Graphene-mxene composite heavy-duty anticorrosion material and application thereof

Abstract

The application provides a graphene-MXene composite heavy-duty anticorrosive material and application thereof, and relates to the technical field of anticorrosive materials.The graphene-MXene composite heavy-duty anticorrosive material comprises an epoxy zinc-rich primer with a solid content of 50%-70% arranged on the surface of a body to be anticorrosive, an epoxy sealing paint with a solid content of 50%-70%, and an epoxy thick paste paint with a solid content of 50%-70%, wherein the epoxy zinc-rich primer is subjected to graphene-MXene modification treatment, the epoxy zinc-rich primer, the epoxy sealing paint and the epoxy thick paste paint all contain a rare earth chelating agent, and all powder materials in the epoxy zinc-rich primer, the epoxy sealing paint and the epoxy thick paste paint are subjected to silane modification treatment.The graphene-MXene composite heavy-duty anticorrosive material has excellent chemical resistance, adhesion, salt spray resistance, aging resistance and wear resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of anticorrosive materials, in particular to a graphene-MXene composite heavy-duty anticorrosive material and application thereof. BACKGROUND

[0002] Steel structures such as bridges, ships and petrochemical equipment are often damaged by oxidation, corrosion, fatigue and other factors, causing economic and safety losses. Therefore, in order to ensure the long-term durability and safety of bridges, ships and other steel structures and petrochemical equipment, effective corrosion protection measures must be taken. Traditional organic coating anticorrosive technology has been unable to meet the high requirements of environmental protection and durability, and therefore there is an urgent need for a heavy-duty anticorrosive material that is resistant to water, acid and alkali, chemicals and weathering. SUMMARY

[0003] The problem solved by the present application is that traditional organic coating anticorrosive technology has been unable to meet the high requirements of environmental protection and durability.

[0004] To solve the above problems, the present application provides a graphene-MXene composite heavy-duty anticorrosive material, which comprises an epoxy zinc-rich primer with a solid content of 50-70%, an epoxy sealing paint with a solid content of 50-70%, and an epoxy thick paste paint with a solid content of 50-70%, which are arranged in sequence on the surface of a body to be protected. The epoxy zinc-rich primer is modified by graphene-MXene. The epoxy zinc-rich primer, the epoxy sealing paint and the epoxy thick paste paint all contain a rare earth chelating agent, and all the powder materials in the epoxy zinc-rich primer, the epoxy sealing paint and the epoxy thick paste paint are modified by silane.

[0005] Alternatively, the preparation method of the graphene-MXene comprises: adding modified MXene nanosheet powder and modified graphene nanosheet into 45-55 mL of NMP with an initial concentration of 22-28 mg / mL-1, under nitrogen protection, ultrasonic treatment at a temperature of 28-32℃ for 4-6h to obtain a graphene-MXene double nanosheet suspension, and after centrifugation and washing until the supernatant PH is 7, the graphene-MXene is obtained.

[0006] Alternatively, the preparation method of the modified MXene nanosheet powder and the modified graphene nanosheet comprises: ultrasonic cleaning the graphene nanosheet and the MXene nanosheet powder in ethanol for 25-35 minutes, dispersing them in DMF solvent, ultrasonic stirring for 10-20 minutes to obtain a dispersion liquid, adding a siloxane coupling agent with a mass fraction of 5% into the dispersion liquid, stirring and heating to 90-100℃, and then reacting for 3 hours, and after centrifugation and washing, the modified MXene nanosheet powder and the modified graphene nanosheet treated by siloxane are obtained.

[0007] Optionally, the method of silane modification treatment comprises: after the powder material is added into deionized water and ultrasonic cleaned for 25-35 minutes, the powder material is added into a 5% mass fraction silane coupling agent ethanol solution, sealed, and placed on a constant temperature 80℃ magnetic stirrer for continuous stirring for 2.5-3.5 hours, and then the modified powder material is obtained after filtration, washing, and drying to a constant weight.

[0008] Optionally, the silane coupling agent comprises one of methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane.

[0009] Optionally, the weight composition of the epoxy zinc-rich primer comprises: graphene 0.5%-1.5%, MXene 0.5%-1.5%, liquid epoxy resin 10-12%, 800-1000 mesh zinc powder 62.5-67.8%, DMP-30 accelerator 1-2%, polyamide curing agent 11-13%, phosphorus iron powder 5-10%, active diluent 5-8%, zinc phosphate 1-2%, REC-1 rare earth ytterbium chelate 0.1-0.5%, and REC-2 rare earth yttrium chelate 0.1-0.5%.

[0010] Optionally, the weight composition of the epoxy sealing paint comprises: epoxy resin 50%, alumina 5-20%, titanium oxide 1-5%, iron oxide 5-10%, DMP-30 accelerator 1.5%, active diluent 2-8%, polyamide curing agent 25-27%, REC-1 type rare earth ytterbium chelate 0.1-0.5%, and REC-2 type rare earth yttrium chelate 0.1-0.5%.

[0011] Optionally, the weight composition of the epoxy thick paste paint comprises: epoxy resin 40%, mica powder 7%, talc powder 17%, alumina 7-10%, precipitated barium sulfate 3-5%, iron oxide 5-7%, DMP-30 accelerator 1.5%, active diluent 2-5%, polyamide curing agent 20-22%, REC-1 type rare earth ytterbium chelate 0.1-0.5%, and REC-2 type rare earth yttrium chelate 0.1-0.5%.

[0012] Optionally, the epoxy zinc-rich primer is 1 layer, and the thickness is 59-61μm; the epoxy sealing paint is 1 layer, and the thickness is 139-141μm; the epoxy thick paste paint is 2 layers, and the thickness of each layer of the epoxy thick paste paint is 79-81μm.

[0013] Compared with the prior art, the graphene-MXene composite heavy-duty anticorrosion material consists of graphene-MXene modified epoxy zinc-rich primer, high solid content epoxy sealing paint and high solid content epoxy thick paste paint. Firstly, as nanomaterials, the raw materials graphene and MXene of graphene-MXene have strong corrosion resistance, which can significantly improve the corrosion resistance of the coating and prolong the service life. Secondly, graphene and MXene also have good electrical conductivity and thermal conductivity, which can form an electrically conductive network and a heat conduction channel inside the coating, improving the overall performance. In addition, graphene and MXene also have excellent mechanical properties, which can enhance the tensile resistance, wear resistance and impact resistance of the coating. At the same time, graphene and MXene materials are environmentally friendly, non-toxic and harmless, and the prepared coating has good environmental friendliness. Finally, graphene and MXene materials are easy to process and apply, and the prepared composite nanosheet is stable and reliable, and is suitable for use in the field of anticorrosion materials. Therefore, the application of graphene and MXene makes the heavy-duty anticorrosion material have many advantages, including impact resistance, shielding of corrosion factor diffusion, excellent interface bonding and passivation ability, aging resistance and cathodic protection properties. In addition, combined with rare earth chelating agents, the graphene-MXene modified heavy-duty anticorrosion material can complex the ferrous ions generated by rust in time, and form a hard, dense and not easy to fall off protective layer on the surface of the steel structure, effectively preventing the steel structure from being eroded and damaged by factors such as atmosphere, water and soil, and improving the service life of the steel structure. Moreover, all the powder materials in the epoxy zinc-rich primer, the epoxy sealing paint and the epoxy thick paste paint are subjected to silane modification treatment, which reduces the oil absorption and greatly reduces the emission of harmful gases, meeting the modern environmental protection requirements and having a wide application prospect.

[0014] To solve the above problems, the application also provides an application of the graphene-MXene composite heavy-duty anticorrosion material, specifically, the graphene-MXene composite heavy-duty anticorrosion material is coated on the surface of a steel structure building or a petrochemical equipment for corrosion protection.

[0015] The application of the graphene-MXene composite heavy-duty anticorrosion material has the same advantages as the graphene-MXene composite heavy-duty anticorrosion material relative to the prior art, and will not be described here. BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1 The figure is a structural schematic diagram of the graphene-MXene composite heavy-duty anticorrosion material in the embodiments of the application.

[0017] BRIEF DESCRIPTION OF DRAWINGS

[0018] 1-epoxy zinc-rich primer, 2-epoxy sealing paint, 3-epoxy thick paste paint. DETAILED DESCRIPTION

[0019] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings.

[0020] The description of the term “some embodiments” means that the specific features, structures, materials or characteristics described in combination with the embodiments or examples are included in at least one embodiment or example of the present application. In the present specification, the illustrative description of the above-mentioned terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0021] As shown in Figure 1 The present embodiment provides a graphene-MXene composite heavy-duty anticorrosion material, which comprises an epoxy zinc-rich primer 1 with a solid content of 50%-70% arranged on the surface of a body to be anticorrosion, an epoxy sealing paint 2 with a solid content of 50%-70% arranged on the surface of the epoxy zinc-rich primer 1, and an epoxy thick-film paint 3 with a solid content of 50%-70% arranged on the surface of the epoxy sealing paint 2. The epoxy zinc-rich primer 1 is subjected to a graphene-MXene modification treatment. The epoxy zinc-rich primer 1, the epoxy sealing paint 2 and the epoxy thick-film paint 3 all contain a rare earth chelating agent. All the powder materials in the epoxy zinc-rich primer 1, the epoxy sealing paint 2 and the epoxy thick-film paint 3 are subjected to a silane modification treatment.

[0022] The graphene-MXene composite heavy-duty anticorrosion material described in this embodiment is composed of graphene-MXene modified epoxy zinc-rich primer 1, high solid content epoxy sealing paint 2 and high solid content epoxy thick paste paint 3. First, the raw materials of graphene and MXene of graphene-MXene are nanomaterials, both of which have strong corrosion resistance and can significantly improve the corrosion resistance of the coating and prolong the service life. Second, graphene and MXene also have good electrical conductivity and thermal conductivity, which can form a conductive network and a heat conduction channel inside the coating, improving the overall performance. In addition, graphene and MXene also have excellent mechanical properties, which can enhance the tensile, wear and impact resistance of the coating. At the same time, graphene and MXene materials are environmentally friendly, non-toxic and harmless, and the prepared coating has good environmental friendliness. Finally, graphene and MXene materials are easy to process and apply, and the prepared composite nanosheet is stable and reliable, and is suitable for use in the field of anticorrosion materials. Therefore, the application of graphene and MXene makes the heavy-duty anticorrosion material have many advantages, including impact resistance, shielding of corrosion factor diffusion, excellent interface bonding and passivation ability, aging resistance and cathodic protection properties. In addition, combined with rare earth chelating agents, the graphene-MXene modified heavy-duty anticorrosion material can complex the ferrous ions generated by rust in time, forming a hard, dense and not easy to fall off protective layer on the surface of the steel structure, effectively preventing the steel structure from being eroded and damaged by atmospheric, water, soil and other factors, and improving the service life of the steel structure. All powder materials in the epoxy zinc-rich primer 1, the epoxy sealing paint 2 and the epoxy thick paste paint 3 are treated by silane modification, which reduces the oil absorption and greatly reduces the emission of harmful gases, meets the modern environmental protection requirements, and has a wide application prospect.

[0023] It should be noted that the epoxy sealing paint 2 in this embodiment can provide better adhesion in the corrosion protection system, block the epoxy zinc-rich primer 1 and enhance the weather resistance of the coating.

[0024] In some specific embodiments, the preparation method of the graphene-MXene includes: adding modified MXene nanosheet powder and modified graphene nanosheet into a solution with an initial concentration of 22-28 mg / mL -1The graphene-MXene double nanosheet suspension is obtained by ultrasonicating the graphene nanosheets and the MXene nanosheet powder in 45-55 mL of NMP under nitrogen protection at a temperature of 28-32°C for 4-6 h. After centrifugation and washing until the supernatant has a pH of 7, the modified graphene-MXene is obtained. Through the steps of ultrasonicating and centrifugation and washing, impurities and incomplete nanosheets can be effectively removed, ensuring the purity and integrity of the preparation, thereby improving the performance and reliability of the application. In addition, by adding it to the NMP solvent and further treating it by ultrasonicating and pH adjustment, the nanosheets can be uniformly dispersed in the solution and maintain stability for a long time. This dispersibility and stability make the graphene-MXene double nanosheet more convenient and feasible in the field of coatings and other fields.

[0025] In some specific embodiments, the preparation method of the modified MXene nanosheet powder and the modified graphene nanosheet comprises: ultrasonicating the graphene nanosheet and the MXene nanosheet powder in ethanol for 25-35 min, respectively, dispersing them in DMF solvent, ultrasonicating and stirring for 10-20 min to obtain a dispersion liquid, adding a siloxane coupling agent with a mass fraction of 5% to the dispersion liquid, stirring and heating to 90-100°C, and reacting for 3 hours. After centrifugation and washing, the modified MXene nanosheet powder and the modified graphene nanosheet treated by siloxane are obtained. By adding a siloxane coupling agent to the dispersion liquid and performing a thermal reaction, the surface modification of the graphene nanosheet and the MXene nanosheet powder can be realized. The modified nanosheet has higher surface activity and chemical stability, can better combine with other materials, and exhibits better stability in an acid or alkaline environment. In addition, the modified graphene nanosheet and the MXene nanosheet powder have a low oil absorption, and the surface has a low adsorption capacity for oil and other liquids, which improves the waterproof performance of the coating material, reduces the possibility of wetting and pollution, and reduces the content of VOCs in the coating material and the impact on the environment.

[0026] In some specific embodiments, the silane modification treatment method comprises: ultrasonicating the powder material in deionized water for 25-35 min, adding it to an ethanol solution of a silane coupling agent with a mass fraction of 5%, sealing, and placing it on a magnetic stirrer at a constant temperature of 80°C for continuous stirring for 2.5-3.5 hours. After suction filtration, washing, and drying to a constant weight, the modified powder material is obtained. The method is simple, and the powder with low oil absorption is formed after silane modification treatment, which greatly reduces the emission of harmful gases and meets the modern environmental protection requirements.

[0027] In some preferred embodiments, the silane coupling agent comprises one of methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane. The powder material is modified by the silane coupling agent, which is simple to operate, easy to obtain, and has good modification effect. The methyltrimethoxysilane coupling agent can make the coating have good adhesion and improve weather resistance; the phenyltrimethoxysilane coupling agent can make the coating improve chemical resistance and enhance water resistance; the methyltriethoxysilane coupling agent can make the coating improve smoothness and enhance high temperature resistance; the ethyltrimethoxysilane coupling agent can make the coating increase flexibility; and the ethyltriethoxysilane coupling agent can make the coating obtain excellent wear resistance. The use of appropriate silane coupling agents can improve the adhesion, chemical resistance, weather resistance, water resistance, lubricity, high temperature resistance, flexibility, and wear resistance of the coating, thereby effectively improving the corrosion resistance and service life of the bridge.

[0028] In some specific embodiments, the weight composition of the epoxy zinc-rich primer 1 comprises: graphene 0.5%-1.5%, MXene 0.5%-1.5%, liquid epoxy resin 10-12%, 800-1000 mesh zinc powder 62.5-67.8%, DMP-30 accelerator 1-2%, polyamide curing agent 11-13%, phosphorus iron powder 5-10%, active diluent 5-8%, zinc phosphate 1-2%, REC-1 rare earth ytterbium chelate 0.1-0.5%, and REC-2 rare earth yttrium chelate 0.1-0.5%.

[0029] In this embodiment, MXene acts as a filler to fill the corrosion medium transmission path, and the generated titanium oxide can block the corrosion path in situ. Secondly, MXene also has a physical barrier effect, adsorbing and consuming water and oxygen, and blocking the corrosion medium transmission path through oxidation products, thereby bringing excellent corrosion resistance. Graphene improves the corrosion resistance of the coating by blocking and strengthening cathodic protection. In addition, the adsorption of water molecules on the surface of MXene is stable, and a hydrogen peroxide structure can be formed, while the adsorption of water molecules and oxygen on the edge of MXene is also stable, and a titanium-oxygen bond is formed. The use of graphene and MXene can enhance the intermolecular bonding force of the coating, improve the bonding force with the steel surface, and remove water and oxygen in the coating, thereby improving the corrosion resistance.

[0030] The epoxy resin as a base material provides excellent adhesion and protective performance in the coating; zinc phosphate as a flame retardant in the coating provides a function of preventing the spread of flame; phosphorus iron powder has an anticorrosive effect in the coating, which can improve the durability and corrosion resistance of the coating, zinc powder as a barrier layer in the coating can provide excellent anti-rust performance and corrosion resistance, titanium oxide as a white pigment in the coating provides hiding power, gloss and weather resistance of the coating; the active diluent is glycidyl ether, preferably ethylene glycol diglycidyl ether, which is used to adjust the viscosity of the coating to facilitate the construction and coating process; the polyamide curing agent reacts with the epoxy resin to promote the curing and hardening of the coating; the rare earth ytterbium chelate and the rare earth yttrium chelate complex the ferrous ions produced by rust in the coating in time to block further rusting, and the DMP-30 accelerator can accelerate the reaction rate of the epoxy resin and the polyamide curing agent to promote faster curing of the coating.

[0031] In some specific embodiments, the weight composition of the epoxy sealant 2 includes: epoxy resin 50%, alumina 5-20%, titanium oxide 1-5%, iron oxide 5-10%, DMP-30 accelerator 1.5%, active diluent 2-8%, polyamide curing agent 25-27%, REC-1 type rare earth ytterbium chelate 0.1-0.5%, and REC-2 type rare earth yttrium chelate 0.1-0.5%.

[0032] In this embodiment, the epoxy resin as a base material provides excellent adhesion and protective performance in the coating, the active diluent is glycidyl ether, preferably ethylene glycol diglycidyl ether, which is used to adjust the viscosity of the coating to facilitate the construction and coating process, the polyamide curing agent reacts with the epoxy resin to promote the curing and hardening of the coating, the titanium oxide as a white pigment in the coating provides hiding power, gloss and weather resistance of the coating, the alumina as a filler in the coating has wear resistance, high temperature resistance and chemical corrosion resistance, the iron oxide in the coating has color and hiding property, which can provide color and aesthetics of the coating; the rare earth ytterbium chelate and the rare earth yttrium chelate complex the ferrous ions produced by rust in the coating in time to block further rusting.

[0033] In some specific embodiments, the weight composition of the epoxy thick paste paint 3 includes: epoxy resin 40%, mica powder 7%, talc powder 17%, alumina 7-10%, precipitated barium sulfate 3-5%, iron oxide 5-7%, DMP-30 accelerator 1.5%, active diluent solvent 2-5%, polyamide curing agent 20-22%, REC-1 type rare earth ytterbium chelate 0.1-0.5%, and REC-2 type rare earth yttrium chelate 0.1-0.5%.

[0034] In this embodiment, the epoxy resin is used as a base material to provide excellent adhesion and protection performance in the coating layer; the mica powder is used as a filler in the coating layer to provide heat resistance, electrical insulation and fireproof performance of the coating layer; the aluminum oxide is used as a filler in the coating layer to provide wear resistance, high temperature resistance and chemical corrosion resistance; the iron oxide provides color and hiding power in the coating layer to provide color and aesthetic appearance of the coating layer; the talc powder is used as a filler in the coating layer to improve the smoothness, wear resistance and corrosion resistance of the coating layer; the precipitated barium sulfate is used as a barrier layer in the coating layer to provide excellent flame retardant performance and corrosion resistance; the active diluent is glycidyl ether, preferably ethylene glycol diglycidyl ether, which is used to adjust the viscosity of the coating layer to facilitate the construction and coating process; the polyamide curing agent reacts with the epoxy resin to promote the curing and hardening of the coating layer; the DMP-30 accelerator can accelerate the reaction rate of the epoxy resin and the polyamide curing agent to promote faster curing of the coating layer; the rare earth ytterbium chelate and the rare earth yttrium chelate complex the ferrous ions produced by rust in the coating layer to prevent further rusting.

[0035] In some specific embodiments, the epoxy zinc-rich primer 1 is 1 pass with a thickness of 59-61 μm; the epoxy sealing paint 2 is 1 pass with a thickness of 139-141 μm; the epoxy thick paste paint 3 is 2 passes, and the thickness of each pass of the epoxy thick paste paint 3 is 79-81 μm. Among them, two passes of high solid content epoxy thick paste paint 3 can increase the thickness and uniformity of the coating, provide a better physical barrier layer to prevent the penetration and corrosion of external corrosion factors, improve the corrosion resistance and anticorrosive effect of the coating, and further enhance the corrosion resistance of the coating, prolong the service life of the anticorrosive system.

[0036] It should be noted that the powder material in the graphene-MXene composite heavy anti-corrosion material described in this embodiment includes aluminum oxide, titanium oxide, iron oxide, precipitated barium sulfate, mica powder, talc powder and phosphorus iron powder, which is easy to form paint.

[0037] In addition, in the graphene-MXene composite heavy-duty anticorrosive material described in the embodiment, the phosphorus iron powder in the epoxy zinc-rich primer 1 and the aluminum oxide in the epoxy sealing paint 2 can chemically react to form a hard and dense protective layer. This protective layer can increase the corrosion resistance of the coating, preventing the erosion and invasion of corrosion factors. The zinc powder in the epoxy zinc-rich primer 1 and the iron oxide in the epoxy sealing paint 2 can together form an anticorrosive layer, which can increase the wear resistance and corrosion resistance of the coating, improving the anticorrosive effect of the coating. The aluminum oxide in the epoxy sealing paint 2 and the talc powder in the epoxy thick paste paint 3 can combine with each other to increase the wear resistance and corrosion resistance of the coating. This interaction can improve the compactness and barrier property of the coating, further enhancing the anticorrosive effect of the coating. The iron oxide in the epoxy sealing paint 2 and the precipitated barium sulfate in the epoxy thick paste paint 3 can chemically react to form a barrier layer. This barrier layer can improve the anticorrosive property of the coating, preventing the penetration and erosion of corrosion factors. This synergistic effect can increase the impermeability and waterproof performance of the coating, further improving the anticorrosive performance of the coating. Through the above interactions and mutual promotion, the epoxy zinc-rich primer 1, the epoxy sealing paint 2, and the epoxy thick paste paint 3 can jointly promote the anticorrosive effect and service life of the coating. The epoxy zinc-rich primer 1 provides anticorrosive components, the epoxy sealing paint 2 forms a hard protective layer, and the epoxy thick paste paint 3 provides fillers and reinforcement. The superimposed effect of this three-layer coating system makes the anticorrosive system have better anticorrosive performance and durability.

[0038] Another embodiment of the present application also provides an application of the graphene-MXene composite heavy-duty anticorrosive material, specifically, the graphene-MXene composite heavy-duty anticorrosive material is coated on the surface of a steel structure building or a petrochemical equipment for anticorrosive protection.

[0039] The application of the graphene-MXene composite heavy-duty anticorrosive material described in the embodiment has the same advantages as the graphene-MXene composite heavy-duty anticorrosive material relative to the prior art, and will not be described here.

[0040] Embodiment 1

[0041] The present embodiment provides a graphene-MXene composite heavy-duty anticorrosive material, which comprises an epoxy zinc-rich primer modified by graphene-MXene, an epoxy sealing paint, and an epoxy thick paste paint arranged in sequence on the surface of a body to be anticorrosive. The epoxy zinc-rich primer is one layer with a thickness of 60 μm; the epoxy sealing paint is one layer with a thickness of 140 μm; and the epoxy thick paste paint is two layers, each layer having a thickness of 80 μm.

[0042] Specifically, in the present embodiment,

[0043] The epoxy zinc-rich primer comprises, by weight fraction: graphene 3 parts, MXene 3 parts, liquid epoxy resin 24 parts, 800-1000 mesh zinc powder 136 parts, accelerator (DMP-30) 4 parts, polyamide curing agent 26 parts, phosphorus iron powder 20 parts, active diluent 16 parts, zinc phosphate 4 parts, REC-1 type rare earth ytterbium chelate 1 part, and REC-2 type rare earth yttrium chelate 1 part.

[0044] The epoxy sealing paint comprises, by weight fraction: epoxy resin 100 parts, aluminum oxide 25 parts, titanium oxide 6 parts, iron oxide 15 parts, DMP-30 accelerator 3 parts, active diluent (ethylene glycol diglycidyl ether) 10 parts, polyamide curing agent 62 parts, REC-1 type rare earth ytterbium chelate 1 part, and REC-2 type rare earth yttrium chelate 1 part.

[0045] The epoxy thick paste paint comprises, by weight fraction: epoxy resin 80 parts, talc powder 34 parts, aluminum oxide 17 parts, mica powder 14 parts, precipitated barium sulfate 8 parts, iron oxide 12 parts, DMP-30 accelerator 3 parts, active diluent solvent (ethylene glycol diglycidyl ether) 7 parts, polyamide curing agent 42 parts, REC-1 type rare earth ytterbium chelate 1 part, and REC-2 type rare earth yttrium chelate 1 part.

[0046] The preparation method of the epoxy zinc-rich primer comprises the following steps: mixing liquid epoxy resin, zinc phosphate, zinc powder, and phosphorus iron powder at a rotation speed of 600 r / min for 2 hours, then adding a proper amount of modified graphene MXene-bilayer nanosheet, rare earth chelate, active diluent, phosphorus iron powder, and DMP-30 accelerator, and stirring and mixing at a rotation speed of 800 r / min for 2 hours, and finally adding polyamide curing agent, and stirring fully at a rotation speed of 800 r / min for 1-2 hours until a uniform paste is formed.

[0047] The preparation method of the modified graphene MXene-bilayer nanosheet comprises the following steps:

[0048] The graphene nanosheet and the MXene nanosheet are respectively ultrasonically cleaned in ethanol for 30 minutes, then dispersed in a DMF solvent, ultrasonically stirred for 15 min to make the dispersion uniform, a proper amount of siloxane coupling agent is added to the dispersion, stirring is maintained and heating is performed to 95 ℃, and then reaction is performed for 3 h, after the reaction is completed, centrifugation is performed at a speed of 4500 rpm for 30 minutes, and washing is performed with the DMF solvent for three times, and finally drying is performed to obtain the graphene and MXene nanosheet modified by siloxane;

[0049] 1 g of the modified MXene nanosheet powder and 1 g of the modified graphene nanosheet are respectively added to a solution of 25 mg / mL -1The graphene-MXene double nanosheet suspension was obtained by ultrasonic treatment of 50 mL of NMP with an ultrasonic machine at 40 kHz for 5 h under continuous nitrogen protection, with the ultrasonic temperature controlled at about 30℃. Large particles were removed by centrifugation at a speed of 3000 rpm for 1 h. Finally, the stable modified graphene-MXene double nanosheet colloidal suspension was obtained by repeatedly washing with deionized water until the supernatant PH was about 7.

[0050] The preparation method of the epoxy sealing paint is as follows: first, the epoxy resin, aluminum oxide, titanium oxide, and iron oxide are fully mixed at a speed of 800 r / min for 3 hours, then the DMP-30 accelerator, active diluent, REC-1 type rare earth ytterbium chelate, and REC-2 type rare earth yttrium chelate are further mixed at a speed of 800 r / min for 1 hour, and finally the polyamide curing agent is fully stirred at a speed of 1200 r / min for 2 hours to form a uniform slurry.

[0051] The preparation method of the epoxy thick paste paint is as follows: first, the epoxy resin, talc powder, aluminum oxide, mica powder, precipitated barium sulfate, and iron oxide are stirred and mixed at a speed of 1200 r / min for 4 hours, then the DMP-30 accelerator, active diluent, REC-1 type rare earth ytterbium chelate, and REC-2 type rare earth yttrium chelate are further stirred and mixed at a speed of 800 r / min for 1 hour, and finally the polyamide curing agent is fully stirred at a speed of 1500 r / min for 2 hours to form a uniform slurry.

[0052] In addition, it should be noted that all the powder materials in this embodiment are subjected to silane modification treatment. The silane modification method includes: adding the powder material into deionized water and ultrasonic cleaning for 30 minutes, then adding a 5% mass fraction of silane coupling agent ethanol solution, sealing and placing on a constant temperature 80℃ magnetic stirrer for continuous stirring for 3 hours. After the reaction is completed, the obtained product is washed three times by suction filtration and dried in an oven for 12h to constant weight to obtain the modified powder filler. The powder materials include aluminum oxide, titanium oxide, iron oxide, precipitated barium sulfate, mica powder, talc powder, and phosphorus iron powder.

[0053] It should be further noted that the graphene nanosheet in this embodiment is from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0054] The silane coupling agent is one of methyltrimethoxysilane (Younshine Chemical Co., Ltd.), phenyltrimethoxysilane (Zhejiang Woxing Chemical Co., Ltd.), methyltriethoxysilane (Shandong Duoli Chemical Co., Ltd.), ethyltrimethoxysilane (Qufu Yishun Chemical Co., Ltd.), and ethyltriethoxysilane (Qufu Yishun Chemical Co., Ltd.).

[0055] Polyamide curing agent, amine value 200±20(mgKOH / g), viscosity 2000-4000mpa.s, Jinan Yuanbaolai Chemical Technology Co., Ltd.

[0056] REC-1 type rare earth ytterbium chelate and REC-2 type rare earth yttrium chelate are purchased from Shaanxi Xitai Xingbang Material Technology Co., Ltd.

[0057] DPM-30 accelerator is purchased from Jinan Qingtian Chemical Technology Co., Ltd.

[0058] Ethylene glycol diglycidyl ether is purchased from Shandong Jinghao Chemical Co., Ltd.

[0059] Graphene and MXene nanosheet are purchased from Suzhou Beikeman Nanotechnology Co., Ltd.

[0060] Example 2

[0061] The difference between this embodiment and example 1 is that the graphene-MXene composite heavy anti-corrosion material provided by this embodiment comprises a graphene-MXene modified epoxy zinc-rich primer, an epoxy sealing paint and an epoxy thick paste paint arranged on the surface of the body to be anticorrosive in sequence, wherein:

[0062] The epoxy zinc-rich primer comprises, by weight fraction: graphene 1 part, MXene 3 parts, liquid epoxy resin 22 parts, 800-1000 mesh zinc powder 131 parts, accelerator (DMP-30) 3 parts, polyamide curing agent 24 parts, phosphorus iron powder 15 parts, active diluent 13 parts, zinc phosphate 3 parts, REC-1 type rare earth ytterbium chelate 1 part, and REC-2 type rare earth yttrium chelate 1 part.

[0063] The epoxy sealing paint comprises, by weight fraction: epoxy resin 100 parts, aluminum oxide 25 parts, titanium oxide 6 parts, iron oxide 15 parts, DMP-30 accelerator 3 parts, active diluent (ethylene glycol diglycidyl ether) 10 parts, polyamide curing agent 62 parts, REC-1 type rare earth ytterbium chelate 1 part, and REC-2 type rare earth yttrium chelate 1 part.

[0064] The epoxy thick paste paint comprises, by weight fraction: epoxy resin 80 parts, talc powder 34 parts, aluminum oxide 17 parts, mica powder 14 parts, precipitated barium sulfate 8 parts, iron oxide 12 parts, DMP-30 accelerator 3 parts, active diluent solvent (ethylene glycol diglycidyl ether) 7 parts, polyamide curing agent 42 parts, REC-1 type rare earth ytterbium chelate 1 part, and REC-2 type rare earth yttrium chelate 1 part.

[0065] Example 3

[0066] The difference between the embodiment and embodiment 1 is that the graphene-MXene composite heavy anti-corrosion material provided by the embodiment comprises a graphene-MXene modified epoxy zinc-rich primer, an epoxy sealing paint and an epoxy thick paste paint which are sequentially arranged on the surface of a body to be anticorrosion, wherein the graphene-MXene modified epoxy zinc-rich primer comprises graphene 2 parts, MXene 2 parts, liquid epoxy resin 22 parts, 800-1000 mesh zinc powder 131 parts, accelerator (DMP-30) 3 parts, polyamide curing agent 24 parts, phosphorus iron powder 15 parts, active diluent 13 parts, zinc phosphate 3 parts, REC-1 type rare earth ytterbium chelate 1 part and REC-2 type rare earth yttrium chelate 1 part.

[0067] The epoxy sealing paint comprises, by weight fraction, epoxy resin 100 parts, aluminum oxide 25 parts, titanium oxide 6 parts, iron oxide 15 parts, DMP-30 accelerator 3 parts, active diluent (glycol diglycidyl ether) 10 parts, polyamide curing agent 62 parts, REC-1 type rare earth ytterbium chelate 1 part and REC-2 type rare earth yttrium chelate 1 part.

[0068] The epoxy sealing paint comprises, by weight fraction, epoxy resin 100 parts, aluminum oxide 25 parts, titanium oxide 6 parts, iron oxide 15 parts, DMP-30 accelerator 3 parts, active diluent (glycol diglycidyl ether) 10 parts, polyamide curing agent 62 parts, REC-1 type rare earth ytterbium chelate 1 part and REC-2 type rare earth yttrium chelate 1 part.

[0069] The epoxy thick paste paint comprises, by weight fraction, epoxy resin 80 parts, talc powder 34 parts, aluminum oxide 17 parts, mica powder 14 parts, precipitated barium sulfate 8 parts, iron oxide 12 parts, DMP-30 accelerator 3 parts, active diluent solvent (glycol diglycidyl ether) 7 parts, polyamide curing agent 42 parts, REC-1 type rare earth ytterbium chelate 1 part and REC-2 type rare earth yttrium chelate 1 part.

[0070] Embodiment 4

[0071] The difference between the embodiment and embodiment 1 is that the graphene-MXene composite heavy anti-corrosion material provided by the embodiment comprises a graphene-MXene modified epoxy zinc-rich primer, an epoxy sealing paint and an epoxy thick paste paint which are sequentially arranged on the surface of a body to be anticorrosion, wherein the graphene-MXene modified epoxy zinc-rich primer comprises graphene 2 parts, MXene 2 parts, liquid epoxy resin 22 parts, 800-1000 mesh zinc powder 131 parts, accelerator (DMP-30) 3 parts, polyamide curing agent 24 parts, phosphorus iron powder 15 parts, active diluent 13 parts, zinc phosphate 3 parts, REC-1 type rare earth ytterbium chelate 1 part and REC-2 type rare earth yttrium chelate 1 part.

[0072] The epoxy sealing paint comprises, by weight fraction, epoxy resin 100 parts, aluminum oxide 25 parts, titanium oxide 6 parts, iron oxide 15 parts, DMP-30 accelerator 3 parts, active diluent (glycol diglycidyl ether) 10 parts, polyamide curing agent 62 parts, REC-1 type rare earth ytterbium chelate 1 part and REC-2 type rare earth yttrium chelate 1 part.

[0073] The epoxy sealing paint comprises, by weight fraction, epoxy resin 100 parts, aluminum oxide 25 parts, titanium oxide 6 parts, iron oxide 15 parts, DMP-30 accelerator 3 parts, active diluent (glycol diglycidyl ether) 10 parts, polyamide curing agent 62 parts, REC-1 type rare earth ytterbium chelate 1 part and REC-2 type rare earth yttrium chelate 1 part.

[0074] The epoxy thick paste paint comprises, in parts by weight: epoxy resin 80 parts, talcum powder 34 parts, aluminum oxide 17 parts, mica powder 14 parts, precipitated barium sulfate 8 parts, iron oxide 12 parts, DMP-30 accelerator 3 parts, active diluent (glycol diglycidyl ether) 7 parts, polyamide curing agent 42 parts, REC-1 type rare earth ytterbium chelate 1 part, and REC-2 type rare earth yttrium chelate 1 part.

[0075] Example 5

[0076] The difference between the present embodiment and Example 1 is that the present embodiment provides a graphene-MXene composite heavy-duty anticorrosive material, which comprises a graphene-MXene modified epoxy zinc-rich primer, an epoxy sealing paint and an epoxy thick paste paint arranged on the surface of a body to be anticorrosive in sequence, wherein:

[0077] The epoxy zinc-rich primer comprises, in parts by weight: graphene 1 part, MXene 1 part, liquid epoxy resin 20 parts, 800-1000 mesh zinc powder 126 parts, accelerator (DMP-30) 2 parts, polyamide curing agent 22 parts, phosphorus iron powder 10 parts, active diluent 10 parts, zinc phosphate 2 parts, REC-1 type rare earth ytterbium chelate 1 part, and REC-2 type rare earth yttrium chelate 1 part.

[0078] The epoxy sealing paint comprises, in parts by weight: epoxy resin 100 parts, aluminum oxide 25 parts, titanium oxide 6 parts, iron oxide 15 parts, DMP-30 accelerator 3 parts, active diluent (glycol diglycidyl ether) 10 parts, polyamide curing agent 62 parts, REC-1 type rare earth ytterbium chelate 1 part, and REC-2 type rare earth yttrium chelate 1 part.

[0079] The epoxy thick paste paint comprises, in parts by weight: epoxy resin 80 parts, talcum powder 34 parts, aluminum oxide 17 parts, mica powder 14 parts, precipitated barium sulfate 8 parts, iron oxide 12 parts, DMP-30 accelerator 3 parts, active diluent (glycol diglycidyl ether) 7 parts, polyamide curing agent 42 parts, REC-1 type rare earth ytterbium chelate 1 part, and REC-2 type rare earth yttrium chelate 1 part.

[0080] Comparative Example 1

[0081] The difference between the present embodiment and Example 1 is that the present embodiment provides a graphene-MXene composite heavy-duty anticorrosive material, which comprises a graphene-MXene modified epoxy zinc-rich primer, an epoxy sealing paint and an epoxy thick paste paint arranged on the surface of a body to be anticorrosive in sequence, wherein:

[0082] The epoxy zinc-rich primer comprises, by weight fraction: graphene 1 part, MXene 1 part, liquid epoxy resin 20 parts, 800-1000 mesh zinc powder 126 parts, accelerator (DMP-30) 2 parts, polyamide curing agent 22 parts, phosphorus iron powder 10 parts, active diluent 10 parts, zinc phosphate 2 parts.

[0083] The epoxy sealing paint comprises, by weight fraction: epoxy resin 100 parts, alumina 25 parts, titanium oxide 6 parts, iron oxide 15 parts, DMP-30 accelerator 3 parts, active diluent (glycol diglycidyl ether) 10 parts, polyamide curing agent 62 parts.

[0084] The epoxy thick paste paint comprises, by weight fraction: epoxy resin 80 parts, talc powder 34 parts, alumina 17 parts, mica powder 14 parts, precipitated barium sulfate 8 parts, iron oxide 12 parts, DMP-30 accelerator 3 parts, active diluent solvent (glycol diglycidyl ether) 7 parts, polyamide curing agent 42 parts.

[0085] Comparative Example 2

[0086] The difference between Example 1 is that the heavy anti-corrosion material provided by the embodiment comprises an epoxy zinc-rich primer, an epoxy sealing paint and an epoxy thick paste paint arranged on the surface of the body to be anticorrosion in sequence, wherein: all the powder materials are not subjected to silane modification treatment, the epoxy zinc-rich primer does not contain graphene and MXene, and the epoxy zinc-rich primer, the epoxy sealing paint and the epoxy thick paste paint do not contain rare earth chelating agent, and specifically comprises:

[0087] The epoxy zinc-rich primer comprises, by weight fraction: liquid epoxy resin 20 parts, 800-1000 mesh zinc powder 126 parts, accelerator (DMP-30) 2 parts, polyamide curing agent 22 parts, phosphorus iron powder 10 parts, active diluent 10 parts, zinc phosphate 2 parts.

[0088] The epoxy sealing paint comprises, by weight fraction: epoxy resin 100 parts, alumina 25 parts, titanium oxide 6 parts, iron oxide 15 parts, DMP-30 accelerator 3 parts, active diluent (glycol diglycidyl ether) 10 parts, polyamide curing agent 62 parts.

[0089] The epoxy thick paste paint comprises, by weight fraction: epoxy resin 80 parts, talc powder 34 parts, alumina 17 parts, mica powder 14 parts, precipitated barium sulfate 8 parts, iron oxide 12 parts, DMP-30 accelerator 3 parts, active diluent solvent (glycol diglycidyl ether) 7 parts, polyamide curing agent 42 parts.

[0090] The heavy-duty anticorrosive materials in Examples 1-5 and Comparative Examples 1-2 were all subjected to salt spray resistance test (referring to GB / T 10125), VOCs test (referring to GB / T 23985-2009), aging resistance test (referring to GB / T 1865-2009), hardness test (referring to GB / T 6739-2006), adhesion test (referring to GB 1720-79), wear resistance test (referring to GB / T 1768-2006), water resistance test (referring to GB / T 1766-2008), and chemical resistance test (referring to GB / T 9274-2010).

[0091] The test results are shown in the following table.

[0092] Table 1 Performance test results of the heavy-duty anticorrosive materials in Examples 1-5 and Comparative Examples 1-2

[0093]

[0094]

[0095] As can be seen from Comparative Example 1 and Comparative Example 2, the addition of graphene and MXene helps to improve the water resistance, chemical resistance, salt spray resistance, aging resistance, and wear resistance of the heavy-duty anticorrosive material, and is more environmentally friendly. In addition, as can be seen from the performance test results of the heavy-duty anticorrosive materials in Examples 1-5 and Comparative Examples 1-2, the heavy-duty anticorrosive material obtained in Examples 1-5 has excellent water resistance, chemical resistance, salt spray resistance, aging resistance, and wear resistance compared to the heavy-duty anticorrosive material obtained in Comparative Examples 1 and 2. Thus, it can be seen that the silane modification treatment of the powder material, the graphene-MXene modification treatment, and the addition of the rare earth chelating agent have a significant effect on improving the salt spray resistance, aging resistance, wear resistance, and environmental friendliness of the heavy-duty anticorrosive material. As can be seen from Examples 1-4 and Example 5, the content of graphene and MXene has an impact on the chemical resistance, adhesion, salt spray resistance, aging resistance, and wear resistance of the heavy-duty anticorrosive material, i.e., as the content of graphene and MXene decreases, the chemical resistance, adhesion, salt spray resistance, aging resistance, and wear resistance of the heavy-duty anticorrosive material decrease.

[0096] Although the present disclosure is as above, the protection scope of the present disclosure is not limited to this. Those skilled in the art can make various modifications and changes without departing from the spirit and scope of the present disclosure, and these modifications and changes shall fall within the protection scope of the present disclosure.

Claims

1. A graphene-MXene composite heavy-duty anticorrosion material, characterized in that, The application relates to an anticorrosive coating, which comprises an epoxy zinc-rich primer (1) with a solid content of 50-70% arranged on the surface of a body to be protected, an epoxy sealing paint (2) with a solid content of 50-70% and an epoxy thick paste paint (3) with a solid content of 50-70% arranged in sequence on the surface of the body to be protected, wherein the weight composition of the epoxy zinc-rich primer (1) comprises: graphene 0.5-1.5%, MXene 0.5-1.5%, liquid epoxy resin 10-12%, 800-1000 mesh zinc powder 62.5-67.8%, DMP-30 accelerator 1-2%, polyamide curing agent 11-13%, phosphorus iron powder 5-10%, active diluent 5-8%, zinc phosphate 1-2%, REC-1 rare earth ytterbium chelate 0.1-0.5% and REC-2 rare earth yttrium chelate 0.1-0.5%, the epoxy sealing paint (2) comprises, in terms of weight fraction: epoxy resin 100 parts, aluminum oxide 25 parts, titanium oxide 6 parts, iron oxide 15 parts, DMP-30 accelerator 3 parts, active diluent 10 parts, polyamide curing agent 62 parts, REC-1 type rare earth ytterbium chelate 1 part and REC-2 type rare earth yttrium chelate 1 part, the epoxy thick paste paint (3) comprises, in terms of weight fraction: epoxy resin 80 parts, talc powder 34 parts, aluminum oxide 17 parts, mica powder 14 parts, precipitated barium sulfate 8 parts, iron oxide 12 parts, DMP-30 accelerator 3 parts, active diluent 7 parts, polyamide curing agent 42 parts, REC-1 type rare earth ytterbium chelate 1 part and REC-2 type rare earth yttrium chelate 1 part, the epoxy zinc-rich primer (1) is subjected to graphene-MXene modification treatment, the epoxy zinc-rich primer (1), the epoxy sealing paint (2) and the epoxy thick paste paint (3) all contain rare earth chelating agents, and all the powder materials in the epoxy zinc-rich primer (1), the epoxy sealing paint (2) and the epoxy thick paste paint (3) are subjected to silane modification treatment, and the preparation method of the graphene-MXene comprises the following steps: graphene nanosheets and MXene nanosheet powders are respectively subjected to ultrasonic cleaning in ethanol for 25-35 minutes, are dispersed in DMF solvents and are subjected to ultrasonic stirring for 10-20 minutes to obtain a dispersion liquid, 5% siloxane coupling agent is added into the dispersion liquid, stirring and heating are conducted to 90-100 DEG C, reaction is conducted for 3 hours, modified MXene nanosheet powders and modified graphene nanosheets treated by siloxane are obtained through centrifugation and washing, and the modified MXene nanosheet powders and the modified graphene nanosheets are used to prepare the graphene-MXene. 2.The graphene-MXene composite heavy-duty anticorrosion material according to claim 1, characterized in that, The modified MXene nanosheet powder and the modified graphene nanosheet are used to prepare the graphene-MXene, including: the modified MXene nanosheet powder and the modified graphene nanosheet are respectively added into 45-55 mL of NMP with an initial concentration of 22-28 mg / mL, and ultrasonic treatment is carried out under nitrogen protection at a temperature of 28-32℃ for 4-6 h to obtain a graphene-MXene double nanosheet suspension, and then centrifugation and washing are carried out until the supernatant has a pH of 7 to obtain the graphene-MXene. 3.The graphene-MXene composite heavy-duty anticorrosion material of claim 1, characterized in that, The method for the silane modification treatment includes: after the powder material is added into deionized water and ultrasonic cleaning is carried out for 25-35 minutes, the powder material is added into an ethanol solution of a silane coupling agent with a mass fraction of 5%, sealed, and placed on a magnetic stirrer at a constant temperature of 80℃ for continuous stirring for 2.5-3.5 hours, and then the modified powder material is obtained after filtration, washing, and drying to a constant weight.

4. The graphene-MXene composite heavy-duty anticorrosion material according to claim 3, characterized in that, The silane coupling agent includes one of methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane. 5.The graphene-MXene composite heavy-duty anticorrosion material of claim 1, wherein, The epoxy zinc-rich primer (1) is 1 layer, and the thickness is 59-61 μm; the epoxy sealing paint (2) is 1 layer, and the thickness is 139-141 μm; and the epoxy thick paste paint (3) is 2 layers, and the thickness of each layer of the epoxy thick paste paint (3) is 79-81 μm.

6. Use of the graphene-MXene composite heavy-duty anticorrosion material according to any one of claims 1-5, characterized in that, The graphene-MXene composite heavy-duty anticorrosive material is coated on the surface of a steel structure building or a petrochemical equipment for anticorrosive protection.

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