CN113337166B - Two-dimensional graphene supermolecule self-repairing hydrophobic protection composite material, preparation method and application - Google Patents

Two-dimensional graphene supermolecule self-repairing hydrophobic protection composite material, preparation method and application Download PDF

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CN113337166B
CN113337166B CN202110682399.6A CN202110682399A CN113337166B CN 113337166 B CN113337166 B CN 113337166B CN 202110682399 A CN202110682399 A CN 202110682399A CN 113337166 B CN113337166 B CN 113337166B
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dimensional graphene
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supramolecular polymer
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CN113337166A (en
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刘立伟
郑梦鸽
李奇
陈明亮
李伟伟
宋鹏豪
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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Abstract

The invention discloses a two-dimensional graphene supermolecule self-repairing hydrophobic protection composite material, and a preparation method and application thereof. The preparation method comprises the following steps: performing an assembly reaction on two-dimensional graphene, a first supramolecular polymer and a second supramolecular polymer to obtain a two-dimensional graphene supramolecular material; shaping and soaking the two-dimensional graphene supramolecular material to obtain a two-dimensional graphene supramolecular self-repairing material; performing surface hydrophobization modification treatment on the two-dimensional graphene supramolecular self-repairing material to obtain a two-dimensional graphene supramolecular self-repairing hydrophobic material; and fully contacting the two-dimensional graphene supramolecular self-repairing hydrophobic material with an organic solution for impregnation treatment to obtain the two-dimensional graphene supramolecular self-repairing hydrophobic protection composite material. The composite material prepared by the invention has the characteristics of corrosion resistance, self-repairing, stress resistance, shape memory, efficient interface protection and the like, and has wide application prospect in the fields of ocean engineering protection, transportation and the like.

Description

Two-dimensional graphene supermolecule self-repairing hydrophobic protection composite material, preparation method and application
Technical Field
The invention belongs to the technical field of production technology and application of functional protection materials, and particularly relates to a two-dimensional graphene supermolecular self-repairing hydrophobic protection composite material, and a preparation method and application thereof.
Background
With the vigorous development in the fields of aerospace, ocean, traffic, construction and the like, the application of metal and metal alloy materials is particularly wide. Due to the metal activity, electrochemical corrosion and microorganism attachment cannot be avoided, so that economic loss which is difficult to estimate is brought, and unexpected potential safety hazard is brought. In recent years, the proposals of 'ocean forcing country', 'traffic forcing country' and new capital construction put higher demands on the protective performance of metal materials. The traditional protective material mainly forms a protective layer by epoxy resin and other high polymer resins to block corrosive media and microorganisms, but has single performance, short service life and poor adhesion with a metal interface. The graphene material has infinite potential in the field of functional protection by virtue of unique properties, and can endow the material with excellent protection performance, mechanical property and other properties by virtue of structure regulation and design, so that a long-acting service cycle of the material is realized. However, due to the excellent conductivity of graphene, galvanic corrosion occurs after the protective material is cracked, and therefore, it is particularly important to find a preparation method of a two-dimensional graphene-based protective material with good self-repairing, impact-resistant, barrier and corrosion-resistant properties.
Disclosure of Invention
The invention mainly aims to provide a two-dimensional graphene supermolecular self-repairing hydrophobic composite material, and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a two-dimensional graphene supermolecular self-repairing hydrophobic protection composite material, which comprises the following steps:
providing two-dimensional graphene;
performing an assembly reaction on the two-dimensional graphene, the first supramolecular polymer and the second supramolecular polymer to obtain a two-dimensional graphene supramolecular material, wherein the first supramolecular polymer and the second supramolecular polymer can react with each other;
shaping and soaking the two-dimensional graphene supramolecular material to obtain a two-dimensional graphene supramolecular self-repairing material;
performing surface hydrophobization modification on the two-dimensional graphene supramolecular self-repairing material to obtain a two-dimensional graphene supramolecular self-repairing hydrophobic material;
and fully contacting the two-dimensional graphene supramolecular self-repairing hydrophobic material with an organic solution for impregnation treatment to obtain the two-dimensional graphene supramolecular self-repairing hydrophobic protection composite material.
The embodiment of the invention also provides the two-dimensional graphene supramolecular self-repairing hydrophobic protection composite material prepared by the method, wherein the content of the two-dimensional graphene in the two-dimensional graphene supramolecular self-repairing hydrophobic protection composite material is 0.025-0.2 wt%.
The embodiment of the invention also provides application of the two-dimensional graphene supermolecular self-repairing hydrophobic protection composite material in the field of metal surface protection.
The embodiment of the invention also provides a metal protection method, which comprises the following steps: preparing a two-dimensional graphene supermolecular self-repairing hydrophobic protection composite material on the surface of a metal matrix by adopting the method; or encapsulating the two-dimensional graphene supermolecule self-repairing hydrophobic protection composite material on the surface of a metal matrix.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, the alternating assembly of the graphene material and the supermolecule is successfully realized through the interaction between the two-dimensional graphene material and the supermolecule polymer molecules, and the uniform dispersion performance of the graphene material is further improved and the corrosion resistance is further improved through the interaction between the hydrogen bond of the polymer molecular chain and the graphene material; in addition, the synergistic effect of the two is further enhanced through the flowing entanglement and the shaping process of the molecular chain of the supramolecular polymer; meanwhile, the two-dimensional graphene supermolecular self-repairing hydrophobic protection composite material has the characteristics of corrosion resistance, self repairing, stress resistance, shape memory, efficient interface protection and the like, and has wide application prospects in the fields of ocean engineering, aerospace and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIGS. 1 a-1 b are scanning electron microscope pictures of the above-mentioned supramolecular repair effect prepared in example 1 of the present invention;
fig. 2a to fig. 2b are scanning electron microscope pictures of the repairing effect of the two-dimensional graphene supramolecular self-repairing material prepared in example 2 of the present invention;
fig. 3 a-3 b are scanning electron microscope pictures of the repairing effect of the two-dimensional graphene supramolecular self-repairing hydrophobic material prepared in example 3 of the present invention;
4 a-4 b are scanning electron microscope pictures of the repairing effect of the two-dimensional graphene supramolecular self-repairing hydrophobic protective composite prepared in the embodiment 4 of the invention;
fig. 5a to 5d are scanning electron microscope pictures, surface contact angle characterization graphs and material schematic diagrams of the repairing effect of the two-dimensional graphene supramolecular self-repairing hydrophobic protective composite material prepared in example 5 of the present invention after being repeatedly stretched for 500 times;
fig. 6 is an electrochemical test chart of the protective performance of the two-dimensional graphene supramolecular self-repairing hydrophobic protective composite material prepared in embodiment 4 of the invention;
FIG. 7 is an electrochemical test chart of the protective properties of the supramolecular material prepared in comparative example 1 of the present invention;
fig. 8 is an electrochemical test chart of the protective performance of the two-dimensional graphene supramolecular composite prepared in comparative example 2 of the present invention;
FIG. 9 is an electrochemical test chart of the protective performance of the two-dimensional graphene supramolecular self-repairing hydrophobic protective material prepared in comparative example 3 in accordance with the present invention;
FIG. 10 is an electrochemical test chart of protective performance of the two-dimensional graphene supramolecular self-repairing protective composite prepared in comparative example 4 of the present invention;
fig. 11 is an electrochemical test chart of the protection performance of the two-dimensional graphene supramolecular self-repairing hydrophobic protection composite material prepared in embodiment 5 provided by the invention, which protects for 1000 hours after being repeatedly stretched for 500 times.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long studied and largely practiced to propose the technical solution of the present invention, which will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
According to the invention, the two-dimensional graphene is used as a two-dimensional lamellar material with an ultrahigh specific surface area, so that the two-dimensional graphene has the advantages of excellent labyrinth effect, low density, super-strong mechanical property and the like, the molecular chain of a high-molecular self-repairing polymer (such as polyvinyl alcohol, polyethyleneimine, polyacrylic acid and the like) has high crosslinking density, and the molecular chain contains a large amount of groups based on hydrogen bond connection and electrostatic interaction. When the graphene and the silicon nitride are combined and applied to the self-repairing protective coating, the labyrinth effect brought by the graphene structure is used for constructing a physical barrier for blocking corrosive media (such as water and oxygen) for the coating, and the path for the coating to reach a base metal material is prolonged; the polymer material with self-repairing performance triggers molecular chain movement and molecular chain re-crosslinking in a section area after the physical barrier is broken, so that the shielding performance of the coating in the protection process is improved; in addition, the flexibility of the two-dimensional graphene material and the polymer material can also endow the composite coating with good toughness.
Specifically, the two-dimensional graphene supramolecular material with the functions of corrosion prevention and water consumption is designed to be used for metal surface protection mainly through the synergistic effect of a two-dimensional graphene sheet material and a supramolecular polymer, and then the two-dimensional graphene supramolecular material is molded to obtain the self-repairable graphene/supramolecular composite material (namely the two-dimensional graphene supramolecular self-repairing hydrophobic protection composite material).
One aspect of the embodiment of the invention provides a preparation method of a two-dimensional graphene supramolecular self-repairing hydrophobic protection composite material, which comprises the following steps:
performing an assembly reaction on two-dimensional graphene, a first supramolecular polymer and a second supramolecular polymer to obtain a two-dimensional graphene supramolecular material, wherein the first supramolecular polymer and the second supramolecular polymer can react with each other;
shaping and soaking the two-dimensional graphene supramolecular material to obtain a two-dimensional graphene supramolecular self-repairing material;
performing surface hydrophobization modification treatment on the two-dimensional graphene supramolecular self-repairing material to obtain a two-dimensional graphene supramolecular self-repairing hydrophobic material;
and fully contacting the two-dimensional graphene supramolecular self-repairing hydrophobic material with an organic solution for impregnation treatment to obtain the two-dimensional graphene supramolecular self-repairing hydrophobic protection composite material.
In some more specific embodiments, the first supramolecular polymer is selected from any one of acidic supramolecular polymer, basic supramolecular polymer, and the second supramolecular polymer is selected from the other.
Further, the acidic supramolecular polymer includes polyacrylic acid and/or polyglycolic acid 140, and is not limited thereto.
Further, the basic supramolecular polymer includes any one or a combination of two or more of polyethyleneimine, polyacrylamide and polyaniline, and is not limited thereto.
Further, when the first supramolecular polymer is selected from acidic supramolecular polymers, the second supramolecular polymer is selected from basic supramolecular polymers.
Further, when the first supramolecular polymer is selected from basic supramolecular polymers, the second supramolecular polymer is selected from acidic supramolecular polymers.
In some more specific embodiments, the preparation method specifically comprises:
respectively dispersing two-dimensional graphene and an acidic supramolecular polymer in water to form a two-dimensional graphene dispersion liquid and an acidic supramolecular polymer solution, and mixing the two-dimensional graphene dispersion liquid and the acidic supramolecular polymer solution to obtain a two-dimensional graphene/acidic supramolecular polymer dispersion liquid, wherein the pH value of the two-dimensional graphene/acidic supramolecular polymer dispersion liquid is controlled to be 3.0-3.5, the concentration of the two-dimensional graphene dispersion liquid is 0.25-1.5 mg/ml, and the concentration of the acidic supramolecular polymer solution is 3-5 mg/ml;
dispersing an alkaline supramolecular polymer in water to form an alkaline supramolecular polymer solution, wherein the pH value of the alkaline supramolecular polymer solution is controlled to be 10.0-10.5, and the concentration of the alkaline supramolecular polymer solution is 3-5 mg/ml;
and carrying out alternate assembly reaction on the two-dimensional graphene/acidic supramolecular polymer dispersion liquid and the alkaline supramolecular polymer solution for 12-24 hours to obtain the two-dimensional graphene supramolecular material.
Further, the reagents used for adjusting the pH values of the two-dimensional graphene/acidic supramolecular polymer dispersion liquid and the alkaline supramolecular polymer solution comprise acid liquor and/or alkali liquor.
Further, the acid solution includes a hydrochloric acid solution, and is not limited thereto.
Further, the alkali solution includes a sodium hydroxide solution, and is not limited thereto.
In some more specific embodiments, the method for preparing the two-dimensional graphene supramolecular material may include: placing the two-dimensional graphene in deionized water for ultrasonic treatment, and dispersing to obtain a two-dimensional graphene dispersion liquid with the concentration of 0.25 mg/ml-1.5 mg/ml; dissolving an acidic supramolecular polymer in a deionized water solution to obtain an acidic supramolecular polymer solution with the concentration of 2mg/ml, adding the two-dimensional graphene dispersion liquid with the concentration of 0.25 mg/ml-1.5 mg/ml into the acidic supramolecular polymer solution, stirring and mixing, and adjusting the pH value of the mixed solution to 3-3.5 by acid liquor or alkali liquor to obtain a two-dimensional graphene/acidic supramolecular polymer solution;
dispersing an alkaline supramolecular polymer in deionized water to obtain an alkaline supramolecular polymer solution with the concentration of 2mg/ml, and adjusting the pH value of the alkaline supramolecular polymer solution to 10-10.5 by acid liquor or alkali liquor;
and alternately assembling the two-dimensional graphene/acidic supramolecular polymer and the basic supramolecular polymer for 12h, and then centrifuging and washing to obtain the two-dimensional graphene supramolecular material.
Preferably, the ultrasonic time is 15 min-1.0 h.
As a preferred scheme, the mixing and stirring speed of the two-dimensional graphene dispersion liquid and the acidic supramolecular polymer solution is 800-1000 r/min, and the stirring temperature is 20-30 ℃.
Preferably, the acid solution or the alkali solution comprises hydrochloric acid or sodium hydroxide.
As a preferable scheme, the solution used for washing is deionized water, the washing amount is 40mL, the centrifugal washing rotating speed is 8000rpm/min, and the washing time is 6 min.
In some more specific embodiments, the preparation method specifically comprises:
respectively dispersing the two-dimensional graphene and the alkaline supramolecular polymer in water to form a two-dimensional graphene dispersion liquid and an alkaline supramolecular polymer solution, and mixing the two-dimensional graphene dispersion liquid and the alkaline supramolecular polymer solution to obtain a two-dimensional graphene/alkaline supramolecular polymer dispersion liquid, wherein the pH value of the two-dimensional graphene/alkaline supramolecular polymer dispersion liquid is controlled to be 10.0-10.5, the concentration of the two-dimensional graphene dispersion liquid is 0.25-1.5 mg/ml, and the concentration of the alkaline supramolecular polymer solution is 3-5 mg/ml;
dispersing an acidic supramolecular polymer in water to form an acidic supramolecular polymer solution, wherein the pH value of the acidic supramolecular polymer solution is controlled to be 3.0-3.5, and the concentration of the acidic supramolecular polymer solution is 3-5 mg/ml;
and carrying out alternate assembly reaction on the two-dimensional graphene/alkaline supramolecular polymer dispersion liquid and the acidic supramolecular polymer solution for 12-24 hours to obtain the two-dimensional graphene supramolecular material.
Further, the reagent used for adjusting the pH values of the two-dimensional graphene/alkaline supramolecular polymer dispersion liquid and the acidic supramolecular polymer solution comprises an acid solution and/or an alkali solution.
Further, the acid solution includes a hydrochloric acid solution, and is not limited thereto.
Further, the alkali solution includes a sodium hydroxide solution, and is not limited thereto.
In some more specific embodiments, the preparation method specifically comprises: and (3) performing molding treatment on the two-dimensional graphene supramolecular material for 3-5 days under the molding pressure of 3-15 GPa, and then soaking the two-dimensional graphene supramolecular material in water for 10-24 hours to obtain the two-dimensional graphene supramolecular self-repairing material.
Further, the temperature of the shaping treatment is-20-25 ℃.
In some more specific embodiments, the method for preparing the two-dimensional graphene supramolecular self-repairing material can include:
placing the two-dimensional graphene supramolecular material in a template for molding for 3 days under certain molding pressure, and then placing the molded two-dimensional graphene supramolecular material in deionized water for soaking for 10 hours to obtain the two-dimensional graphene supramolecular self-repairing material; the shaping pressure is 3GPa, the template used for plasticity is 25.4mm multiplied by 76.2mm, and the thickness is 1-1.2 mm. The shaping environment is any one or combination of more than two of room temperature, heating and freezing.
Preferably, the two-dimensional graphene supramolecular material is placed in a glass sheet with the specification of 25.4mm multiplied by 76.2mm and the thickness of 1-1.2 mm for shaping for 3 days under the pressure of 3GPa, and then the glass sheet is placed in deionized water for 10 hours to obtain the two-dimensional graphene supramolecular self-repairing material, wherein the glass sheet used for shaping is two or more.
In some more specific embodiments, the preparation method specifically comprises: and (3) soaking the two-dimensional graphene supramolecular self-repairing material in a solution containing a hydrophobic modifier for 10-15 h, and then reacting at 40-60 ℃ for 2.0-3.0 h to obtain the two-dimensional graphene supramolecular self-repairing hydrophobic material.
Further, the hydrophobic modifier includes any one or a combination of two or more of polydimethylsiloxane, polyvinylidene fluoride, polytetrafluoroethylene, and polystyrene, and is not limited thereto.
In some more specific embodiments, the method for preparing the two-dimensional graphene supramolecular self-repairing hydrophobic material may include: placing the two-dimensional graphene supramolecular self-repairing material in a hydrophobic modifier solution with the concentration of 0.5-1.5 mol/L, compounding for 10-15 hours, and then heating at 40-60 ℃ for 2-3 hours to obtain the two-dimensional graphene supramolecular self-repairing hydrophobic material, wherein the hydrophobic modifier used for hydrophobic modification of the surface of the two-dimensional graphene supramolecular self-repairing material is any one or combination of more than two of polydimethylsiloxane, polyvinylidene fluoride, polytetrafluoroethylene and polystyrene; the heating mode is any one of hydrothermal heating, vacuum heating and stirring heating.
In some more specific embodiments, the preparation method specifically comprises: and (3) placing the two-dimensional graphene supramolecular self-repairing hydrophobic material in an organic solution, and carrying out dipping treatment for 5-10 h at 20-30 ℃ to obtain the two-dimensional graphene supramolecular self-repairing hydrophobic protection composite material.
Further, the organic solution includes any one or a combination of two or more of perfluoropolyether, epoxy resin, and polyethylene glycol, and is not limited thereto.
Further, the concentration of the organic solution is 0.1-2.0 mol/L.
In some more specific embodiments, the preparation method of the two-dimensional graphene supramolecular self-repairing hydrophobic protective composite material can comprise the following steps: placing the two-dimensional graphene supermolecule self-repairing hydrophobic material in an organic solution with the concentration of 0.1-2 mol/L for dipping and packaging treatment, and then, removing redundant organic solution by inclining for 3-15 hours at the angle of 30-75 degrees to obtain the two-dimensional graphene supermolecule self-repairing hydrophobic protective composite material, wherein the organic solution for dipping and packaging treatment is any one of perfluoropolyether, epoxy resin and polyethylene glycol; the dipping and packaging environment is any one of room temperature, hydrothermal and vacuum heating.
The solvent and the dispersion medium used in the method are deionized water, and the method for preparing the two-dimensional graphene/supramolecular polymer material has the advantages of cleanness and environmental protection.
Specifically, the two-dimensional graphene and the supramolecular polymer are connected through electrostatic interaction and hydrogen bonds, the defect that the graphene material serving as a filler is not uniformly dispersed when being added with a self-repairing coating is overcome, the strength and the self-repairing performance of cross-linking among molecular chains are enhanced through interaction, and the labyrinth effect is enhanced through uniform dispersion of the graphene. The maze effect and the self-repairing effect cooperate to realize the integral optimization of the protective function of the composite material.
In conclusion, the two-dimensional graphene supramolecular material with corrosion resistance and water absorption functions is designed to be used for metal surface protection mainly through the synergistic effect of the two-dimensional graphene sheet layer material and the supramolecular polymer, and then the two-dimensional graphene supramolecular self-repairing hydrophobic protection composite material with self-repairing performance is obtained through shaping and surface hydrophobic modification.
In another aspect of the embodiment of the invention, the two-dimensional graphene supramolecular self-repairing hydrophobic protective composite material prepared by the method is provided, and the content of the two-dimensional graphene in the two-dimensional graphene supramolecular self-repairing hydrophobic protective composite material is 0.025wt% -0.2 wt%.
Further, the thickness of the two-dimensional graphene supermolecule self-repairing hydrophobic protection composite material is 1-2 mm.
Further, the contact angle between the two-dimensional graphene supermolecule self-repairing hydrophobic protection composite material and water is 140-147 degrees.
Furthermore, the tensile length of the two-dimensional graphene supermolecule self-repairing hydrophobic protection composite material is 3-5 cm, and the two-dimensional graphene supermolecule self-repairing hydrophobic protection composite material has good flexibility.
Further, after the two-dimensional graphene supermolecule self-repairing hydrophobic protection composite material is broken, the self-repairing time is 2-24 hours.
Furthermore, after the two-dimensional graphene supermolecular self-repairing hydrophobic protection composite material is stretched for 500 times and passes through a service period of 1000 hours, the corrosion current of the composite material is 10-9A·cm-2～10-6A·cm-2。
Further, the two-dimensional graphene supermolecule self-repairing hydrophobic protection composite material is placed in 3.5 wt% of NaCl solution to be subjected to alternating current impedance test within the range of 0.01 Hz-100000 Hz. In order to prove the synergy and surface hydrophobization modification effects of the two-dimensional graphene and the supramolecular polymer, the alternating current impedance test is carried out on the supramolecular material without the two-dimensional graphene, the supramolecular self-repairing material of the two-dimensional graphene, the supramolecular self-repairing hydrophobic material of the two-dimensional graphene after surface hydrophobization treatment and the two-dimensional supramolecular self-repairing hydrophobic protection composite material after impregnation packaging in a protection period. The test result shows that the physical barrier effect of the two-dimensional graphene and the self-repairing effect of the supramolecular polymer have a positive effect on the surface protection of the metal material, and have a better synergistic effect under the condition of low content of the two-dimensional graphene.
Furthermore, the protective performance of the two-dimensional graphene supermolecular self-repairing hydrophobic protective composite material is tested by an electrochemical workstation. Cutting the protective material into 8 × 8mm2Is encapsulated on the metal surface, and is subjected to alternating current impedance test in the range of 0.01 Hz-100000 Hz.
The embodiment of the invention also provides application of the two-dimensional graphene supramolecular self-repairing hydrophobic protection composite material in the field of metal surface protection.
For example, the two-dimensional graphene supermolecular self-repairing hydrophobic protection composite material is applied to the fields of functional protection materials, protection coatings, ocean oil and gas platforms, aerospace and the like.
Another aspect of the embodiments of the present invention also provides a metal protection method, including: preparing a two-dimensional graphene supermolecular self-repairing hydrophobic protection composite material on the surface of a metal matrix by adopting the method; or encapsulating the two-dimensional graphene supermolecule self-repairing hydrophobic protection composite material on the surface of a metal matrix.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
(1) Respectively dissolving 0.1g of polyacrylic acid and 0.1g of polyethyleneimine in 50mL of deionized water, and stirring at room temperature for 15min to obtain a uniform solution with the concentration of 2 mg/mL; respectively adjusting the pH values of the polyacrylic acid solution and the polyethyleneimine solution to be 3 and 10 by using 2mol/L NaOH solution and HCl solution;
(2) alternately dropping the polyacrylic acid solution and the polyethyleneimine solution with the concentration of 2mg/mL into another container after the pH is adjusted, and reacting for 12h at room temperature;
(3) collecting the reaction product, and centrifugally washing at room temperature, wherein the centrifugal speed is 8000r/min, and the centrifugal time is 6 min;
(4) placing the centrifuged product in a glass sheet with the thickness of 1-1.2 mm and the thickness of 25.4mm multiplied by 76.2mm for shaping for 3 days under the pressure of 3GPa, and then soaking in water to obtain a polyacrylic acid/polyethyleneimine material; cutting the polyacrylic acid/polyethyleneimine material into a sheet material with the specification of 8mm multiplied by 8mm, and scribing an artificial scratch with the length of 5mm and the width of 1mm by a blade;
(5) respectively polishing the base metal material by using 400-mesh, 800-mesh, 1000-mesh and 1200-mesh sand paper, then placing the polished base metal material in acetone and ethanol for ultrasonic washing for 15min, and then packaging the scratched polyacrylic acid/polyethyleneimine material on the surface of the metal material and placing the metal material in 3.5 wt% NaCl solution.
Example 2
(1) Respectively dissolving 0.1g of polyacrylic acid and 0.1g of polyethyleneimine in 50mL of deionized water, and stirring at room temperature for 15min to obtain a uniform solution with the concentration of 2 mg/mL; dispersing 0.5mg of two-dimensional graphene in 2mL of deionized water, and carrying out ultrasonic treatment for 15min to obtain a two-dimensional graphene dispersion liquid; mixing and stirring the two-dimensional graphene dispersion liquid and a polyacrylic acid solution uniformly to obtain a graphene/polyacrylic acid dispersion liquid; respectively adjusting the pH values of the two-dimensional graphene/polyacrylic acid dispersion liquid and the polyethyleneimine solution to be 3 and 10 by 2mol/L NaOH and HCl solutions;
(2) alternately dropping the two-dimensional graphene/polyacrylic acid dispersion liquid with the concentration of 2mg/mL and the polyethyleneimine solution into another container after the pH is adjusted, and reacting for 12 hours at room temperature;
(3) collecting the reaction product, and centrifugally washing at room temperature, wherein the centrifugal speed is 8000r/min, and the centrifugal time is 6 min;
(4) placing the centrifuged product in a glass sheet with the thickness of 1mm and the thickness of 25.4mm multiplied by 76.2mm, shaping for 3 days under the pressure of 3GPa, and then soaking in water to obtain the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing material; cutting the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing material into a sheet material with the specification of 8mm multiplied by 8mm, and scribing an artificial scratch with the length of 5mm and the width of 1mm by using a blade;
(5) respectively polishing a base metal material by using 400-mesh, 800-mesh, 1000-mesh and 1200-mesh sand paper, then placing the polished base metal material in acetone and ethanol for ultrasonic washing for 15min, and then encapsulating the scratched two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing material on the surface of the metal material in 3.5 wt% of NaCl solution.
Example 3
(1) Respectively dissolving 0.1g of polyacrylic acid and 0.1g of polyethyleneimine in 50mL of deionized water, and stirring at room temperature for 15min to obtain a uniform solution with the concentration of 2 mg/mL; dispersing 0.5mg of two-dimensional graphene in 2mL of deionized water, and carrying out ultrasonic treatment for 15min to obtain a two-dimensional graphene dispersion liquid; mixing and stirring the two-dimensional graphene dispersion liquid and a polyacrylic acid solution uniformly to obtain a two-dimensional graphene/polyacrylic acid dispersion liquid; respectively adjusting the pH values of the two-dimensional graphene/polyacrylic acid dispersion liquid and the polyethyleneimine solution to be 3 and 10 by 2mol/L NaOH and HCl solutions;
(2) alternately dropping the two-dimensional graphene/polyacrylic acid dispersion liquid with the concentration of 2mg/mL and the polyethyleneimine solution into another container after the pH is adjusted, and reacting for 12 hours at room temperature;
(3) collecting the reaction product, and centrifugally washing at room temperature, wherein the centrifugal speed is 8000r/min, and the centrifugal time is 6 min;
(4) placing the centrifuged product in a glass sheet with the thickness of 1mm and the thickness of 25.4mm multiplied by 76.2mm for shaping for 3 days under the pressure of 3GPa, and then soaking in water to obtain the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing material;
(5) the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing material is placed in polydimethylsiloxane with the concentration of 1mol/L for compounding, and the reaction time is 10 hours, so that the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic material is obtained; then cutting the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic material into a sheet material with the specification of 8mm multiplied by 8mm, and scribing artificial scratches with the length of 5mm and the width of 1mm by using a blade;
(6) respectively polishing a base metal material by using 400-mesh, 800-mesh, 1000-mesh and 1200-mesh sand paper, then placing the polished base metal material in acetone and ethanol for ultrasonic washing for 15min, and then encapsulating the scratched two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic material on the surface of the metal material in 3.5 wt% of NaCl solution.
Example 4
(1) Respectively dissolving 0.1g of polyacrylic acid and 0.1g of polyethyleneimine in 50mL of deionized water, and stirring at room temperature for 15min to obtain a uniform solution with the concentration of 2 mg/mL; dispersing 0.5mg of two-dimensional graphene in 2mL of deionized water, and carrying out ultrasonic treatment for 15min to obtain a two-dimensional graphene dispersion liquid; mixing and stirring the two-dimensional graphene dispersion liquid and a polyacrylic acid solution uniformly to obtain a two-dimensional graphene/polyacrylic acid dispersion liquid; respectively adjusting the pH values of the two-dimensional graphene/polyacrylic acid dispersion liquid and the polyethyleneimine solution to be 3 and 10 by 2mol/L NaOH and HCl solutions;
(2) alternately dropping the two-dimensional graphene/polyacrylic acid dispersion liquid with the concentration of 2mg/mL and the polyethyleneimine solution into another container after the pH is adjusted, and reacting for 12 hours at room temperature;
(3) collecting the reaction product, and centrifugally washing at room temperature, wherein the centrifugal speed is 8000r/min, and the centrifugal time is 6 min;
(4) placing the centrifuged product in a glass sheet with the thickness of 1mm and the thickness of 25.4mm multiplied by 76.2mm for shaping for 3 days under the pressure of 3GPa, and then soaking in water to obtain the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing material;
(5) the two-dimensional graphene/polyacrylic acid/polyethyleneimine material is placed in polydimethylsiloxane with the concentration of 1mol/L for compounding, the reaction time is 10 hours, and then the two-dimensional graphene/polyacrylic acid/polyethyleneimine material reacts at 50 ℃ for 1.5 hours to obtain a two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic material;
(6) placing the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic material in a perfluoropolyether organic solution with the concentration of 0.5mol/L for dipping treatment, and then placing at an inclined angle of 45 degrees for 10 hours to remove redundant organic solution to obtain a two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic composite material; cutting the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic composite material into a sheet material with the specification of 8mm multiplied by 8mm, and scribing an artificial scratch with the length of 5mm and the width of 1mm by using a blade;
(7) respectively polishing a base metal material by using 400-mesh, 800-mesh, 1000-mesh and 1200-mesh sand paper, then placing the polished base metal material in acetone and ethanol for ultrasonic washing for 15min, and then encapsulating the scratched two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic composite material on the surface of the metal material and placing the encapsulated metal material in 3.5 wt% of NaCl solution.
Example 5
(1) Respectively dissolving 0.1g of polyacrylic acid and 0.1g of polyethyleneimine in 50mL of deionized water, and stirring at room temperature for 15min to obtain a uniform solution with the concentration of 2 mg/mL; dispersing 0.5mg of two-dimensional graphene in 2mL of deionized water, and carrying out ultrasonic treatment for 15min to obtain a two-dimensional graphene dispersion liquid; mixing and stirring the two-dimensional graphene dispersion liquid and a polyacrylic acid solution uniformly to obtain a two-dimensional graphene/polyacrylic acid dispersion liquid; respectively adjusting the pH values of the two-dimensional graphene/polyacrylic acid dispersion liquid and the polyethyleneimine solution to be 3 and 10.5 by 2mol/L NaOH and HCl solutions;
(2) alternately dropping the two-dimensional graphene/polyacrylic acid dispersion liquid with the concentration of 2mg/mL and the polyethyleneimine solution into another container after the pH is adjusted, and reacting for 12 hours at room temperature;
(3) collecting the reaction product, and centrifugally washing at room temperature, wherein the centrifugal speed is 8000r/min, and the centrifugal time is 6 min;
(4) placing the centrifuged product in a glass sheet with the thickness of 1mm and the thickness of 25.4mm multiplied by 76.2mm for shaping for 3 days under the pressure of 3GPa, and then soaking in water to obtain the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing material;
(5) the two-dimensional graphene/polyacrylic acid/polyethyleneimine material is placed in polydimethylsiloxane with the concentration of 1mol/L for compounding, the reaction time is 10 hours, and then the two-dimensional graphene/polyacrylic acid/polyethyleneimine material reacts at 50 ℃ for 1.5 hours to obtain a two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic material;
(6) placing the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic material in a perfluoropolyether organic solution with the concentration of 0.5mol/L for dipping treatment, and then placing at an inclined angle of 45 degrees for 10 hours to remove redundant organic solution to obtain a two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic composite material; repeatedly stretching the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic composite material for 500 times, cutting the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic composite material into a sheet material with the specification of 8mm multiplied by 8mm, and scribing artificial scratches with the length of 5mm and the width of 1mm by a blade;
(7) respectively polishing a base metal material by using 400-mesh, 800-mesh, 1000-mesh and 1200-mesh sand paper, then placing the polished base metal material in acetone and ethanol for ultrasonic washing for 15min, and then encapsulating the scratched two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic composite material on the surface of the metal material and placing the encapsulated metal material in 3.5 wt% of NaCl solution.
And (3) performance characterization:
the functional protective materials prepared by the processes described in examples 1-5 were characterized and studied for their synergistic protective mechanism, as follows:
referring to fig. 1 a-1 b, which are scanning electron microscope pictures of the supramolecular material before and after the supramolecular material in example 1 is repaired, it can be seen from fig. 1 a-1 b that the polyacrylic acid/polyethyleneimine supramolecular material can repair scratches after being manually scratched, but the repaired material has an uneven surface and many defects;
fig. 2 a-2 b are scanning electron microscope pictures of the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing material prepared in example 2, and it can be seen from fig. 2 a-2 b that the material after the polyacrylic acid/polyethyleneimine supramolecular material and graphene assembly reaction still maintains the self-repairing effect, but the surface defects of the repaired material are increased;
fig. 3a to 3b are scanning electron microscope pictures of the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic material prepared in example 3, and it can be seen from fig. 3a to 3b that the material after hydrophobic modification still maintains self-repairing performance, but the surface of the material after repair is uneven;
fig. 4a to 4b are scanning electromagnetic microscope pictures of the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic protection composite material subjected to the dip-encapsulation treatment in example 4, and it can be seen from fig. 4a to 4b that the self-repairing performance of the material subjected to the assembly reaction, the shaping, the hydrophobic modification, and the dip-encapsulation treatment is more excellent, and the surface defects of the treated material are reduced.
Fig. 5a to 5d are scanning electron microscope pictures, surface contact angle test charts and material schematic diagrams before and after the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic protection composite material in example 4 is stretched for 500 times, and it can be seen from fig. 5a to 5b that the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic protection composite material still maintains the self-repairing capability after being stretched for 500 times, the surface of the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic protection composite material still has hydrophobicity, and the material recovers after being stretched.
Fig. 6 is an electrochemical test chart of the protective performance of the two-dimensional graphene supramolecular self-repairing hydrophobic protective composite material prepared in embodiment 4 of the invention;
fig. 11 is an electrochemical test chart of the protection performance of the two-dimensional graphene supramolecular self-repairing hydrophobic protection composite material prepared in embodiment 5 provided by the invention, which protects for 1000 hours after being repeatedly stretched for 500 times.
Example 6
(1) Respectively dissolving 0.1g of polyacrylic acid and 0.1g of polyethyleneimine in 10mL of deionized water, and stirring at room temperature for 15min to obtain a uniform solution with the concentration of 5 mg/mL; dispersing 0.5mg of two-dimensional graphene in 2mL of deionized water, and carrying out ultrasonic treatment for 15min to obtain a two-dimensional graphene dispersion liquid; mixing and stirring the two-dimensional graphene dispersion liquid and a polyacrylic acid solution uniformly to obtain a two-dimensional graphene/polyacrylic acid dispersion liquid; respectively adjusting the pH values of the two-dimensional graphene/polyacrylic acid dispersion liquid and the polyethyleneimine solution to be 3.5 and 10.5 by using 2mol/L NaOH and HCl solutions;
(2) alternately dropping the two-dimensional graphene/polyacrylic acid dispersion liquid with the concentration of 2mg/mL and the polyethyleneimine solution into another container after the pH is adjusted, and reacting for 24 hours at room temperature;
(3) collecting the reaction product, and centrifugally washing at room temperature, wherein the centrifugal speed is 8000r/min, and the centrifugal time is 6 min;
(4) placing the centrifuged product in a glass sheet with the thickness of 1.2mm and the temperature of 20 ℃ and the pressure of 15GPa for shaping for 3 days, and then soaking in water to obtain the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing material;
(5) the two-dimensional graphene/polyacrylic acid/polyethyleneimine material is placed in polydimethylsiloxane with the concentration of 1mol/L for compounding, the reaction time is 10 hours, and then the two-dimensional graphene/polyacrylic acid/polyethyleneimine material reacts at the temperature of 60 ℃ for 2.0 hours to obtain a two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic material;
(6) placing the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic material in a perfluoropolyether organic solution with the concentration of 0.5mol/L for dipping treatment, and then placing at an inclined angle of 45 degrees for 10 hours to remove redundant organic solution to obtain a two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic composite material; repeatedly stretching the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic composite material for 500 times, cutting the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic composite material into a sheet material with the specification of 8mm multiplied by 8mm, and scribing artificial scratches with the length of 5mm and the width of 1mm by a blade;
(7) respectively polishing a base metal material by using 400-mesh, 800-mesh, 1000-mesh and 1200-mesh sand paper, then placing the polished base metal material in acetone and ethanol for ultrasonic washing for 15min, and then encapsulating the scratched two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic composite material on the surface of the metal material and placing the encapsulated metal material in 3.5 wt% of NaCl solution.
Example 7
(1) Respectively dissolving 0.1g of polyacrylic acid and 0.1g of polyethyleneimine in 50mL of deionized water, and stirring at room temperature for 15min to obtain a uniform solution with the concentration of 2 mg/mL; dispersing 0.5mg of two-dimensional graphene in 2mL of deionized water, and carrying out ultrasonic treatment for 15min to obtain a two-dimensional graphene dispersion liquid; mixing and stirring the two-dimensional graphene dispersion liquid and a polyacrylic acid solution uniformly to obtain a two-dimensional graphene/polyacrylic acid dispersion liquid; respectively adjusting the pH values of the two-dimensional graphene/polyacrylic acid dispersion liquid and the polyethyleneimine solution to be 3.0 and 10.0 by using 2mol/L NaOH and HCl solutions;
(2) alternately dropping the two-dimensional graphene/polyacrylic acid dispersion liquid with the concentration of 2mg/mL and the polyethyleneimine solution into another container after the pH is adjusted, and reacting for 12 hours at room temperature;
(3) collecting the reaction product, and centrifugally washing at room temperature, wherein the centrifugal speed is 8000r/min, and the centrifugal time is 6 min;
(4) placing the centrifuged product in a glass sheet with the thickness of 1.2mm and the temperature of-20 ℃ and the pressure of 3.0GPa for shaping for 5 days, and then soaking in water to obtain the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing material;
(5) the two-dimensional graphene/polyacrylic acid/polyethyleneimine material is placed in polydimethylsiloxane with the concentration of 1mol/L for compounding, the reaction time is 12 hours, and then the two-dimensional graphene/polyacrylic acid/polyethyleneimine material reacts at 50 ℃ for 1.5 hours to obtain a two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic material;
(6) placing the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic material in a perfluoropolyether organic solution with the concentration of 0.1mol/L for dipping treatment, and then placing at an inclined angle of 30 degrees for 3 hours to remove redundant organic solution to obtain a two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic composite material; repeatedly stretching the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic composite material for 500 times, cutting the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic composite material into a sheet material with the specification of 8mm multiplied by 8mm, and scribing artificial scratches with the length of 5mm and the width of 1mm by a blade;
(7) respectively polishing a base metal material by using 400-mesh, 800-mesh, 1000-mesh and 1200-mesh sand paper, then placing the polished base metal material in acetone and ethanol for ultrasonic washing for 15min, and then encapsulating the scratched two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic composite material on the surface of the metal material and placing the encapsulated metal material in 3.5 wt% of NaCl solution.
Example 8
(1) Respectively dissolving 0.1g of polyacrylic acid and 0.1g of polyethyleneimine in 50mL of deionized water, and stirring at room temperature for 15min to obtain a uniform solution with the concentration of 2 mg/mL; dispersing 0.5mg of two-dimensional graphene in 2mL of deionized water, and carrying out ultrasonic treatment for 15min to obtain a two-dimensional graphene dispersion liquid; mixing and stirring the two-dimensional graphene dispersion liquid and a polyacrylic acid solution uniformly to obtain a two-dimensional graphene/polyacrylic acid dispersion liquid; respectively adjusting the pH values of the two-dimensional graphene/polyacrylic acid dispersion liquid and the polyethyleneimine solution to be 3.5 and 10.5 by using 2mol/L NaOH and HCl solutions;
(2) alternately dropping the two-dimensional graphene/polyacrylic acid dispersion liquid with the concentration of 2mg/mL and the polyethyleneimine solution into another container after the pH is adjusted, and reacting for 12 hours at room temperature;
(3) collecting the reaction product, and centrifugally washing at room temperature, wherein the centrifugal speed is 8000r/min, and the centrifugal time is 6 min;
(4) placing the centrifuged product in a glass sheet with the thickness of 1.2mm and the temperature of 25 ℃ and the pressure of 6GPa for shaping for 4 days to obtain the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing material, wherein the glass sheet is 25.4mm multiplied by 76.2 mm;
(5) the two-dimensional graphene/polyacrylic acid/polyethyleneimine material is placed in polydimethylsiloxane with the concentration of 1mol/L for compounding, the reaction time is 15 hours, and then the two-dimensional graphene/polyacrylic acid/polyethyleneimine material reacts at 40 ℃ for 3.0 hours to obtain a two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic material;
(6) placing the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic material in a perfluoropolyether organic solution with the concentration of 2mol/L for dipping treatment, and then placing at an inclined angle of 75 degrees for 15 hours to remove redundant organic solution to obtain the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic composite material; repeatedly stretching the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic composite material for 500 times, cutting the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic composite material into a sheet material with the specification of 8mm multiplied by 8mm, and scribing artificial scratches with the length of 5mm and the width of 1mm by a blade;
(7) respectively polishing a base metal material by using 400-mesh, 800-mesh, 1000-mesh and 1200-mesh sand paper, then placing the polished base metal material in acetone and ethanol for ultrasonic washing for 15min, and then encapsulating the scratched two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic composite material on the surface of the metal material and placing the encapsulated metal material in 3.5 wt% of NaCl solution.
Comparative example 1
(1) Respectively dissolving 0.1g of polyacrylic acid and 0.1g of polyethyleneimine in 50mL of deionized water, and stirring at room temperature for 15min to obtain a uniform solution with the concentration of 2 mg/mL; respectively adjusting the pH values of the two-dimensional graphene/polyacrylic acid dispersion liquid and the polyethyleneimine solution to be 3 and 10 by 2mol/L NaOH and HCl solutions;
(2) alternately dropping the two-dimensional graphene/polyacrylic acid dispersion liquid with the concentration of 2mg/mL and the polyethyleneimine solution into another container after the pH is adjusted, and reacting for 12 hours at room temperature;
(3) collecting the reaction product, and centrifugally washing at room temperature, wherein the centrifugal speed is 8000r/min, and the centrifugal time is 6 min;
(4) placing the centrifuged product in a glass sheet with the thickness of 1mm and the thickness of 25.4mm multiplied by 76.2mm for shaping for 3 days under the pressure of 3GPa to obtain the polyacrylic acid/polyethyleneimine self-repairing material;
(5) compounding the polyacrylic acid/polyethyleneimine material in lmol/L polydimethylsiloxane for 10 hours to obtain a two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic material;
(6) placing the polyacrylic acid/polyethyleneimine self-repairing hydrophobic material in a perfluoropolyether organic solution with the concentration of 0.5mol/L for dipping treatment, heating at the temperature of 50 ℃ for 2 hours, and then placing at an inclined angle of 45 degrees for 10 hours to remove redundant organic solution to obtain the polyacrylic acid/polyethyleneimine self-repairing hydrophobic composite material; cutting the polyacrylic acid/polyethyleneimine self-repairing hydrophobic composite material into a sheet material with the specification of 8mm multiplied by 8mm, and scribing an artificial scratch with the length of 5mm and the width of 1mm by a blade;
(7) respectively polishing a base metal material by using 400-mesh, 800-mesh, 1000-mesh and 1200-mesh sand paper, then placing the polished base metal material in acetone and ethanol for ultrasonic washing for 15min, and then packaging the polyacrylic acid/polyethyleneimine self-repairing hydrophobic composite material with scratches on the surface of the metal material in 3.5 wt% of NaCl solution.
Through testing, the electrochemical test chart of the impedance modulus of the polyacrylic acid/polyethyleneimine material in the low frequency region obtained in the comparative example can be seen in fig. 7.
Comparative example 2
(1) Respectively dissolving 0.1g of polyacrylic acid and 0.1g of polyethyleneimine in 50mL of deionized water, and stirring at room temperature for 15min to obtain a uniform solution with the concentration of 2 mg/mL; dispersing 0.5mg of two-dimensional graphene in 2mL of deionized water, and carrying out ultrasonic treatment for 15min to obtain a two-dimensional graphene dispersion liquid; mixing and stirring the two-dimensional graphene dispersion liquid and a polyacrylic acid solution uniformly to obtain a graphene oxide/polyacrylic acid dispersion liquid; respectively adjusting the pH values of the two-dimensional graphene/polyacrylic acid dispersion liquid and the polyethyleneimine solution to be 3 and 10 by 2mol/L NaOH and HCl solutions;
(2) alternately dropping the two-dimensional graphene/polyacrylic acid dispersion liquid with the concentration of 2mg/mL and the polyethyleneimine solution into another container after the pH is adjusted, and reacting for 12 hours at room temperature;
(3) collecting the reaction product, and centrifugally washing at room temperature, wherein the centrifugal rotating speed is 8000r/min, and the centrifugal time is 6min to obtain the two-dimensional graphene/polyacrylic acid/polyethyleneimine composite material;
(4) placing the two-dimensional graphene/polyacrylic acid/polyethyleneimine composite material in 1mol/L polydimethylsiloxane for compounding, wherein the reaction time is 10 hours, so as to obtain a two-dimensional graphene/polyacrylic acid/polyethyleneimine composite hydrophobic material;
(5) placing the two-dimensional graphene/polyacrylic acid/polyethyleneimine composite material in a perfluoropolyether organic solution with the concentration of 0.5mol/L for dipping treatment, heating at the temperature of 50 ℃ for 2 hours, and then placing at an inclined angle of 45 degrees for 10 hours to remove redundant organic solution to obtain the two-dimensional graphene/polyacrylic acid/polyethyleneimine hydrophobic composite material;
(6) cutting the two-dimensional graphene/polyacrylic acid/polyethyleneimine hydrophobic composite material into a sheet material with the specification of 8mm multiplied by 8mm, and scribing an artificial scratch with the length of 5mm and the width of 1mm by using a blade;
(7) respectively polishing a base metal material by using 400-mesh, 800-mesh, 1000-mesh and 1200-mesh sand paper, then placing the polished base metal material in acetone and ethanol for ultrasonic washing for 15min, and then encapsulating the scratched two-dimensional graphene/polyacrylic acid/polyethyleneimine hydrophobic composite material on the surface of the metal material and placing the encapsulated metal material in 3.5 wt% NaCl solution.
Through testing, a low-frequency zone impedance modulus electrochemical test chart of the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing material obtained in the comparative example can be seen in fig. 8.
Comparative example 3
(1) Respectively dissolving 0.1g of polyacrylic acid and 0.1g of polyethyleneimine in 50mL of deionized water, and stirring at room temperature for 15min to obtain a uniform solution with the concentration of 2 mg/mL; dispersing 0.5mg of two-dimensional graphene in 2mL of deionized water, and carrying out ultrasonic treatment for 15min to obtain a two-dimensional graphene dispersion liquid; mixing and stirring the two-dimensional graphene dispersion liquid and a polyacrylic acid solution uniformly to obtain a two-dimensional graphene/polyacrylic acid dispersion liquid; respectively adjusting the pH values of the two-dimensional graphene/polyacrylic acid dispersion liquid and the polyethyleneimine solution to be 3 and 10 by 2mol/L NaOH and HCl solutions;
(2) alternately dropping the two-dimensional graphene/polyacrylic acid dispersion liquid with the concentration of 2mg/mL and the polyethyleneimine solution into another container after the pH is adjusted, and reacting for 12 hours at room temperature;
(3) collecting the reaction product, and centrifugally washing at room temperature, wherein the centrifugal speed is 8000r/min, and the centrifugal time is 6 min;
(4) and (3) placing the centrifuged product in a glass sheet with the thickness of 1mm and the thickness of 25.4mm multiplied by 76.2mm for shaping for 3 days under the pressure of 3Gpa to obtain the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing material.
(5) The two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing material is placed in polydimethylsiloxane with the concentration of lmol/L for compounding, and the reaction time is 10 hours, so that the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic material is obtained; then cutting the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic material into a sheet material with the specification of 8mm multiplied by 8mm, and scribing artificial scratches with the length of 5mm and the width of 1mm by using a blade;
(6) respectively polishing a base metal material by using 400-mesh, 800-mesh, 1000-mesh and 1200-mesh sand paper, then placing the polished base metal material in acetone and ethanol for ultrasonic washing for 15min, and then encapsulating the scratched two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic material on the surface of the metal material in 3.5 wt% of NaCl solution.
Through testing, the electrochemical test chart of the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing hydrophobic material in the low-frequency region for the impedance modulus can be seen in fig. 9.
Comparative example 4
(1) Respectively dissolving 0.1g of polyacrylic acid and 0.1g of polyethyleneimine in 50mL of deionized water, and stirring at room temperature for 15min to obtain a uniform solution with the concentration of 2 mg/mL; dispersing 0.5mg of two-dimensional graphene in 2mL of deionized water, and carrying out ultrasonic treatment for 15min to obtain a two-dimensional graphene dispersion liquid; mixing and stirring the two-dimensional graphene dispersion liquid and a polyacrylic acid solution uniformly to obtain a two-dimensional graphene/polyacrylic acid dispersion liquid; respectively adjusting the pH values of the two-dimensional graphene/polyacrylic acid dispersion liquid and the polyethyleneimine solution to be 3 and 10 by 2mol/L NaOH and HCl solutions;
(2) alternately dropping the two-dimensional graphene/polyacrylic acid dispersion liquid with the concentration of 2mg/mL and the polyethyleneimine solution into another container after the pH is adjusted, and reacting for 12 hours at room temperature;
(3) collecting the reaction product, and centrifugally washing at room temperature, wherein the centrifugal speed is 8000r/min, and the centrifugal time is 6 min;
(4) placing the centrifuged product in a glass sheet with the thickness of 1 and the thickness of 25.4mm multiplied by 76.2mm for shaping for 3 days under the pressure of 3Gpa to obtain the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing material;
(6) placing the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing material in a perfluoropolyether organic solution with the concentration of 0.5mol/L for dipping treatment, heating at the temperature of 40-60 ℃ for 2-3 h, and then placing at an inclined angle of 45 degrees for 10h to remove redundant organic solution to obtain the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing composite material; cutting the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing composite material into a sheet material with the specification of 8mm multiplied by 8mm, and scribing an artificial scratch with the length of 5mm and the width of 1mm by using a blade;
(7) respectively polishing a base metal material by using 400-mesh, 800-mesh, 1000-mesh and 1200-mesh sand paper, then placing the polished base metal material in acetone and ethanol for ultrasonic washing for 15min, and then encapsulating the scratched two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing composite material on the surface of the metal material and placing the encapsulated metal material in 3.5 wt% of NaCl solution.
Through testing, a low-frequency zone impedance modulus electrochemical test chart of the two-dimensional graphene/polyacrylic acid/polyethyleneimine self-repairing composite material obtained in the comparative example can be seen in fig. 10.
And (3) performance characterization:
by comparing inventive example 4 with comparative examples 1-5, it was found that:
1. the comparison between the comparative example 1 and the example 4 shows that the material without adding the graphene has poorer protective performance than the material of the example 4;
2. the comparison between the comparative example 2 and the example 4 shows that the two-dimensional graphene and the supramolecular self-repairing material have a synergistic protection effect, no shaping treatment is performed, and the protection performance of the composite material is poorer than that of the example 4;
3. comparison between a comparison example 3 and an example 4 shows that the two-dimensional graphene and the supramolecular self-repairing hydrophobic material have barrier and interface protection effects on a corrosive medium, and the material without impregnation has poorer performance than that of the material in the example 4;
4. comparison between comparative example 4 and example 4 shows that the protection effect is improved by surface hydrophobization treatment of the two-dimensional graphene and the supramolecular self-repairing material, and the protection performance of the material without surface hydrophobization modification treatment is poorer than that of example 4;
in conclusion, the two-dimensional graphene supramolecular self-repairing material is subjected to surface hydrophobization treatment through the assembly of the two-dimensional graphene material and the supramolecular self-repairing material, and the metal interface protection effect is enhanced through the barrier shielding and consumption of a corrosive medium. Further, the performance is improved again by the synergistic effect of the two components, and the internal defects of the two-dimensional graphene supermolecule self-repairing hydrophobic material are encapsulated by impregnation, so that the two-dimensional graphene supermolecule self-repairing hydrophobic protective composite material is obtained, and the protective effect of the composite material is further improved. The two-dimensional graphene supermolecule self-repairing hydrophobic composite material has the characteristics of corrosion resistance, self repairing, stress resistance, shape memory, efficient interface protection and the like, and has wide application prospects in the fields of ocean engineering protection, transportation and the like. In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
It should be understood that the technical solution of the present invention is not limited to the above-mentioned specific embodiments, and all technical modifications made according to the technical solution of the present invention fall within the protection scope of the present invention without departing from the spirit of the present invention and the protection scope of the claims.

Claims (14)

1. A preparation method of a two-dimensional graphene supermolecular self-repairing hydrophobic protection composite material is characterized by comprising the following steps of:
performing an assembly reaction on two-dimensional graphene, a first supramolecular polymer and a second supramolecular polymer to obtain a two-dimensional graphene supramolecular material, wherein the first supramolecular polymer and the second supramolecular polymer can react with each other;
shaping and soaking the two-dimensional graphene supramolecular material to obtain a two-dimensional graphene supramolecular self-repairing material;
performing surface hydrophobization modification treatment on the two-dimensional graphene supramolecular self-repairing material to obtain a two-dimensional graphene supramolecular self-repairing hydrophobic material;
fully contacting the two-dimensional graphene supramolecular self-repairing hydrophobic material with an organic solution for dipping treatment to obtain a two-dimensional graphene supramolecular self-repairing hydrophobic protection composite material;
the first supramolecular polymer is selected from any one of acidic supramolecular polymer, basic supramolecular polymer, and the second supramolecular polymer is selected from the other one;
the acidic supramolecular polymer is selected from polyacrylic acid and/or polyglycolic acid 140; the alkaline supramolecular polymer is selected from one or the combination of more than two of polyethyleneimine, polyacrylamide and polyaniline.
2. The method according to claim 1, comprising:
respectively dispersing the two-dimensional graphene and the acidic supramolecular polymer in water to form a two-dimensional graphene dispersion liquid and an acidic supramolecular polymer solution, and mixing the two-dimensional graphene dispersion liquid and the acidic supramolecular polymer solution to obtain a two-dimensional graphene/acidic supramolecular polymer dispersion liquid, wherein the pH value of the two-dimensional graphene/acidic supramolecular polymer dispersion liquid is controlled to be 3.0-3.5, the concentration of the two-dimensional graphene dispersion liquid is 0.25-1.5 mg/ml, and the concentration of the acidic supramolecular polymer solution is 3-5 mg/ml;
dispersing an alkaline supramolecular polymer in water to form an alkaline supramolecular polymer solution, wherein the pH value of the alkaline supramolecular polymer solution is controlled to be 10.0-10.5, and the concentration of the alkaline supramolecular polymer solution is 3-5 mg/ml;
and carrying out alternate assembly reaction on the two-dimensional graphene/acidic supramolecular polymer dispersion liquid and the alkaline supramolecular polymer solution for 12-24 hours to obtain the two-dimensional graphene supramolecular material.
3. The method of claim 2, wherein: adjusting the pH values of the two-dimensional graphene/acidic supramolecular polymer dispersion liquid and the alkaline supramolecular polymer solution by adopting a reagent selected from acid liquid and/or alkali liquid; the acid solution is selected from hydrochloric acid solution; the alkali liquor is selected from sodium hydroxide solution.
4. The method according to claim 1, comprising:
respectively dispersing the two-dimensional graphene and the alkaline supramolecular polymer in water to form a two-dimensional graphene dispersion liquid and an alkaline supramolecular polymer solution, and mixing the two-dimensional graphene dispersion liquid and the alkaline supramolecular polymer solution to obtain a two-dimensional graphene/alkaline supramolecular polymer dispersion liquid, wherein the pH value of the two-dimensional graphene/alkaline supramolecular polymer dispersion liquid is controlled to be 10.0-10.5, the concentration of the two-dimensional graphene dispersion liquid is 0.25-1.5 mg/ml, and the concentration of the alkaline supramolecular polymer solution is 3-5 mg/ml;
dispersing an acidic supramolecular polymer in water to form an acidic supramolecular polymer solution, wherein the pH value of the acidic supramolecular polymer solution is controlled to be 3.0-3.5, and the concentration of the acidic supramolecular polymer solution is 3-5 mg/ml;
and carrying out alternate assembly reaction on the two-dimensional graphene/alkaline supramolecular polymer dispersion liquid and the acidic supramolecular polymer solution for 12-24 hours to obtain the two-dimensional graphene supramolecular material.
5. The method of claim 4, wherein: adjusting the pH values of the two-dimensional graphene/alkaline supramolecular polymer dispersion liquid and the acidic supramolecular polymer solution by adopting a reagent selected from acid liquor and/or alkali liquor; the acid solution is selected from hydrochloric acid solution; the alkali liquor is selected from sodium hydroxide solution.
6. The method according to claim 1, comprising: and (3) performing molding treatment on the two-dimensional graphene supramolecular material for 3-5 days under the molding pressure of 3-15 GPa, and then soaking the two-dimensional graphene supramolecular material in water for 10-24 hours to obtain the two-dimensional graphene supramolecular self-repairing material.
7. The method of claim 6, wherein: the temperature of the shaping treatment is-20-25 ℃.
8. The method according to claim 1, comprising: and (3) soaking the two-dimensional graphene supramolecular self-repairing material in a solution containing a hydrophobic modifier for 10-15 h, and then reacting at 40-60 ℃ for 2.0-3.0 h to obtain the two-dimensional graphene supramolecular self-repairing hydrophobic material.
9. The method of claim 8, wherein: the hydrophobic modifier is selected from any one or the combination of more than two of polydimethylsiloxane, polyvinylidene fluoride, polytetrafluoroethylene and polystyrene.
10. The method according to claim 1, comprising: and (3) placing the two-dimensional graphene supramolecular self-repairing hydrophobic material in an organic solution, and carrying out dipping treatment for 5-10 h at 20-30 ℃ to obtain the two-dimensional graphene supramolecular self-repairing hydrophobic protection composite material.
11. The method of manufacturing according to claim 10, wherein: the organic solution is selected from one or the combination of more than two of perfluoropolyether, epoxy resin and polyethylene glycol; the concentration of the organic solution is 0.1-2 mol/L.
12. The two-dimensional graphene supramolecular self-repairing hydrophobic protection composite material prepared by the preparation method of any one of claims 1 to 11, wherein the content of the two-dimensional graphene in the two-dimensional graphene supramolecular self-repairing hydrophobic protection composite material is 0.025wt% to 0.2 wt%;
the thickness of the two-dimensional graphene supermolecular self-repairing hydrophobic protection composite material is 1-2 mm;
the contact angle of the two-dimensional graphene supermolecular self-repairing hydrophobic protection composite material and water is 140-147 degrees;
the stretching length of the two-dimensional graphene supermolecular self-repairing hydrophobic protection composite material is 3-5 cm;
after the two-dimensional graphene supermolecular self-repairing hydrophobic protection composite material is broken, the self-repairing time is 2-24 h;
after the two-dimensional graphene supermolecular self-repairing hydrophobic protection composite material is stretched for 500 times and passes through a service period of 1000h, the corrosion current of the composite material is 10-9A•cm-2~10-6A•cm-2。
13. Use of the two-dimensional graphene supramolecular self-repairing hydrophobic protective composite material as claimed in claim 12 in the field of metal surface protection.
14. A method of metal protection, comprising:
preparing a two-dimensional graphene supramolecular self-repairing hydrophobic protective composite material on the surface of a metal matrix by adopting the method of any one of claims 1 to 11; or, the two-dimensional graphene supramolecular self-repairing hydrophobic protective composite material as claimed in claim 12 is packaged on the surface of a metal matrix.
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