of the metal sample plated with the graphene coating is corroded and the corrosion condition. Wherein, no corrosion: the graphene coating on the surface layer of the metal sample is complete and difficult to scrape, and pitting corrosion does not occur on the surface of the metal; level 1 corrosion: the graphene coating on the surface layer of the metal sample is complete and difficult to scrape, and a small amount of pitting corrosion appears on the surface of the metal; and 2, corrosion of grade 2: the graphene coating on the surface layer of the metal sample is complete but can be scraped off, and a small amount of pitting corrosion appears on the surface of the metal sample; and 3, corrosion of grade 3: the graphene coating on the surface layer of the metal sample is incomplete, partial peeling occurs, and a large amount of pitting corrosion appears on the metal surface; and 4, corrosion of grade 4: the graphene coating on the surface layer of the metal sample is completely peeled off, and more pitting corrosion or surface corrosion occurs on the metal surface.
Pressing depth: micrometer scratch tester MST adopting hundred Hege instruments3The penetration depth of the tip was measured by scoring the tip with a ball and applying a normal load of 10N.
Adhesion force: GB/T5270-1985, method for testing the adhesion strength of a metal coating on a metal substrate.
TABLE 1
| Zeta potential/mV | Degree of corrosion | Depth of penetration/. mu.m | adhesion/MPa | |
| Example 1 | 32 | No corrosion | 4.3 | 0.20 |
| Example 2 | 41 | No corrosion | 3.1 | 0.32 |
| Example 3 | 30 | No corrosion | 3.4 | 0.31 |
| Example 4 | 39 | No corrosion | 3.6 | 0.32 |
| Example 5 | 36 | No corrosion | 3.3 | 0.32 |
| Example 6 | 25 | No corrosion | 3.8 | 0.16 |
| Example 7 | 42 | No corrosion | 3.7 | 0.18 |
| Example 8 | 15 | Corrosion at level 4 | 4.8 | 0.03 |
| Example 9 | 45 | Level 2 corrosion | 4.3 | 0.12 |
| Example 10 | 37 | No corrosion | 3.1 | 0.10 |
| Example 11 | 42 | No corrosion | 3.5 | 0.28 |
| Example 12 | 22 | Corrosion at level 4 | 3.2 | 0.05 |
| Example 13 | 43 | Level 2 corrosion | 3.5 | 0.11 |
| Comparative example 1 | 12 | Corrosion at level 4 | 5.0 | 0.02 |
| Comparative example 2 | 6 | Corrosion at level 4 | 4.6 | 0.04 |
The results in table 1 show that the graphene oxide electroplating solution prepared by the method has good uniformity and stability by interacting the components in the graphene oxide electroplating solution, further regulating the content of the components and further controlling the concentrations of the surfactant and the stabilizer within a specific range, and the Zeta potential of the prepared graphene oxide electroplating solution is 25-42 mV; the graphene coating prepared from the graphene oxide electroplating solution provided by the invention has good compactness, and the pressing depth is 3.1-4.3 mu m; meanwhile, the prepared graphene coating has high adhesive force on the metal surface, the adhesive force is 0.1-0.32 MPa, and after a metal sample plated with the graphene coating is placed in 3% hydrochloric acid spray for 24 hours, the graphene coating on the surface layer of the metal sample is complete and difficult to scrape, and no obvious corrosion phenomenon exists, so that the graphene coating prepared from the graphene oxide electroplating solution provided by the invention has good corrosion resistance.
Compared with example 2, if the content of the surfactant in the graphene oxide electroplating solution is low (example 8), the prepared graphene oxide electroplating solution has poor stability, the Zeta potential of the graphene oxide electroplating solution is only 15mV, the adhesion of the graphene coating prepared from the graphene oxide electroplating solution to the metal surface is low and is 0.03MPa, and meanwhile, after the graphene coating sample is placed in 3% hydrochloric acid spray for 24 hours, 4-level corrosion occurs, the graphene coating on the surface layer of the metal sample is completely peeled off, and the corrosion resistance of the graphene coating is poor; if the content of the surfactant in the graphene oxide electroplating solution is high (example 9), although the prepared graphene oxide electroplating solution has good stability and a Zeta potential of 45mV, the adhesion of the graphene coating prepared from the graphene oxide electroplating solution on the metal surface is low and is 0.12MPa, and the corrosion resistance is poor, and after the graphene oxide electroplating solution is put into 3% hydrochloric acid spray for 24 hours, grade 1 corrosion occurs. Therefore, when the concentration range of the surfactant is not in a specific range, the prepared graphene oxide is poor in stability, and the further prepared graphene coating is low in adhesive force on the metal surface and poor in corrosion resistance.
Compared with the example 2, if the content of the stabilizer in the graphene oxide electroplating solution is low (example 12), the prepared graphene oxide electroplating solution is poor in stability, the Zeta potential of the graphene oxide electroplating solution is 22mV, the adhesion of the further prepared graphene coating on the metal surface is low and is 0.05MPa, the graphene coating is poor in corrosion resistance, and after the graphene coating is placed in 3% hydrochloric acid spray for 24 hours, 4-level corrosion occurs; if the content of the stabilizer in the graphene oxide electroplating solution is high (example 13), the adhesion of the prepared graphene coating on the metal surface is low and is 0.11MPa, and the graphene coating has poor corrosion resistance, and after the graphene coating is put into 3% hydrochloric acid spray for 24 hours, 2-level corrosion occurs. Therefore, when the concentration range of the stabilizer is not in a specific range, the prepared graphene oxide is poor in stability, and the further prepared graphene coating is low in adhesive force on the metal surface and poor in corrosion resistance.
Compared with example 2, if the graphene oxide electroplating solution does not contain the surfactant (comparative example 1), the prepared graphene oxide electroplating solution is poor in stability, the Zeta potential of the graphene oxide electroplating solution is 12mV, the adhesion and the corrosion resistance of the graphene coating on the metal surface are poor, the adhesion is 0.02MPa, after the graphene coating is put into 3% hydrochloric acid spray for 24 hours, 4-level corrosion occurs, and the graphene coating on the surface layer of the metal sample is completely peeled off.
Compared with example 2, if the graphene oxide electroplating solution does not contain a stabilizer (comparative example 2), the prepared graphene oxide electroplating solution is poor in stability, the Zeta potential of the graphene oxide electroplating solution is 6mV, the adhesion and the corrosion resistance of the graphene coating on the metal surface are poor, the adhesion is 0.04MPa, and after the graphene coating is placed in 3% hydrochloric acid spray for 24 hours, 4-level corrosion occurs.
In conclusion, through the interaction among the components in the graphene oxide electroplating solution, and further controlling the concentration of the surfactant and the stabilizer within a specific range, the prepared graphene oxide electroplating solution has better uniformity and stability, and the prepared graphene coating has better compactness and corrosion resistance and higher adhesive force with the metal surface.
The applicant states that the process flow of the present invention is illustrated by the above examples, but the present invention is not limited to the above detailed process flow, i.e. it is not meant that the present invention must rely on the above detailed process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A graphene oxide electroplating solution, comprising a combination of graphene oxide, a surfactant, a stabilizer, and a conductive agent.
2. The graphene oxide electroplating solution according to claim 1, wherein the concentration of graphene oxide in the graphene oxide electroplating solution is 0.1 to 1g/L, and more preferably 0.2 to 0.5 g/L;
preferably, the surfactant is selected from a nonionic surfactant and/or an anionic surfactant;
preferably, the nonionic surfactant is selected from any one or a combination of at least two of an emulsifier OP-10, a fluorine surfactant, polyethylene oxide polypropylene oxide monobutyl ether, C8-C10 alcohol polyoxyethylene ether or castor oil polyoxyethylene ether;
preferably, the anionic surfactant is selected from any one or a combination of at least two of sodium dodecyl sulfate, sodium methylene dinaphthalene sulfonate, polyacrylamide, sodium alkyl benzene sulfonate, sodium alpha-olefin sulfonate, sodium alkyl sulfonate, sodium succinate sulfonate, sodium alkyl naphthalene sulfonate or sodium lignin sulfonate;
preferably, the concentration of the surfactant in the graphene oxide electroplating solution is 0.01 to 0.2g/L, and more preferably 0.05 to 0.1 g/L.
3. The graphene oxide electroplating solution according to claim 1 or 2, wherein the stabilizer is selected from any one of or a combination of at least two of polyvinylpyrrolidone, sodium cholate, sodium polystyrene sulfonate, or polyvinyl alcohol;
preferably, the concentration of the stabilizer in the graphene oxide electroplating solution is 0.03-0.2 g/L, and more preferably 0.05-0.1 g/L;
preferably, the conductive agent is a soluble sulfate and/or a soluble chloride;
preferably, the soluble sulfate is selected from any one of potassium sulfate, sodium sulfate or ammonium sulfate or a combination of at least two of the same;
preferably, the soluble chloride is selected from any one of sodium chloride, potassium chloride or ammonium chloride or a combination of at least two thereof;
preferably, the concentration of the conductive agent in the graphene oxide electroplating solution is 1-100 g/L, and more preferably 5-50 g/L.
4. The graphene oxide electroplating solution according to any one of claims 1 to 3, further comprising a buffer;
preferably, the buffer is an acetate buffer and/or a phosphate buffer;
preferably, the solute in the acetate buffer comprises a combination of acetic acid and sodium acetate;
preferably, the solute in the phosphate buffer comprises a combination of sodium monohydrogen phosphate and sodium dihydrogen phosphate;
preferably, the concentration of the buffer in the graphene oxide electroplating solution is 0.2-1 mol/L, and more preferably 0.4-0.6 mol/L.
5. The graphene oxide electroplating solution according to any one of claims 1 to 4, further comprising an anodic depolarizer;
preferably, the anode depolarizer is selected from any one or a combination of at least two of hydroxylamine hydrochloride, hydrazine sulfate or potassium sodium tartrate;
preferably, the concentration of the anode depolarizer in the graphene oxide electroplating solution is 0.05 to 0.5g/L, and more preferably 0.1 to 0.3 g/L.
6. The graphene oxide electroplating solution according to any one of claims 1 to 5, further comprising other additives;
preferably, the other additive is selected from any one of or a combination of at least two of fluorophenol, fluoroaniline or fluoroacetic acid;
preferably, the concentration of other additives in the graphene oxide electroplating solution is 0.01-0.2 g/L, and more preferably 0.03-0.05 g/L;
preferably, the solvent of the graphene oxide electroplating solution is deionized water;
preferably, the pH of the graphene oxide electroplating solution is 5 to 8, and more preferably 6 to 7.
7. A method of preparing the graphene oxide electroplating solution according to any one of claims 1 to 6, wherein the method comprises the steps of:
and mixing and dispersing graphene oxide, a surfactant, a stabilizer and a conductive agent to obtain the graphene oxide electroplating solution.
8. The preparation method according to claim 7, wherein the temperature of the mixing and dispersing is 0-30 ℃;
preferably, the mixing and dispersing time is 10-360 min;
preferably, the mixing and dispersing method is grinding and/or ultrasonic dispersing;
preferably, the power of the ultrasonic dispersion is 400-1000 kW.
9. The method according to claim 7 or 8, comprising the following steps:
under the condition of 0-30 ℃, carrying out grinding dispersion and/or ultrasonic dispersion on graphene oxide, a surfactant, a stabilizer, a conductive agent, an optional buffering agent, an optional anode depolarizer, optional other additives and deionized water for 10-360 min to obtain the graphene oxide electroplating solution;
in the graphene oxide electroplating solution, the concentration of graphene oxide is 0.1-1 g/L, the concentration of a surfactant is 0.01-0.2 g/L, the concentration of a stabilizer is 0.03-0.2 g/L, the concentration of a conductive agent is 1-100 g/L, the concentration of an optional buffering agent is 0.2-1 mol/L, the concentration of an optional anode depolarizer is 0.05-0.5 g/L, and the concentration of optional other additives is 0.01-0.2 g/L; the pH value of the graphene oxide electroplating solution is 5-8.
10. Use of a graphene oxide electroplating solution according to any one of claims 1 to 6 for preparing a graphene coating;
preferably, the graphene coating is used as a metal anticorrosion coating.
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