CN114854237A - Method for inhibiting oxidation of MXene nano material and application of MXene nano material in anticorrosive paint - Google Patents

Method for inhibiting oxidation of MXene nano material and application of MXene nano material in anticorrosive paint Download PDF

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CN114854237A
CN114854237A CN202210386187.8A CN202210386187A CN114854237A CN 114854237 A CN114854237 A CN 114854237A CN 202210386187 A CN202210386187 A CN 202210386187A CN 114854237 A CN114854237 A CN 114854237A
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mxene
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coating
silane
graphene
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CN114854237B (en
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段继周
周子扬
塞皮德·波哈森
董续成
孙佳文
侯保荣
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Institute of Oceanology of CAS
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/10Metal compounds
    • C08K3/14Carbides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/28Nitrogen-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances
    • C08K9/06Ingredients treated with organic substances with silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/10Encapsulated ingredients

Abstract

The invention relates to an anticorrosive nano-filler, in particular to a method for inhibiting the oxidation of MXene nano-materials and application of obtained stable materials as the anticorrosive nano-filler in a polymer coating. And forming a protective layer on the surface of the MXene nano-sheet, so that the complete two-dimensional sheet structure of the MXene nano-material is maintained, and oxidation is inhibited. The resulting non-oxidized MXene nanoplates with defect-free, lamellar structures are used as anticorrosive nanofillers in polymer coatings to develop long-term corrosion resistant coatings on metal structures. Therefore, the oxidation of MXene nanosheets is inhibited through covalent functionalization with alkoxysilane or hybridization with graphene-based nanomaterial, while improving the dispersion quality of MXene nanosheets in the polymer matrix. The modified MXene-based nanosheets are used as nanofillers in a polymer coating and can exert long-acting anticorrosion performance in a polymer matrix.

Description

Method for inhibiting oxidation of MXene nano material and application of MXene nano material in anticorrosive paint
Technical Field
The invention relates to an anticorrosive nano-filler, in particular to a method for inhibiting the oxidation of MXene nano-materials and application of obtained stable materials as the anticorrosive nano-filler in a polymer coating.
Background
MXene is a two-dimensional transition metal carbide, nitride or carbonitride having the chemical formula M n+1 AX n (n ═ 1,2,3) as the MAX phase, where M is a transition metal (e.g., titanium), a is a main group IIIA or IV element (e.g., aluminum), and X is a carbon atom or a nitrogen atom. MXene can be synthesized by chemical etching of the "a" element in compounds of MAX phase crystal structure. As a result of this process, the MAX phase will recrystallize to 3D M n+1 X n MXene, which is converted to exfoliated two-dimensional platelet morphology and hexagonal crystallinity by vigorous stirring and centrifugation.
The MXene nano-sheet has the potential of developing an anticorrosive nano-composite polymer coating and can effectively block the diffusion path of corrosive ions in a coating substrate. Meanwhile, MXene has high hydrophilicity due to the existence of hydrophilic functional groups (such as-F, -OH and ═ O) on the surface of the MXene, and is comparable to other two-dimensional hydrophobic materials such as graphene, and the aqueous dispersion of the MXene nano material can be uniformly dispersed in the polymer composite material. However, MXene is highly susceptible to oxidative degradation due to exposure to air or water, making it the most challenging for widespread use.
In fact, MXene has excellent dispersibility in aqueous solutions because oxygen and water molecules in the solution easily react with hydroxyl groups on the MXene surface, and oxidative degradation occurs. MXene is converted to metal oxide particles (TiO) due to oxidation problems of MXene 2 ) And the sheet will break up from the edges into small fragments. However, the two-dimensional structure of MXene, which has a large surface area, is an important feature for achieving high barrier performance in corrosion resistant nanocomposite polymer coatings, which is greatly impaired by oxidation reactions.
Although the oxidation of MXene nanosheets can be inhibited by removing dissolved oxygen as a main oxidation source, controlling the time for storing MXene in an inert atmosphere, or storing at a lower temperature, the MXene nanomaterial can still undergo rapid oxidative decomposition once put into use, thereby affecting the properties of the material. Therefore, the application of stable MXene nanomaterials in polymer coatings still presents some challenges.
Disclosure of Invention
The invention aims at a method for inhibiting the oxidation of MXene nano materials and application of obtained stable materials as anticorrosive nano fillers in polymer coatings.
In order to realize the purpose, the invention adopts the technical scheme that:
a method for inhibiting the oxidation of MXene nano material is to form a protective layer on the surface of MXene nano sheet so as to keep the complete two-dimensional sheet structure of MXene nano material.
The method specifically comprises the following steps: modifying the MXene nano material by using a silane coupling agent, or hybridizing and coating the MXene nano material by using a graphene-based nano sheet, and modifying by using the silane coupling agent after coating.
The hybrid coating is to combine MXene nanometer material and graphene nanometer material through covalent bond to obtain graphene/MXene nanometer hybrid material.
Further, the weight ratio of the silane coupling agent to the MXene nano material is 0.1-100, preferably 1-50, more preferably 10-20; covalently silane functionalizing the material; wherein the silane coupling agent is one or more of 3- (2-aminoethylamino) propyl trimethoxy silane, 3-chloropropyl trimethoxy silane, 3-mercaptopropyl trimethoxy silane, 3-glycidoxypropyl triethoxy silane, 3-aminopropyl triethoxy silane, 3-iodophenyl trimethoxy silane, 3-bromopropyl trimethoxy silane, 3-trifluoroacetyl oxypropyl trimethoxy silane, heptadecafluorodecyl triethoxy silane or 1H,1H,2H, 2H-perfluorodecyl triethoxy silane.
And refluxing the covalent silane functionalization at 60-100 ℃ for 6-24 hours, wherein the covalent silane functionalization is selected to inhibit the oxidation of MXene, provide a protective layer for the MXene nanosheet and improve the dispersion quality of the nanosheet in the polymer coating. Both of these factors can enhance the performance of the polymeric coating by increasing the barrier properties of the polymeric coating and the crosslink density of the polymeric coating. The weight ratio of the silane coupling agent to the MXene-based nano material can be selected to be in the range of 0.1-100.
Mixing MXene nano material and graphene-based nano material according to the weight ratio of 1:0.1-1: 10 (preferably in the range of 1:0.1-1:5, more preferably in the range of 1:0.1-1: 2) are mixed and subjected to covalent bond bonding by a hydrothermal/solvothermal method to obtain a graphene-based/MXene nano hybrid material, and then the graphene-based/MXene nano hybrid material and a silane coupling agent are mixed according to the weight ratio of 1: 0.5-1: 5, performing covalent silane functionalization on the material; wherein the graphene-based nanomaterial is graphene or graphene oxide.
The hydrothermal/solvothermal reaction is adopted, namely, the stainless steel autoclave lined with polytetrafluoroethylene is subjected to heat treatment at 80-200 ℃ for 4-24 hours, preferably at 100-180 ℃ for 6-18 hours, and most preferably at 120-160 ℃ for 8-16 hours, and the obtained product is washed by deionized water and ethanol and then dried at 40-70 ℃.
Covalent hybrids of MXene nanoplatelets with graphene-based nanomaterials, the graphene nanoplatelets acting as spacers between the MXene nanoplatelets to prevent them from aggregating in the nanocomposite polymer matrix. In addition, graphene-based nanoplatelets can wrap the surface of MXene nanoplatelets to reduce exposure to humidity/air and increase the chemical stability of MXene, the hybrids are further functionally modified with alkoxysilanes.
The stable MXene nano material prepared by the method is applied to an application of the stable MXene nano material as an anticorrosive nano filler in a polymer coating.
A polymeric coating material, the method producing the resulting stabilizing material added to a polymeric matrix, wherein the stabilizing material constitutes 0.005-5 wt.%, preferably in the range of 0.05-2.5 wt.%, more preferably in the range of 0.1-1 wt.% of the mass of the polymeric matrix.
The polymer matrix consists of polymer resin, a curing agent, a filler and a solvent; the nano anticorrosive filler is the stable material;
the materials added to the polymer matrix are all commercially available, and the specific composition is added according to the recommended ingredient ratio of the product.
MXene-based nanomaterials can be used as corrosion inhibiting nanofillers in polymer coatings to increase the service life of metal structures.
The stabilizing material is added to the polymer matrix by a solution mixing process to achieve uniform dispersion of the nanofiller in the polymer matrix.
The solution mixing method is that the materials are added into a medium solvent (water) to be uniformly dispersed into a solution, then the solutions are mixed with each other, and the solution can be added into a polymer matrix through a mechanical mixing method during mixing, so that the uniform dispersion of the nano filler in the coating matrix is realized. The polymer matrix of the nanocomposite polymer coating may be selected from water-borne or solvent-borne polymer matrices of epoxy coating systems or epoxy-modified polydimethylsiloxane coating systems.
The polymer coating material is directly applied to a metal structure to form a nano composite coating for carrying out anticorrosion protection on the metal structure.
However, the optimal amount of MXene-based nanoplatelets can be selected based on the desired properties, polymer matrix, modifier, and other optional components of the coating. The composition may also include dispersants, defoamers, stabilizers, biocides, and other fillers or pigments. The nanocomposite composition can be applied to a surface by brushing, spraying, dipping, spin coating, or powder coating to form a uniform coating.
The coating obtained as described above has a nanocomposite polymer coating with enhanced corrosion protection properties for metallic structures, which coating consists of a polymer (resin and its hardener) and MXene-based nanofillers and other desired pigments.
In the nanocomposite coating embodiment, MXene nanoplatelets are selected as the corrosion-resistant two-dimensional nanofiller. In these embodiments, MXene nanoplatelets should be protected from oxidation and degradation due to exposure to moisture or water, thereby enhancing corrosion of the polymer coating using MXene nanoplatelets having a defect-free two-dimensional platelet morphology and no significant oxidation.
The invention has the advantages that:
the invention improves the oxidation condition of MXene and maintains the chemical stability of MXene through a chemical modification method so as to promote the application of MXene in a nano composite polymer coating. The resulting nanocomposite polymer coating incorporates stable MXene nanomaterials obtained by covering the surface and edges of MXene with appropriate chemical reagents, which prevent oxidation of MXene and promote dispersibility of MXene in the polymer coating, prevent oxidation and degradation of MXene nanoplatelets from exposure to moisture or water.
The stable MXene nano material is modified by a silane coupling agent, so that MXene is oxidized, and the dispersion quality of the nano sheet in a polymer coating is improved. Which is utilized to enhance the barrier properties of the polymeric coating and the crosslink density of the polymeric coating to enhance the properties of the polymeric coating.
Meanwhile, before modifying the MXene nano by using a silane coupling agent, the MXene nano is further subjected to hybridization treatment, namely a hybrid of the MXene nano sheet and the graphene-based nano material. The graphene nanoplatelets act as spacers between the MXene nanoplatelets to prevent them from aggregating in the nanocomposite polymer matrix. In addition, the graphene-based nanosheets can wrap the surface of MXene nanosheets to reduce exposure to humidity/air and improve the chemical stability of MXene, the hybrids are further functionally modified with alkoxysilane to inhibit oxidation and self-stacking of the MXene nanosheets, and then stable MXene nanomaterials are obtained, which also improve the barrier properties of the polymer coating and the crosslinking density of the polymer coating to enhance the properties of the polymer coating.
Drawings
Fig. 1(a) is a transmission electron microscope image of fresh MXene nanoplatelets;
fig. 1(b) is a transmission electron microscope image of the modified MXene nanosheet.
Fig. 2 is a Bode diagram of a pure epoxy coating and a composite resin coating loaded with F-MXene nanomaterial soaked in a 3.5 wt.% sodium chloride solution for different periods of time according to an embodiment of the present invention.
Fig. 3 is a transmission electron microscope image before and after the GO @ MXene nano hybrid is modified according to an embodiment of the present invention, where fig. (a) is the transmission electron microscope image before the GO @ MXene nano hybrid is modified; and (b) is a transmission electron microscope image of the GO @ MXene nano hybrid after modification.
FIG. 4 is a graph of Bode of a composite resin coating loaded with F-GO @ MXene nanomaterial and a pure epoxy coating soaked in a 3.5 wt.% sodium chloride solution for different periods of time, according to an embodiment of the present invention.
FIG. 5 shows the corrosion resistance of the pure epoxy coating and the composite resin coating loaded with the F-GO @ MXene nanomaterial in an accelerated salt spray test box after 30 days according to an embodiment of the invention.
FIG. 6 is an adhesion test of a pure epoxy coating and a composite resin coating loaded with F-GO @ MXene nano-materials according to an embodiment of the present invention.
Detailed Description
The following examples are presented to further illustrate embodiments of the present invention, and it should be understood that the embodiments described herein are for purposes of illustration and explanation only and are not intended to limit the invention.
The stable MXene nano material can prevent the oxidation of MXene and the dispersibility of MXene in the polymer coating in different modes, so that the barrier property and the corrosion resistance of the polymer coating are enhanced, and the long-term corrosion protection of a metal structure is realized.
Specifically, silane coupling agents are used to modify the surface of MXene, specifically, the-OH and-O functional groups on the surface of MXene are reaction points for forming bonds on the surface and edges of MXene by reacting with chemical reagents, and alkoxy silane is a suitable candidate for covalent surface functionalization of MXene nanosheets. The alkoxy is converted into silanol (Si-OH) groups in a hydrolysis reaction, the silanol groups can form chemical bonds with hydroxyl on the surface of the MXene nano-sheets to form an organic-inorganic hybrid material, the oxidation of fresh MXene nano-sheets can be inhibited, and the adhesion of MXene to an organic polymer can be increased. At the same time, condensation reactions between silanol groups result in the formation of cross-linked Si-O-Si bonds.
In another mode, MXene nanosheets are covalently hybridized with graphene-based nanomaterials (e.g., graphene oxide) to obtain hybrids, and then are functionalized with alkoxysilanes, wherein the chemical stability of the MXene nanosheets is significantly improved due to the presence of the graphene-based materials, and stacking of the MXene nanosheets is prevented by the presence of the graphene-based nanomaterials.
Example 1
Fresh MXene nanoplatelets (transmission electron microscopy image shown in fig. 1 (a)) were prepared by dispersing 0.5g MXene in 95mL:5mL toluene: and (3) continuously stirring the 3-aminopropyltriethoxysilane solution for 12 hours at 80 ℃ under a reflux system to obtain the silane functionalized MXene nano material (F-MXene), which is shown in figure 1 (b).
0.1g of the MXene nanosheet functionalized by the silane is added into 40g of Epoxy resin (MU-618) and stirred vigorously at room temperature for 30min in a solution mixing manner for full dispersion, and then mixed with 20g of curing agent (CU-600) to obtain the uniformly dispersed nano composite coating (Epoxy/F-MXene).
The epoxy resin is epoxy resin (MU-618) and curing agent (CU-600) which is available from Shanghai carbon-rich Material science and technology, Inc.
The nanocomposite coating obtained above was painted on a Q235 steel substrate with a paintbrush, cured at room temperature for 72 hours, then cured in an oven at 80 ℃ for 90 minutes, and then placed for 7 days for electrochemical testing. The corrosion resistance of the coating was evaluated by the electrochemical workstation PARSTAT 4000 +. Before the experiment, the sample is subjected to open-circuit potential test in a 3.5% NaCl solution, and is subjected to electrochemical impedance spectrum test after the open-circuit potential is stable, wherein the frequency range is 105 Hz-0.01 Hz, and the amplitude of an alternating current sinusoidal disturbance signal is 20 mV.
Meanwhile, a pure epoxy resin (PE) (epoxy resin (MU-618)) was coated on a Q235 steel substrate in the above manner, and electrochemical tests were performed as a control. (see FIG. 2).
As can be seen from fig. 2, the composite coating loaded with fresh MXene nanoplates is shown to have superior corrosion resistance compared to the pure epoxy resin sample.
Example 2
50mL of Graphene Oxide (GO) (10mg/mL) and 20mL of ethanol were mixed, mixed and sonicated in a water bath for 60 minutes. Then, 50mL of a fresh aqueous MXene solution (10mg/mL) was added to the mixture, and the mixture was magnetically stirred at room temperature for 1 hour. The resulting mixture was transferred to a 200mL Teflon lined autoclave and heated at 120 ℃ for 4 hours. Finally, the resulting solution was centrifuged and washed several times with water and ethanol and freeze dried to give the nano hybrid (GO @ MXene) as shown in fig. 3 (a).
Silane functionalization was performed by refluxing 0.5g of the nanohybrid in a mixture of 3-aminopropyltriethoxysilane (5mL) and deionized water (95mL) at 80 ℃ for 12 h. Washing the reflux product with absolute ethyl alcohol and deionized water for several times, and finally freeze-drying to obtain the modified nano hybrid (F-GO @ MXene), as shown in figure 3.
As shown in fig. 3(a), GO and MXene are closely connected together, so that a folded structure of GO and a complete nanosheet structure of MXene can be clearly seen, and GO and MXene have similar structural characteristics as two-dimensional nanomaterials and are easy to match and fuse with each other to form a strong interaction; panel (b) is a transmission electron microscope image of F-GO @ MXene, showing that silane functionalization does not alter the predominant morphology of GO @ MXene, while the wrinkled structure of GO becomes less pronounced and the appearance of the nano-hybrid becomes darker, which can be attributed to the modification of the surface silane agent.
Then, 0.1 wt.% of the modified nano hybrid obtained in the mass ratio is mixed with 40g of Epoxy resin (MU-618) in a solution mixing manner, stirred vigorously at room temperature for 30min and dispersed fully, and then 20g of curing agent (CU-600) is added and mixed, so that the uniformly mixed nano composite coating material (Epoxy/F-GO @ MXene) is obtained.
The nanocomposite coating material obtained above was painted on a Q235 steel substrate with a paintbrush, cured at room temperature for 72 hours, then cured in an oven at 80 ℃ for 90 minutes, and then left at room temperature for 7 days before being subjected to electrochemical testing (see fig. 4).
Meanwhile, a pure epoxy resin (PE) (epoxy resin (MU-618)) was coated on a Q235 steel substrate in the above manner, and electrochemical tests were performed as a control.
As can be seen from fig. 4, the composite coating loaded with the F-GO @ MXene nano hybrid can provide superior corrosion resistance compared to the pure epoxy sample.
To further confirm the corrosion resistance, the nanocomposite coating formed from the nanocomposite coating material of example 2 above and the coating formed from pure epoxy resin were placed in an accelerated salt spray box for 30 days and observed for surface corrosion (see fig. 5). As can be seen in fig. 5, the pure epoxy coating (PE) exhibited severe corrosion propagation at day 30, indicating failure of the coating; the nano composite coating (Epoxy/F-GO @ MXene) has no obvious corrosion diffusion condition and still shows good corrosion resistance.
Finally, the adhesion strength of the coatings on the steel substrate was tested by a pull test on the two coatings, and the results are shown in fig. 6, which shows that the adhesion strength of the pure Epoxy coating (PE) to the steel plate is the lowest (3.7 ± 0.2MPa), and the adhesion strength of the nanocomposite coating (Epoxy/F-GO @ MXene) to the steel plate is 7.5 ± 0.6MPa, indicating that the addition of silane functionalized nanomaterials into the polymer matrix is an effective method for improving the adhesion strength of the coating to the metal substrate.

Claims (9)

1. A method for inhibiting MXene nano material oxidation is characterized in that: and forming a protective layer on the surface of the MXene nano-sheet, so that the complete two-dimensional sheet structure of the MXene nano-material is maintained, and oxidation is inhibited.
2. The method of claim 1, wherein: modifying the MXene nano material by using a silane coupling agent, or hybridizing and coating the MXene nano material by using a graphene-based nano sheet, and modifying by using the silane coupling agent after coating.
3. The method of claim 2, wherein: the hybrid coating is to combine MXene nanometer material and graphene nanometer material through covalent bond to obtain graphene/MXene nanometer hybrid material.
4. The method of claim 2, wherein: performing covalent silane functionalization on the material by using a silane coupling agent and an MXene nano material according to the weight ratio of 0.1-100; wherein the silane coupling agent is one or more of 3- (2-aminoethylamino) propyl trimethoxy silane, 3-chloropropyl trimethoxy silane, 3-mercaptopropyl trimethoxy silane, 3-glycidoxypropyl triethoxy silane, 3-aminopropyl triethoxy silane, 3-iodophenyl trimethoxy silane, 3-bromopropyl trimethoxy silane, 3-trifluoroacetyl oxypropyl trimethoxy silane, heptadecafluorodecyl triethoxy silane or 1H,1H,2H, 2H-perfluorodecyl triethoxy silane.
5. A method according to claim 2 or 3, characterized in that: mixing MXene nano material and graphene-based nano material according to the weight ratio of 1:0.1-1: 10, mixing the mixture, performing covalent bond bonding by a hydrothermal/solvothermal method to obtain the graphene/MXene nano hybrid material, and then mixing the graphene/MXene nano hybrid material with a silane coupling agent according to the weight ratio of 1: 0.5-1: 5, performing covalent silane functionalization on the material; wherein the graphene-based nanomaterial is graphene or graphene oxide.
6. Use of the stabilized MXene nanomaterial prepared by the method of claim 1, wherein the method comprises: the use of a stabilising material as an anti-corrosive nano-filler in a polymer coating.
7. A polymeric coating material characterized by: the stabilized material prepared according to claim 1, wherein the stabilized material is added to the polymer matrix in an amount of 0.005-5 wt.% based on the mass of the polymer matrix.
8. The polymeric coating material of claim 7, wherein: the stabilizing material is added to the polymer matrix by a solution mixing process to achieve uniform dispersion of the nanofiller in the polymer matrix.
9. The polymeric coating material of claim 7, wherein: the polymer coating material is directly applied to a metal structure to form a nano composite coating for carrying out anticorrosion protection on the metal structure.
CN202210386187.8A 2022-04-13 2022-04-13 Method for inhibiting oxidation of MXene nano material and application of MXene nano material in anticorrosive paint Active CN114854237B (en)

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CN115814155A (en) * 2022-12-08 2023-03-21 上海大学 Micro-nano net-shaped MoO x @Mo 2 Preparation method of C implant surface coating material
CN115819788B (en) * 2022-12-08 2024-02-02 万华化学集团股份有限公司 Preparation method of high-adhesion high-wear-resistance lightweight nylon powder
CN115814155B (en) * 2022-12-08 2024-02-02 上海大学 Micro-nano net MoO x @Mo 2 Preparation method of C implant surface coating material
CN116200091A (en) * 2023-02-18 2023-06-02 辽宁大学 High-compactness multi-scale aqueous epoxy corrosion-resistant coating and preparation method and application thereof
CN116410644A (en) * 2023-03-07 2023-07-11 北京科技大学 Functional two-dimensional material reinforced water-based anticorrosive paint and preparation method and application thereof

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