CN113371696A - Surface-modified oversized graphene for efficient corrosion prevention and preparation and application thereof - Google Patents
Surface-modified oversized graphene for efficient corrosion prevention and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of functionalized modification of a molecular layer of graphene, and provides surface-modified oversized graphene for efficient corrosion prevention and preparation and application thereof, wherein the surface-modified oversized graphene is subjected to surface modification on the oversized graphene by adopting a reducing agent, and block copolymerization is carried out on the surface of the graphene to form a water-dispersible modified layer of the molecular layer; the mass ratio of the reducing agent to the oversized graphene oxide is (8-15) to 1; the reducing agent is a reaction product of an anhydride and an electroactive monomer. The prepared oversized graphene with the modified surface is formed into dispersed slurry, has wide applicability, is suitable for a water-based epoxy resin system, a water-based acrylic resin system and a water-based polyurethane system, and saves a large amount of cost for large-scale production.
Description
Technical Field
The invention relates to the technical field of graphene molecular level functionalized modification, in particular to surface-modified oversized graphene for efficient corrosion prevention and preparation and application thereof.
Background
Graphene, a novel two-dimensional material, is attracting attention because of its excellent physical and chemical properties. At present, graphene is widely applied to the fields of photoelectric devices, sensors, novel functional composite materials and energy storage. At present, the problems of poor dispersibility, easy stacking of sheets and the like easily exist in the using process of graphene, which is one of the bottlenecks limiting further industrial application of graphene. A large number of research results show that the problems of poor graphene dispersibility and easy stacking are in a certain relationship with the structure of graphene, the graphene is easy to form a large number of oxygen-containing functional groups (epoxy groups, hydroxyl groups, carboxyl groups and other functional groups) and defects on a lamellar structure of the graphene in the preparation process, and interaction force is easy to exist among the functional groups and the defects to cause the stacking phenomenon; however, in view of the existence of the oxygen-containing functional group of the lamellar structure, researchers remove the oxygen-containing functional group on the lamellar structure of the graphene to a certain extent by a reduction method, but easily damage the conjugated structure of the graphene in the reduction process, and simultaneously cause new defects and holes on the surface of the graphene, so that the intrinsic excellent physicochemical properties of the reduced graphene and the graphene still have great difference, and the dispersibility of the reduced graphene in the actual use process is not expected. However, most researchers have adopted the method of improving the dispersibility of graphene in water by performing a functionalization reaction such as ring opening, esterification and amidation of oxygen-containing functional groups on the surface of a graphene lamellar structure, and reducing the occurrence of stacking phenomenon between graphene by utilizing intercalation of small molecules between graphene.
Another commercial application of graphene is to prepare a coating by compounding the graphene with a composite material for metal corrosion prevention. The graphene has a unique two-dimensional honeycomb lamellar structure, a large specific surface area and excellent thermal stability and chemical stability, so that an effective physical barrier layer can be formed after the graphene is compounded with an aqueous resin system, and water vapor and corrosive media are effectively prevented from permeating. At present, the most technologies are adopted in the using process of the coating, namely, the graphene is directly added into a resin system, but the technical problems of poor graphene dispersibility and the like exist; secondly, some functionalized graphene is added into a coating system, but the added graphene is generally poor in compatibility with the system or the functionalized graphene is complicated in preparation process and increased in production cost; more importantly, a large amount of defects which cannot be repaired exist on the surface of some functionalized graphene, so that the physical barrier effect of the graphene added into the coating as an anti-corrosion coating is reduced, and the application range of the graphene is greatly limited.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides surface-modified oversized graphene for efficient corrosion prevention and preparation and application thereof.
The purpose of the invention is realized by the following technical scheme:
the invention provides surface-modified oversized graphene for efficient corrosion prevention, which is subjected to surface modification by adopting a reducing agent and is polymerized on the surface of the graphene to form a water-dispersible modification layer on a molecular layer; the mass ratio of the reducing agent to the oversized graphene oxide is (8-15) to 1; the reducing agent is a reaction product of an acid anhydride and an electroactive monomer; the thickness of the oversized graphene is 0.34-1 nm, and the sheet diameter is 20-100 microns.
Preferably, the mass ratio of the acid anhydride to the electroactive monomer is 1: (0.3-3).
Preferably, the acid anhydride is a binary acid anhydride, specifically selected from one or more of maleic anhydride, succinic anhydride, cinnamic anhydride and glutaric anhydride.
Preferably, the electroactive monomer is one or more of aniline, methylaniline and ethylaniline.
The invention also provides a preparation method of the surface-modified oversized graphene for efficient corrosion prevention, which comprises the following steps:
A. weighing oversized graphene oxide according to the mass ratio, adding the oversized graphene oxide into water, and performing ultrasonic dispersion to form uniform graphene oxide dispersion liquid;
B. weighing a reducing agent according to a mass ratio, adding the reducing agent into a mixed solution formed by water and an organic solvent, uniformly stirring, adding the mixture into the graphene oxide dispersion liquid prepared in the step A, and stirring to form a uniform dispersion liquid;
C. reacting the uniform dispersion liquid prepared in the step B at the temperature of 60-120 ℃ for 18-72 hours to form a black dispersion liquid;
D. and D, repeatedly washing the black dispersion liquid completely reacted in the step C to obtain the surface-modified oversized graphene.
Preferably, in the step a, the mass concentration of the oversized graphene oxide in the graphene oxide dispersion liquid is 0.05-5 mg/ml; in the step B, the mixing mass ratio of the deionized water to the organic solvent is 1: (0.25 to 3).
Preferably, the organic solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide; the mass concentration of the oversized graphene oxide in the graphene oxide dispersion liquid is 1-2 mg/ml.
Preferably, in the step C, the uniform dispersion liquid reacts for 24-36 hours at the temperature of 80-95 ℃.
Preferably, in step D, the solvent used for the washing is 1: 4: 1, acetone, deionized water and ethyl acetate.
The invention also provides a water-based slurry prepared from the surface-modified oversized graphene for efficient corrosion prevention, wherein the water-based slurry is obtained by dispersing the surface-modified oversized graphene in water; in the aqueous slurry, the concentration of the surface-modified oversized graphene is 0.1-1 wt.%.
Preferably, the dispersion is carried out by any dispersion method such as ultrasonic, high-speed stirring, grinding dispersion and the like and a combination dispersion method thereof.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the method, a reactant of anhydride and an electroactive aniline monomer is selected as a reducing agent to reduce the oversized graphene oxide, the oversized graphene oxide is subjected to in-situ polymerization on the surface of the oversized graphene, and the thickness of a modified layer formed on the surface of the graphene by a copolymer is controlled by controlling reaction temperature, reaction time and the proportion of an organic solvent and deionized water; secondly, due to the existence of electrostatic physical adsorption and conjugation, the copolymer grows along the surface plane of the graphene to form a two-dimensional sheet layered structure; moreover, as the molecular layer hydrolyzed anhydride grafted electroactive polymer exists on the surface of the graphene and contains hydrophilic carboxylic acid groups, the stacking effect between graphene layers is weakened, and the dispersion effect of the graphene in an aqueous system is improved;
2. after the graphene surface modification molecular layer carboxylic acid group is grafted with the electroactive polymer, the electroactive polymer is added into a water-based coating system, the carboxylic acid group forms an imide structure under the heating condition, the hydrophobicity of the coating is greatly improved, the physical shielding effect of the graphene lamellar structure can be fully utilized by the layered hydrophobic structure converted from hydrophilicity, the surface modification electroactive polymer has better conductivity, and after the electroactive polymer is added into the coating system, a passivation layer can be quickly formed on the metal surface under the condition of existence of a corrosion medium, so that the corrosion resistance of the coating is further improved;
3. in the preparation process of the graphene water dispersion slurry, safe and pollution-free water, ethanol, methanol, propylene glycol, isopropanol and the like are used as reaction solvents, no additional oxidant is needed to initiate polymerization of a molecular layer polymer, and high temperature and long-time reaction are not needed, so that a large amount of cost is saved for large-scale production;
4. the prepared graphene dispersion slurry has wide applicability, and is suitable for a water-based epoxy resin system, a water-based acrylic resin system and a water-based polyurethane system;
5. a small amount of graphene dispersion slurry is added into a water-based anticorrosive coating system, so that the anticorrosive performance, the adhesive force and the storage stability of the water-based coating can be effectively improved, because large-size graphene has a better lamellar spreading effect in a resin system after being modified by a conjugated block copolymer molecular layer, the physical barrier effect of resin can be improved, in addition, under the condition that a corrosive medium exists, an electroactive polymer modified by the graphene surface has electronegativity on the surface and selectivity to ions, and can prevent Cl-、SO4 2-When anions permeate into a coating system, the barrier property is effectively improved, wherein the surface drying time of the aqueous anticorrosive coating added with the oversized graphene dispersion slurry is 45min, the coating is dried for 5h, the 50cm drop hammer impact-resistant experimental coating is not damaged, a small amount of cracks exist in a 2mm flexibility test, the salt spray resistance can reach 4500h, the adhesive force is 6MPa, the coating is not layered after being placed at room temperature for 3 months, and the performance is obviously improved compared with the performance without the addition of the aqueous anticorrosive coating.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
fig. 1 is a scanning electron microscope image of an electroactive polymer molecule layer modified oversized graphene prepared in example 5 of the invention;
FIG. 2 is a transmission electron microscope image of an electroactive polymer molecule layer modified oversized graphene prepared in example 5 of the present invention;
fig. 3 is a raman spectrum of the electroactive polymer molecule level modified oversized graphene prepared in example 5 of the present invention;
FIG. 4 is an X-ray photoelectron spectrum of a super-large graphene modified at the molecular level by an electroactive polymer prepared in example 5 of the present invention;
fig. 5 is a coating polarization curve diagram of oversized graphene slurry prepared according to the proportion of examples 1, 2, 3, 4, 5 and 6 of the invention after being added into a water-based anticorrosive coating.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
Weighing 0.1g of oversized graphene oxide (the thickness is 1nm, the sheet diameter is 20 microns) and adding the oversized graphene oxide into 100mL of deionized water, and performing ultrasonic dispersion to form 1mg/mL graphene oxide aqueous dispersion; according to the mass ratio of 1: 1, weighing acid anhydride and an electroactive monomer (the total mass of the monomers is 1g, the acid anhydride is succinic anhydride, and the hydrophobic monomer is aniline), and adding the mixture into 50mL of the mixture in a volume ratio of 1: 0.25 of deionized water and N, N-dimethylformamide mixed solution, stirring and dissolving uniformly, transferring the mixed solution into graphene oxide aqueous dispersion, stirring and dispersing uniformly again, transferring into a three-neck flask, magnetically stirring at 90 ℃, and reacting for 24 hours to form black dispersion; and then repeatedly centrifuging and washing the black dispersion liquid by using a mixed solution of acetone, deionized water and ethyl acetate (mass ratio of 1: 4: 1), thereby obtaining the electroactive polymer molecule layer modified oversized graphene. And (3) transferring the modified oversized graphene into water, and dispersing to form the oversized graphene aqueous slurry for efficient corrosion prevention (the slurry concentration is 1%).
And adding the prepared oversized graphene slurry into a water-based epoxy coating, wherein the mass fraction of graphene is 0.1 wt.%, and dispersing at a high speed to form a uniform system coating for a standby spray plate.
The obtained coating is coated on a steel plate with the surface roughness reaching Sa2.5, the film thickness is controlled to be 60 mu m, experiments and detection show that the surface drying time of the coating is 1.5h, the full drying time is 9h, a 50cm drop hammer impact resistance experiment coating has a small amount of damage, a 2mm flexibility test has a small amount of cracks, a salt spray resistance experiment can reach 1500h, and the adhesive force is 2.8 MPa. The polarization curve of the resulting coating is shown in fig. 5. The corrosion potential was-0.56V.
Example 2
Weighing 0.15g of oversized graphene oxide (the thickness is 1nm, the sheet diameter is 10 microns) and adding the oversized graphene oxide into 100mL of deionized water, and performing ultrasonic dispersion to form 1.5mg/mL graphene oxide aqueous dispersion; according to the mass ratio of 1: 3, weighing acid anhydride and an electroactive monomer (the total mass of the monomers is 1.2g, the acid anhydride is maleic anhydride, and the electroactive monomer is m-methylaniline), and adding the mixture into 50mL of the mixture in a volume ratio of 1: 1, stirring and dissolving the mixed solution of deionized water and N, N-dimethylacetamide uniformly, transferring the mixed solution into graphene water dispersion, stirring and dispersing uniformly again, transferring the graphene water dispersion into a three-neck flask, magnetically stirring the graphene water dispersion at 80 ℃, and reacting for 30 hours to form black dispersion; and then repeatedly centrifuging and washing the black dispersion liquid by using a mixed solution of acetone, deionized water and ethyl acetate (mass ratio of 1: 4: 1), thereby obtaining the conjugated block copolymer molecule layer modified oversized graphene. And (3) transferring the modified oversized graphene into water, and dispersing to form the oversized graphene aqueous slurry for efficient corrosion prevention (the slurry concentration is 1%).
And adding the prepared oversized graphene slurry into a water-based epoxy coating, wherein the mass fraction of graphene is 0.2 wt.%, and dispersing at a high speed to form a uniform system coating for a standby spray plate.
The obtained coating is coated on a steel plate with the surface roughness reaching Sa2.5, the film thickness is controlled to be 60 mu m, the surface drying time of the coating is 1.2h, the full drying time is 7.5h, the 50cm drop hammer impact resistance test coating has a small amount of damage, the 2mm flexibility test has a small amount of cracks, the salt spray resistance test can reach 2200h, and the adhesive force is 3.1 MPa. The polarization curve of the resulting coating is shown in FIG. 5, with a corrosion potential of-0.7V.
Example 3
Weighing 0.2g of oversized graphene oxide (the thickness is 1.2nm, the sheet diameter is 30 microns) and adding the oversized graphene oxide into 100mL of deionized water, and performing ultrasonic dispersion to form 2mg/mL graphene oxide aqueous dispersion; according to the mass ratio of 1: weighing anhydride and electroactive monomer (the total mass of the monomers is 3g, the anhydride is maleic anhydride, and the electroactive monomer is ethyl aniline), adding the weighed materials into a 50mL reactor with a volume ratio of 1: 2, stirring and dissolving the deionized water and the N, N-dimethyl sulfoxide uniformly, transferring the solution into graphene water dispersion, stirring and dispersing uniformly again, transferring the solution into a three-neck flask, magnetically stirring the solution at the temperature of 95 ℃, and reacting the solution for 36 hours to form black dispersion; and then repeatedly centrifuging and washing the black dispersion liquid by using a mixed solution of acetone, deionized water and ethyl acetate (mass ratio of 1: 4: 1), thereby obtaining the conjugated block copolymer molecule layer modified oversized graphene. And (3) transferring the modified oversized graphene into water, and dispersing to form the oversized graphene aqueous slurry for efficient corrosion prevention (the slurry concentration is 5%).
Adding the prepared oversized graphene slurry into a water-based epoxy coating, wherein the mass fraction of graphene is 1 wt.%, and dispersing at a high speed to form a uniform system coating for a standby spray plate.
The obtained coating is coated on a steel plate with the surface roughness reaching Sa2.5, the film thickness is controlled to be 60 mu m, the surface drying time of the coating is 1h, the full drying time is 6h, the 50cm drop hammer impact resistance experiment coating is not damaged through experiments and detection, the 2mm flexibility test is not cracked, the salt spray resistance experiment can reach 3100h, and the adhesive force is 4.6 MPa. The polarization curve of the resulting coating is shown in FIG. 5, with a corrosion potential of-0.355V.
Example 4
Weighing 0.15g of oversized graphene oxide (the thickness is 1.3nm, the sheet diameter is 40 mu m), adding the weighed oversized graphene oxide into 100mL of deionized water, and performing ultrasonic dispersion to form 1.5mg/mL graphene oxide aqueous dispersion; according to a molar ratio of 1: 0.3, weighing acid anhydride and an electroactive monomer (the total mass of the monomers is 1.8g, the acid anhydride is cinnamic anhydride, and the electroactive monomer is ethyl aniline), adding into 50mL of the mixture with the volume ratio of 1: 3, stirring and dissolving the deionized water and the N, N-dimethylformamide uniformly, transferring the mixture into graphene water dispersion, stirring and dispersing uniformly again, transferring the mixture into a three-neck flask, magnetically stirring at 90 ℃ and reacting for 30 hours to form black dispersion; and then repeatedly centrifuging and washing the black dispersion liquid by using a mixed solution of acetone, deionized water and ethyl acetate (mass ratio of 1: 4: 1), thereby obtaining the conjugated block copolymer molecule layer modified oversized graphene. And (3) transferring the modified oversized graphene into water, and dispersing to form the oversized graphene aqueous slurry for efficient corrosion prevention (the slurry concentration is 3%).
And adding the prepared oversized graphene slurry into a water-based epoxy coating, wherein the mass fraction of graphene is 0.2 wt.%, and dispersing at a high speed to form a uniform system coating for a standby spray plate.
The obtained paint is coated on a steel plate with the surface roughness reaching Sa2.5, the film thickness is controlled to be 60 mu m, the surface drying time of the coating is 1.2h, the full drying time is 7h, the 50cm drop hammer impact resistance experiment coating is not damaged through experiments and detection, the 2mm flexibility test is not cracked, the salt spray resistance experiment can reach 2900h, and the adhesive force is 4.1 MPa. The polarization curve of the resulting coating is shown in FIG. 5, with a corrosion potential of-0.28V.
Example 5
(1) Weighing 0.1g of oversized graphene oxide (the thickness is 0.8nm, the sheet diameter is 10 microns) and adding the oversized graphene oxide into 100mL of deionized water, and performing ultrasonic dispersion to form 1mg/mL graphene oxide aqueous dispersion; according to a molar ratio of 1: 2, weighing acid anhydride and an electroactive monomer (the total mass of the monomers is 0.9g, the acid anhydride is glutaric anhydride, and the electroactive monomer is aniline), and adding the weighed materials into a 50mL reactor with a volume ratio of 1: 1, stirring and dissolving the mixed solution of deionized water and N, N-dimethylformamide uniformly, transferring the mixed solution into graphene water dispersion, stirring and dispersing uniformly again, transferring the mixed solution into a three-neck flask, magnetically stirring at 85 ℃, and reacting for 24 hours to form black dispersion; and then repeatedly centrifuging and washing the black dispersion liquid by using a mixed solution of acetone, deionized water and ethyl acetate (mass ratio of 1: 4: 1), thereby obtaining the conjugated block copolymer molecule layer modified oversized graphene. The scanning electron micrograph is shown in figure 1, the transmission electron micrograph is shown in figure 2, the Raman spectrum is shown in figure 3, and the X-ray photoelectron spectroscopy is shown in figure 4.
And transferring the modified oversized graphene into water, and dispersing to form the oversized graphene aqueous slurry for efficient corrosion prevention (the slurry concentration is 3 wt.%).
And adding the prepared oversized graphene slurry into a water-based epoxy coating, wherein the mass fraction of graphene is 0.2 wt.%, and dispersing at a high speed to form a uniform system coating for a standby spray plate.
The obtained coating is coated on a steel plate with the surface roughness reaching Sa2.5, the film thickness is controlled to be 60 mu m, the surface drying time of the coating is 45min through experiments and detection, the full drying time is 5h, the 50cm drop hammer impact resistance experiment coating is not damaged, the 2mm flexibility test is not cracked, the salt spray resistance experiment can reach 4500h, and the adhesive force is 6 MPa. The polarization curve of the resulting coating is shown in FIG. 5, with a corrosion potential of-0.23V.
Example 6
(1) Weighing 0.15g of oversized graphene oxide (with the thickness of nm and the sheet diameter of mum), adding the oversized graphene oxide into 100mL of deionized water, and performing ultrasonic dispersion to form 1.5mg/mL graphene oxide aqueous dispersion; according to a molar ratio of 1: 1.5 weighing acid anhydride and an electroactive monomer (the total mass of the monomers is 1.65g, the acid anhydride is cinnamic anhydride, and the electroactive monomer is ethyl aniline), adding into 50mL of the mixture with the volume ratio of 1: 2, stirring and dissolving the deionized water and ethanol mixed solution uniformly, transferring the solution into graphene water dispersion, stirring and dispersing uniformly again, transferring the solution into a three-neck flask, magnetically stirring the solution at 90 ℃ and reacting the solution for 30 hours to form black dispersion; and then repeatedly centrifuging and washing the black dispersion liquid by using a mixed solution of acetone, deionized water and ethyl acetate (mass ratio of 1: 4: 1), thereby obtaining the conjugated block copolymer molecule layer modified oversized graphene. And transferring the modified oversized graphene into water, and dispersing to form the oversized graphene aqueous slurry for efficient corrosion prevention (the slurry concentration is 3 wt.%).
And adding the prepared oversized graphene slurry into a water-based epoxy coating, wherein the mass fraction of graphene is 0.5 wt.%, and dispersing at a high speed to form a uniform system coating for a standby spray plate.
The obtained coating is coated on a steel plate with the surface roughness reaching Sa2.5, the film thickness is controlled to be 60 mu m, the surface drying time of the coating is 1.5min, the full drying time is 7h, the 50cm drop hammer impact resistance experiment coating is not damaged through experiments and detection, a small amount of cracks exist in a 2mm flexibility test, the salt spray resistance experiment can reach 3500h, and the adhesive force is 4.8 MPa. The polarization curve of the resulting coating is shown in fig. 5. The corrosion potential was-0.35V.
Comparative example 1
The comparative example adopts the water-based epoxy coating used in the above examples, and does not add oversized graphene dispersion slurry.
The coating obtained in the comparative example is coated on a steel plate with the surface roughness reaching Sa2.5, the film thickness is controlled to be 60 mu m, and experiments and detection show that the surface drying time of the coating is 2h, the actual drying time is 8h, the 50cm drop hammer impact resistance experiment coating is damaged, the 2mm flexibility test has cracks, the salt spray resistance experiment is 1500h, and the adhesive force is 3.2 MPa. The corrosion potential was-0.65V.
The invention has many applications, and the above description is only a preferred embodiment of the invention. It should be noted that the above examples are only for illustrating the present invention, and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that various modifications can be made without departing from the principles of the invention and these modifications are to be considered within the scope of the invention.
Claims (10)
1. The utility model provides a high-efficient anticorrosive super large-size graphite alkene with surface modification which characterized in that: the surface of the oversized graphene is modified by adopting a reducing agent, and the graphene surface is polymerized to form a water dispersible modification layer on the molecular layer; the mass ratio of the reducing agent to the oversized graphene oxide is (8-15) to 1; the reducing agent is a reaction product of acid anhydride and an electroactive monomer; the thickness of the oversized graphene is 0.34-1 nm, and the sheet diameter is 20-100 microns.
2. The surface-modified oversized graphene for high-efficiency corrosion prevention according to claim 1, characterized in that: the mass ratio of the acid anhydride to the electroactive monomer is 1: (0.3-3).
3. The surface-modified oversized graphene for efficient corrosion prevention according to claim 1 or 2, characterized in that: the acid anhydride is binary acid anhydride, and is specifically selected from one or a mixture of more of maleic anhydride, succinic anhydride, cinnamic anhydride and glutaric anhydride.
4. The surface-modified oversized graphene for efficient corrosion prevention according to claim 1 or 2, characterized in that: the electroactive monomer is one or a mixture of aniline, methylaniline and ethylaniline.
5. The preparation method of the surface-modified oversized graphene for high-efficiency corrosion prevention according to any one of claims 1-4, characterized by comprising the following steps: the method comprises the following steps:
A. weighing oversized graphene oxide according to the mass ratio, adding the oversized graphene oxide into water, and performing ultrasonic dispersion to form uniform graphene oxide dispersion liquid;
B. weighing a reducing agent precursor according to a mass ratio, adding the reducing agent precursor into a mixed solution formed by water and an organic solvent, uniformly stirring, adding into the graphene oxide dispersion liquid prepared in the step A, and stirring to form a uniform dispersion liquid;
C. reacting the uniform dispersion liquid prepared in the step B at the temperature of 60-120 ℃ for 18-72 hours to form a black dispersion liquid;
D. and D, repeatedly washing the black dispersion liquid completely reacted in the step C to obtain the surface-modified oversized graphene.
6. The preparation method of the surface-modified oversized graphene for high-efficiency corrosion prevention according to claim 5, characterized by comprising the following steps: in the step A, the mass concentration of the oversized graphene oxide in the graphene oxide dispersion liquid is 0.05-5 mg/ml;
in the step B, the mixing mass ratio of the deionized water to the organic solvent is 1: (0.25 to 3).
7. The method for preparing the surface-modified oversized graphene for efficient corrosion prevention according to claim 5 or 6, characterized by comprising the following steps: the organic solvent is one or a mixture of N, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide; the mass concentration of the oversized graphene oxide in the graphene oxide dispersion liquid is 1-2 mg/ml.
8. The preparation method of the surface-modified oversized graphene for efficient corrosion prevention according to claim 5, characterized by comprising the following steps: in the step C, the uniform dispersion liquid reacts for 24-36 hours at the temperature of 80-95 ℃.
9. The preparation method of the surface-modified oversized graphene for efficient corrosion prevention according to claim 5, characterized by comprising the following steps: in the step D, the solvent adopted for washing is 1: 4: 1, acetone, deionized water and ethyl acetate.
10. The aqueous slurry prepared from the surface-modified oversized graphene for high efficiency corrosion prevention according to claim 1, characterized in that: the aqueous slurry is obtained by dispersing surface-modified oversized graphene in water; in the aqueous slurry, the concentration of the surface-modified oversized graphene is 0.1-1 wt.%.
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| CN113897101A (en) * | 2021-10-09 | 2022-01-07 | 中国国家博物馆 | Graphene oxide sealing and protecting method for iron cultural relics |
| CN113897101B (en) * | 2021-10-09 | 2022-10-21 | 中国国家博物馆 | Graphene oxide sealing and protecting method for iron cultural relics |
| GB2621975A (en) * | 2022-08-18 | 2024-03-06 | Sparc Tech Limited | Anticorrosive coating composition comprising graphene |
| GB2622948A (en) * | 2022-08-18 | 2024-04-03 | Sparc Tech Limited | Anticorrosive coating composition comprising graphene |
| CN115536018A (en) * | 2022-09-30 | 2022-12-30 | 深圳市贝特瑞新能源技术研究院有限公司 | Graphene oxide slurry, heat-conducting film and preparation method |
| CN115536018B (en) * | 2022-09-30 | 2024-05-07 | 深圳市贝特瑞新能源技术研究院有限公司 | Graphene oxide slurry, heat conducting film and preparation method |
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