Wear-resistant anticorrosion tungsten steel material and processing technology thereof

Abstract

The present application relates to the technical field of corrosion-resistant coating, in particular to a wear-resistant and corrosion-resistant tungsten steel material and a processing technology thereof.The modified epoxy resin is obtained by adding raw materials such as epoxy resin and dichlorodimethylsilane.Then the modified epoxy resin, epoxy resin, hydrophobic modified graphene, anti-aging modified carbon fiber, modified alumina, curing agent, defoaming agent, leveling agent and wetting dispersant are mixed to obtain the anticorrosive coating.The tungsten steel material with good corrosion resistance is prepared by coating the anticorrosive coating on the surface of the tungsten steel substrate, so it has a wide application prospect in the technical field of corrosion-resistant coating.

Description

Technical Field

[0001] This invention relates to the field of corrosion-resistant coating technology, specifically to a wear-resistant and corrosion-resistant tungsten steel material and its processing technology. Background Technology

[0002] Tungsten carbide (TCC) materials use high-hardness, high-melting-point tungsten carbide particles as a framework, sintered through powder metallurgy to obtain TCC materials with high hardness and high wear resistance. In modern industry, TCC materials have become a key basic material supporting precision manufacturing and improving equipment efficiency. However, the corrosion resistance of TCC materials is relatively poor, which constitutes a major bottleneck for their application in wider and more severe working conditions. Its corrosion resistance limitation mainly stems from the electrochemical instability of the metallic binder phase in corrosive media. In acidic, alkaline, or saline humid environments, the binder phase is prone to selective dissolution, causing the hard tungsten carbide particles to lose support and detach, triggering a synergistic accelerated failure of "corrosion-wear," damaging the structure of the TCC material, and accelerating material failure.

[0003] To overcome the shortcomings of the prior art, the present invention provides a wear-resistant and corrosion-resistant tungsten steel material and its processing technology. Summary of the Invention

[0004] The purpose of this invention is to provide a wear-resistant and corrosion-resistant tungsten steel material and its processing technology to solve the problems raised in the prior art.

[0005] To achieve the above objectives, the present invention provides the following technical solution: A processing technology for wear-resistant and corrosion-resistant tungsten carbide material includes the following steps: Step 1: Mix epoxy resin and ethyl acetate, heat, stir evenly, then add dibutyltin dilaurate, dichlorodimethylsilane and triethylamine in sequence, continue the reaction, and after the reaction is completed, centrifuge, wash and distill under reduced pressure to obtain modified epoxy resin. Step 2: Mix modified epoxy resin, epoxy resin, hydrophobic modified graphene, anti-aging modified carbon fiber, modified alumina, curing agent, defoamer, leveling agent and wetting and dispersing agent, stir and disperse to obtain anti-corrosion coating; apply the anti-corrosion coating evenly to the surface of tungsten carbide substrate, cure to obtain finished product.

[0006] In a more optimized manner, the modified epoxy resin is obtained by stirring and reacting at 50-55℃ for 2-3 hours; and cured at 70-80℃ for 3-4 hours to obtain the finished product; the reaction mass ratio of epoxy resin to dichlorodimethylsilane is 1:(0.13-0.15); and the coating thickness is 20-25μm.

[0007] In a more optimized manner, modified epoxy resin, hydrophobic modified graphene, anti-aging modified carbon fiber, curing agent, wetting and dispersing agent, defoamer, and leveling agent are mixed and stirred and dispersed for 20-30 minutes to obtain an anti-corrosion coating.

[0008] In a more optimized manner, in step two, the composition of the anti-corrosion coating is as follows: by mass parts, 20-30 parts modified epoxy resin, 30-40 parts epoxy resin, 2-3 parts hydrophobic modified graphene, 10-12 parts anti-aging modified carbon fiber, 10-15 parts modified alumina, 8-12 parts curing agent, 1-2 parts wetting and dispersing agent, 1-2 parts defoamer, and 0.5-0.8 parts leveling agent; wherein the curing agent is polyamide.

[0009] A more optimized preparation process for anti-aging modified carbon fiber is as follows: Step S1: Mix carbon fiber and acetone for Soxhlet extraction, reflux for 20-25 h, then wash and dry the fiber to obtain pretreated carbon fiber; then mix the pretreated carbon fiber with hydrogen peroxide solution, stir and react for 10-12 h, and after the reaction is completed, wash and dry to obtain activated carbon fiber. Step S2: Mix activated carbon fibers with anhydrous ethanol, then add 3-mercaptopropyltriethoxysilane, ultrasonically disperse for 20-30 min, add hydrochloric acid solution, adjust the pH of the solution to 4-5, react at 70-75℃ for 6-7 h, after the reaction is completed, wash with alcohol and dry to obtain modified carbon fibers. Step S3: Add 2,4-dihydroxybenzophenone and triethylamine to tetrahydrofuran, stir to dissolve, and then add acryloyl chloride solution dropwise at 0-2℃. Continue the reaction for 6-8 hours. After the reaction is completed, wash, recrystallize and dry to obtain the modified benzophenone anti-aging agent. Step S4: Mix modified carbon fiber, modified benzophenone anti-aging agent, α,α-dimethoxy-α-phenylacetophenone, and chloroform, and react under ultraviolet light for 30-40 minutes. After the reaction is completed, wash and dry to obtain anti-aging modified carbon fiber.

[0010] In a more optimized manner, in step S1, the concentration of hydrogen peroxide solution is 25-28 wt%; in step S2, the reaction mass ratio of activated carbon fiber to 3-mercaptopropyltriethoxysilane is 2:(0.8-1.0); in step S3, the reaction molar ratio of 2,4-dihydroxybenzophenone to acryloyl chloride is 1:(1.3-1.4); and in step S4, the reaction mass ratio of modified carbon fiber to modified benzophenone-based anti-aging agent is 1:(0.03-0.05).

[0011] A more optimized preparation process for hydrophobically modified graphene is as follows: graphene oxide is added to a mixed solution of anhydrous ethanol and deionized water, and after being ultrasonically dispersed evenly, γ-aminopropyltriethoxysilane and perfluorooctyltriethoxysilane are added. The mixture is stirred and reacted at 40-45℃ for 7-8 hours. After the reaction is completed, the graphene is filtered, washed with water, washed with alcohol, and dried to obtain hydrophobically modified graphene.

[0012] The optimal reaction mass ratio of graphene oxide, γ-aminopropyltriethoxysilane, and perfluorooctyltriethoxysilane is 1:(0.20-0.25):(0.4-0.5).

[0013] A more optimized preparation process for modified alumina is as follows: γ-aminopropyltriethoxysilane is added to a mixed solution of anhydrous ethanol and deionized water, stirred for 15-20 min, then alumina powder is added, the temperature is raised to 60-65℃ and stirred for 4-5 h, and after the reaction is completed, the modified alumina is obtained by filtration, washing and drying.

[0014] The optimal reaction mass ratio of alumina powder to γ-aminopropyltriethoxysilane is 1:(0.02-0.03).

[0015] The beneficial effects of this invention are: The key feature of this invention is that pretreated carbon fibers are surface-modified by adding hydrogen peroxide solution to obtain activated carbon fibers with numerous active groups on their surface. The activated carbon fibers are then further surface-modified using the silane coupling agent 3-mercaptopropyltriethoxysilane to obtain mercapto-modified carbon fibers. A substitution reaction is then initiated by adding 2,4-dihydroxybenzophenone, triethylamine, and acryloyl chloride solution to introduce acryloyl groups, yielding a modified benzophenone-based anti-aging agent. The prepared modified benzophenone-based anti-aging agent is then mixed with mercapto-modified carbon fibers, and a mercapto-olefin click reaction is carried out under ultraviolet light irradiation to obtain mercapto-resistant aging-modified carbon fibers.

[0016] Among them, the propyl chain of 3-mercaptopropyltriethoxysilane can form an organosilane film on the fiber surface, with its alkyl chains arranged outwards, reducing surface energy and providing basic hydrophobicity. Furthermore, benzophenone-based anti-aging agents with good anti-aging properties are introduced onto the modified carbon fiber surface via a mercapto-olefin click reaction, resulting in anti-aging modified carbon fibers. On the one hand, the anti-aging agent is chemically bonded to the carbon fiber surface, preventing migration, volatilization, and leaching, thus achieving long-lasting UV shielding; on the other hand, by forming an anti-aging layer on the fiber surface, the anti-aging performance of the material can be effectively reduced.

[0017] The key feature of this invention is that graphene oxide, γ-aminopropyltriethoxysilane, and perfluorooctyltriethoxysilane are mixed and subjected to a hydrolysis-condensation reaction to introduce hydrophobic groups and active amino groups, resulting in hydrophobically modified graphene. Graphene oxide has a surface rich in oxygen functional groups; therefore, after synergistic treatment with the addition of bissilanes, ultra-long perfluoroalkyl chains can be introduced, endowing the material with hydrophobic and oleophobic properties and providing extremely low surface energy. Active amino groups can also be introduced to provide active reaction sites for further chemical modification, i.e., effective crosslinking between the active amino groups and epoxy resin. Furthermore, alumina powder and γ-aminopropyltriethoxysilane are mixed and subjected to a hydrolysis-condensation reaction to introduce active amino groups, resulting in modified alumina.

[0018] The key feature of this invention is the nucleophilic substitution reaction of epoxy resin and dichlorodimethylsilane under the catalysis of dibutyltin dilaurate, yielding a hydrophobically modified epoxy resin. The methylsiloxane segments possess low surface energy, allowing the siloxane structure to be introduced into the epoxy resin structure through a chemical reaction, resulting in an intrinsically hydrophobic resin structure, which is fundamental for the anti-corrosion coating. The modified epoxy resin, epoxy resin, additives, and three different types of modified fillers are then mixed to obtain an anti-corrosion coating. One-dimensional fibers (anti-aging modified carbon fiber) provide mechanical reinforcement, form physical barriers, and actively resist aging. Two-dimensional sheets (hydrophobically modified graphene) provide excellent labyrinth barrier effects and enhance overall hydrophobicity. Zero-dimensional particles (modified alumina) provide good wear resistance and fill voids, optimizing coating density. Furthermore, hydrophobically modified graphene and modified alumina, by introducing active amino groups, not only improve the dispersibility of fillers but also enable effective cross-linking reactions with the epoxy resin matrix, forming a dense and corrosion-resistant coating. Moreover, the surface of the anti-aging modified carbon fiber is covalently grafted with benzophenone-based anti-aging agents via click chemiluminescence, providing a highly efficient and long-lasting anti-aging protection mechanism.

[0019] In summary, this anti-corrosion coating blends epoxy resin, hydrophobically modified epoxy resin, and complementary modified fillers (lamellar barrier, fiber reinforcement, particle filling, and active protection) to construct a dense and robust composite material structure. Therefore, when this anti-corrosion coating is uniformly applied to the surface of a tungsten carbide substrate and cured, the resulting tungsten carbide material exhibits excellent corrosion resistance, thus showing broad application prospects in the field of corrosion-resistant coating technology. Detailed Implementation

[0020] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0021] Raw material source: Graphene oxide, supplied by Zhongke Leiming (Beijing) Technology Co., Ltd., with specifications of 0.5-3μm and >99wt%; carbon fiber, supplied by Carbonene Technology (Shenzhen) Co., Ltd., with a length of 0.5mm; alumina powder, supplied by Qinghe County Chaotai Metal Materials Co., Ltd., with specifications of 500 mesh; epoxy resin, supplied by Jinan Chengwu Chemical Co., Ltd., with grade E-44; polyamide, supplied by Jinan Jibin Chemical Co., Ltd., with model 650651300; wetting and dispersing agent, BYK-220S; leveling agent, BYK-345; defoamer, BYK-066N; by mass, one part is 1g.

[0022] Example 1: Step 1: Step S1: Carbon fiber and acetone were mixed and subjected to Soxhlet extraction. After reflux for 25 hours, the fibers were washed with water and dried to obtain pretreated carbon fiber. The pretreated carbon fiber was then mixed with hydrogen peroxide solution and stirred for 12 hours. After the reaction was completed, the fibers were washed with water and dried to obtain activated carbon fiber. The concentration of the hydrogen peroxide solution was 26 wt%. Step S2: Mix activated carbon fiber and anhydrous ethanol, then add 3-mercaptopropyltriethoxysilane, ultrasonically disperse for 30 min, add hydrochloric acid solution to adjust the pH of the solution to 5, react at 75℃ for 7 h, after the reaction is completed, wash with alcohol and dry to obtain modified carbon fiber; the reaction mass ratio of activated carbon fiber to 3-mercaptopropyltriethoxysilane is 2:0.9; Step S3: Add 2,4-dihydroxybenzophenone and triethylamine to tetrahydrofuran, stir to dissolve, and then add acryloyl chloride solution dropwise at 2°C. Continue the reaction for 8 hours. After the reaction is completed, wash, recrystallize and dry to obtain the modified benzophenone anti-aging agent. The molar ratio of 2,4-dihydroxybenzophenone to acryloyl chloride is 1:1.4. Step S4: The modified carbon fiber, modified benzophenone anti-aging agent, α,α-dimethoxy-α-phenylacetophenone, and chloroform are mixed and reacted under ultraviolet light for 40 minutes. After the reaction is completed, the mixture is washed and dried to obtain anti-aging modified carbon fiber. The mass ratio of modified carbon fiber to modified benzophenone anti-aging agent is 1:0.04. Step 2: Add graphene oxide to a mixed solution of anhydrous ethanol and deionized water, disperse it evenly by ultrasonication, then add γ-aminopropyltriethoxysilane and perfluorooctyltriethoxysilane, and stir the mixture at 45°C for 8 hours. After the reaction is complete, filter, wash with water, wash with alcohol, and dry to obtain hydrophobically modified graphene. The mass ratio of graphene oxide, γ-aminopropyltriethoxysilane, and perfluorooctyltriethoxysilane is 1:0.23:0.45. Step 3: Add γ-aminopropyltriethoxysilane to a mixed solution of anhydrous ethanol and deionized water, stir for 20 min, then add alumina powder, heat to 65℃ and stir for 5 h. After the reaction is complete, filter, wash and dry to obtain modified alumina; the mass ratio of alumina powder to γ-aminopropyltriethoxysilane is 1:0.025. Step 4: Mix epoxy resin and ethyl acetate, heat to 55℃, stir evenly, and then add dibutyltin dilaurate, dichlorodimethylsilane and triethylamine in sequence. Continue the reaction for 3 hours. After the reaction is completed, centrifuge, wash and distill under reduced pressure to obtain modified epoxy resin; the mass ratio of epoxy resin to dichlorodimethylsilane is 1:0.14. Step 5: Mix 25g modified epoxy resin, 35g epoxy resin, 2g hydrophobic modified graphene, 11g anti-aging modified carbon fiber, 12g modified alumina, 10g polyamide, 1.5g wetting and dispersing agent BYK-220S, 1.5g defoamer BYK-066N, and 0.7g leveling agent BYK-345, and stir and disperse for 30 minutes to obtain an anti-corrosion coating; uniformly coat the anti-corrosion coating onto the surface of the tungsten carbide substrate, and cure at 80℃ for 4 hours to obtain the finished product; the coating thickness is 20μm.

[0023] Example 2: Step 1: Step S1: Carbon fibers and acetone were mixed and subjected to Soxhlet extraction. After reflux for 22 hours, the fibers were washed with water and dried to obtain pretreated carbon fibers. The pretreated carbon fibers were then mixed with hydrogen peroxide solution and stirred for 11 hours. After the reaction was completed, the fibers were washed with water and dried to obtain activated carbon fibers. The concentration of the hydrogen peroxide solution was 26 wt%. Step S2: Mix activated carbon fibers and anhydrous ethanol, then add 3-mercaptopropyltriethoxysilane, ultrasonically disperse for 25 min, add hydrochloric acid solution to adjust the pH of the solution to 4.5, react at 72℃ for 6.5 h, wash with alcohol and dry after the reaction to obtain modified carbon fibers; the reaction mass ratio of activated carbon fibers to 3-mercaptopropyltriethoxysilane is 2:0.9; Step S3: Add 2,4-dihydroxybenzophenone and triethylamine to tetrahydrofuran, stir to dissolve, and then add acryloyl chloride solution dropwise at 1°C. Continue the reaction for 7 hours. After the reaction is completed, wash, recrystallize and dry to obtain the modified benzophenone anti-aging agent. The molar ratio of 2,4-dihydroxybenzophenone to acryloyl chloride is 1:1.4. Step S4: The modified carbon fiber, modified benzophenone anti-aging agent, α,α-dimethoxy-α-phenylacetophenone, and chloroform are mixed and reacted under ultraviolet light for 35 minutes. After the reaction is completed, the mixture is washed and dried to obtain anti-aging modified carbon fiber. The reaction mass ratio of modified carbon fiber to modified benzophenone anti-aging agent is 1:0.04. Step 2: Add graphene oxide to a mixed solution of anhydrous ethanol and deionized water, disperse it evenly by ultrasonication, then add γ-aminopropyltriethoxysilane and perfluorooctyltriethoxysilane, and stir the mixture at 42°C for 7.5 h. After the reaction is complete, filter, wash with water, wash with alcohol, and dry to obtain hydrophobically modified graphene. The mass ratio of graphene oxide, γ-aminopropyltriethoxysilane, and perfluorooctyltriethoxysilane is 1:0.23:0.45. Step 3: Add γ-aminopropyltriethoxysilane to a mixed solution of anhydrous ethanol and deionized water, stir for 17 min, then add alumina powder, heat to 62℃ and stir for 4.5 h. After the reaction is complete, filter, wash and dry to obtain modified alumina; the mass ratio of alumina powder to γ-aminopropyltriethoxysilane is 1:0.025. Step 4: Mix epoxy resin and ethyl acetate, heat to 52°C, stir evenly, and then add dibutyltin dilaurate, dichlorodimethylsilane and triethylamine in sequence. Continue the reaction for 2.5 hours. After the reaction is completed, centrifuge, wash and distill under reduced pressure to obtain modified epoxy resin. The mass ratio of epoxy resin to dichlorodimethylsilane is 1:0.14. Step 5: Mix 25g modified epoxy resin, 35g epoxy resin, 2g hydrophobic modified graphene, 11g anti-aging modified carbon fiber, 12g modified alumina, 10g polyamide, 1.5g wetting and dispersing agent BYK-220S, 1.5g defoamer BYK-066N, and 0.7g leveling agent BYK-345, and stir and disperse for 25 minutes to obtain an anti-corrosion coating; uniformly coat the anti-corrosion coating onto the surface of the tungsten carbide substrate, and cure at 75℃ for 3.5 hours to obtain the finished product; the coating thickness is 20μm.

[0024] Example 3: Step 1: Step S1: Carbon fiber and acetone were mixed and subjected to Soxhlet extraction. After reflux for 20 hours, the fiber was washed with water and dried to obtain pretreated carbon fiber. The pretreated carbon fiber was then mixed with hydrogen peroxide solution and stirred for 10 hours. After the reaction was completed, the fiber was washed with water and dried to obtain activated carbon fiber. The concentration of hydrogen peroxide solution was 26 wt%. Step S2: Mix activated carbon fibers and anhydrous ethanol, then add 3-mercaptopropyltriethoxysilane, ultrasonically disperse for 20 min, add hydrochloric acid solution to adjust the pH of the solution to 4, react at 70℃ for 6 h, wash with alcohol and dry after the reaction to obtain modified carbon fibers; the reaction mass ratio of activated carbon fibers to 3-mercaptopropyltriethoxysilane is 2:0.9. Step S3: Add 2,4-dihydroxybenzophenone and triethylamine to tetrahydrofuran, stir to dissolve, and then add acryloyl chloride solution dropwise at 0°C. Continue the reaction for 6 hours. After the reaction is completed, wash, recrystallize and dry to obtain the modified benzophenone anti-aging agent. The molar ratio of 2,4-dihydroxybenzophenone to acryloyl chloride is 1:1.4. Step S4: The modified carbon fiber, modified benzophenone anti-aging agent, α,α-dimethoxy-α-phenylacetophenone, and chloroform are mixed and reacted under ultraviolet light for 30 minutes. After the reaction is completed, the mixture is washed and dried to obtain anti-aging modified carbon fiber. The mass ratio of modified carbon fiber to modified benzophenone anti-aging agent is 1:0.04. Step 2: Add graphene oxide to a mixed solution of anhydrous ethanol and deionized water, disperse it evenly by ultrasonication, then add γ-aminopropyltriethoxysilane and perfluorooctyltriethoxysilane, and stir the mixture at 40°C for 7 hours. After the reaction is complete, filter, wash with water, wash with alcohol, and dry to obtain hydrophobically modified graphene. The mass ratio of graphene oxide, γ-aminopropyltriethoxysilane, and perfluorooctyltriethoxysilane is 1:0.23:0.45. Step 3: Add γ-aminopropyltriethoxysilane to a mixed solution of anhydrous ethanol and deionized water, stir for 15 min, then add alumina powder, heat to 60℃ and stir for 4 h. After the reaction is complete, filter, wash and dry to obtain modified alumina; the mass ratio of alumina powder to γ-aminopropyltriethoxysilane is 1:0.025. Step 4: Mix epoxy resin and ethyl acetate, heat to 50°C, stir evenly, and then add dibutyltin dilaurate, dichlorodimethylsilane and triethylamine in sequence. Continue the reaction for 2 hours. After the reaction is completed, centrifuge, wash and distill under reduced pressure to obtain modified epoxy resin. The mass ratio of epoxy resin to dichlorodimethylsilane is 1:0.14. Step 5: Mix 25g modified epoxy resin, 35g epoxy resin, 2g hydrophobic modified graphene, 11g anti-aging modified carbon fiber, 12g modified alumina, 10g polyamide, 1.5g wetting and dispersing agent BYK-220S, 1.5g defoamer BYK-066N, and 0.7g leveling agent BYK-345, and stir and disperse for 20 minutes to obtain an anti-corrosion coating; uniformly coat the anti-corrosion coating onto the surface of the tungsten carbide substrate, and cure at 70℃ for 3 hours to obtain the finished product; the coating thickness is 20μm.

[0025] Comparative Example 1: The modified epoxy resin was replaced with unmodified epoxy resin provided by Jinan Chengwu Chemical Co., Ltd., and the rest was the same as in Example 1. The specific steps are as follows: Step 1: Step S1: Carbon fiber and acetone were mixed and subjected to Soxhlet extraction. After reflux for 25 hours, the fiber was washed with water and dried to obtain pretreated carbon fiber. The pretreated carbon fiber was then mixed with hydrogen peroxide solution and stirred for 12 hours. After the reaction was completed, it was washed with water and dried to obtain activated carbon fiber. The concentration of hydrogen peroxide solution was 26 wt%. Step S2: Mix activated carbon fiber and anhydrous ethanol, then add 3-mercaptopropyltriethoxysilane, ultrasonically disperse for 30 min, add hydrochloric acid solution to adjust the pH of the solution to 5, react at 75℃ for 7 h, after the reaction is completed, wash with alcohol and dry to obtain modified carbon fiber; the reaction mass ratio of activated carbon fiber to 3-mercaptopropyltriethoxysilane is 2:0.9; Step S3: Add 2,4-dihydroxybenzophenone and triethylamine to tetrahydrofuran, stir to dissolve, and then add acryloyl chloride solution dropwise at 2°C. Continue the reaction for 8 hours. After the reaction is completed, wash, recrystallize and dry to obtain the modified benzophenone anti-aging agent. The molar ratio of 2,4-dihydroxybenzophenone to acryloyl chloride is 1:1.4. Step S4: The modified carbon fiber, modified benzophenone anti-aging agent, α,α-dimethoxy-α-phenylacetophenone, and chloroform are mixed and reacted under ultraviolet light for 40 minutes. After the reaction is completed, the mixture is washed and dried to obtain anti-aging modified carbon fiber. The mass ratio of modified carbon fiber to modified benzophenone anti-aging agent is 1:0.04. Step 2: Add graphene oxide to a mixed solution of anhydrous ethanol and deionized water, disperse it evenly by ultrasonication, then add γ-aminopropyltriethoxysilane and perfluorooctyltriethoxysilane, and stir the mixture at 45°C for 8 hours. After the reaction is complete, filter, wash with water, wash with alcohol, and dry to obtain hydrophobically modified graphene. The mass ratio of graphene oxide, γ-aminopropyltriethoxysilane, and perfluorooctyltriethoxysilane is 1:0.23:0.45. Step 3: Add γ-aminopropyltriethoxysilane to a mixed solution of anhydrous ethanol and deionized water, stir for 20 min, then add alumina powder, heat to 65℃ and stir for 5 h. After the reaction is complete, filter, wash and dry to obtain modified alumina; the mass ratio of alumina powder to γ-aminopropyltriethoxysilane is 1:0.025. Step 4: Mix 60g epoxy resin, 2g hydrophobic modified graphene, 11g anti-aging modified carbon fiber, 12g modified alumina, 10g polyamide, 1.5g wetting and dispersing agent BYK-220S, 1.5g defoamer BYK-066N, and 0.7g leveling agent BYK-345, and stir and disperse for 30 minutes to obtain an anti-corrosion coating; uniformly coat the anti-corrosion coating onto the surface of the tungsten carbide substrate, and cure at 80℃ for 4 hours to obtain the finished product; the coating thickness is 20μm.

[0026] Comparative Example 2: The hydrophobic modified graphene was removed, and the rest was the same as in Example 1. The specific steps are as follows: Step 1: Step S1: Carbon fibers and acetone were mixed and subjected to Soxhlet extraction. After reflux for 25 hours, the fibers were washed with water and dried to obtain pretreated carbon fibers. The pretreated carbon fibers were then mixed with hydrogen peroxide solution and stirred for 12 hours. After the reaction was completed, the fibers were washed with water and dried to obtain activated carbon fibers. The concentration of the hydrogen peroxide solution was 26 wt%. Step S2: Mix activated carbon fiber and anhydrous ethanol, then add 3-mercaptopropyltriethoxysilane, ultrasonically disperse for 30 min, add hydrochloric acid solution to adjust the pH of the solution to 5, react at 75℃ for 7 h, after the reaction is completed, wash with alcohol and dry to obtain modified carbon fiber; the reaction mass ratio of activated carbon fiber to 3-mercaptopropyltriethoxysilane is 2:0.9; Step S3: Add 2,4-dihydroxybenzophenone and triethylamine to tetrahydrofuran, stir to dissolve, and then add acryloyl chloride solution dropwise at 2°C. Continue the reaction for 8 hours. After the reaction is completed, wash, recrystallize and dry to obtain the modified benzophenone anti-aging agent. The molar ratio of 2,4-dihydroxybenzophenone to acryloyl chloride is 1:1.4. Step S4: The modified carbon fiber, modified benzophenone anti-aging agent, α,α-dimethoxy-α-phenylacetophenone, and chloroform are mixed and reacted under ultraviolet light for 40 minutes. After the reaction is completed, the mixture is washed and dried to obtain anti-aging modified carbon fiber. The mass ratio of modified carbon fiber to modified benzophenone anti-aging agent is 1:0.04. Step 2: Add γ-aminopropyltriethoxysilane to a mixed solution of anhydrous ethanol and deionized water, stir for 20 min, then add alumina powder, heat to 65℃ and stir for 5 h. After the reaction is complete, filter, wash and dry to obtain modified alumina; the mass ratio of alumina powder to γ-aminopropyltriethoxysilane is 1:0.025. Step 3: Mix epoxy resin and ethyl acetate, heat to 55℃, stir evenly, and then add dibutyltin dilaurate, dichlorodimethylsilane and triethylamine in sequence. Continue the reaction for 3 hours. After the reaction is completed, centrifuge, wash and distill under reduced pressure to obtain modified epoxy resin; the mass ratio of epoxy resin to dichlorodimethylsilane is 1:0.14. Step 4: Mix 25g modified epoxy resin, 35g epoxy resin, 11g anti-aging modified carbon fiber, 12g modified alumina, 10g polyamide, 1.5g wetting and dispersing agent BYK-220S, 1.5g defoamer BYK-066N, and 0.7g leveling agent BYK-345, and stir and disperse for 30 minutes to obtain an anti-corrosion coating; uniformly coat the anti-corrosion coating onto the surface of the tungsten carbide substrate, and cure at 80℃ for 4 hours to obtain the finished product; the coating thickness is 20μm.

[0027] Comparative Example 3: The hydrophobic modified graphene and anti-aging modified carbon fiber were removed, and the rest was the same as in Example 1. The specific steps are as follows: Step 1: γ-aminopropyltriethoxysilane was added to a mixed solution of anhydrous ethanol and deionized water. After stirring for 20 min, alumina powder was added, and the temperature was raised to 65℃ and stirred for 5 h. After the reaction was completed, the mixture was filtered, washed, and dried to obtain modified alumina. The mass ratio of alumina powder to γ-aminopropyltriethoxysilane was 1:0.025. Step 2: Mix epoxy resin and ethyl acetate, heat to 55℃, stir evenly, and then add dibutyltin dilaurate, dichlorodimethylsilane and triethylamine in sequence. Continue the reaction for 3 hours. After the reaction is completed, centrifuge, wash and distill under reduced pressure to obtain modified epoxy resin. The mass ratio of epoxy resin to dichlorodimethylsilane is 1:0.14. Step 3: Mix 25g modified epoxy resin, 35g epoxy resin, 12g modified alumina, 10g polyamide, 1.5g wetting and dispersing agent BYK-220S, 1.5g defoamer BYK-066N, and 0.7g leveling agent BYK-345, and stir and disperse for 30 minutes to obtain an anti-corrosion coating; apply the anti-corrosion coating evenly to the surface of the tungsten carbide substrate, and cure at 80℃ for 4 hours to obtain the finished product; the coating thickness is 20μm.

[0028] Testing and experimentation: Corrosion resistance test: Referring to GB / T 31588.1-2015 "Determination of resistance to cyclic corrosion environments for paints and varnishes - Part 1: Wet (salt spray) / dry / moisture", the tungsten steel material prepared in this invention was used as a sample and subjected to a neutral salt spray test. The surface condition of the sample was observed after 1500 hours of testing.

[0029] Corrosion resistance stability test: The tungsten steel material prepared by this invention is used as a sample. According to ASTM D3359-09 standard B, scratches are made on the coating surface of the sample, and then the sample is adhered to the coating surface with tape. The tape is pressed with a fixed weight and peeled off the coating surface at 180°. After peeling 10 times, the contact angle of the surface coating is measured.

[0030] Anti-aging performance test: The tungsten steel material prepared according to this invention was used as a sample. The sample was placed in an aging test chamber for 1000 hours. Then, referring to GB / T 9754-2025 "Determination of gloss at 20°, 60° and 85° for paints and varnishes", the gloss change of the coating on the sample surface was tested. The anti-aging performance was judged based on the gloss retention rate of the coating. The results are shown in the table below: Conclusion: The dosages in Examples 1-3 remained unchanged, with only some reaction parameters modified. Experimental data showed no significant fluctuations in the performance of the samples. Comparative Example 1: The modified epoxy resin was replaced with unmodified epoxy resin provided by Jinan Chengwu Chemical Co., Ltd., while the rest remained the same as in Example 1. Experimental data showed that, compared to Example 1, the corrosion resistance test results were as follows: Extensive rust was observed at the marked areas, and the coating showed high peeling. The reason for this is that the modified epoxy resin possesses a resin network with both high cross-linking density and intrinsic hydrophobicity, which is the basis for the coating's corrosion resistance. Therefore, replacing it with ordinary epoxy resin resulted in a decrease in corrosion resistance.

[0031] Comparative Example 2: The hydrophobic modified graphene was removed, and the rest was the same as in Example 1. The experimental data showed that, compared with Example 1, the corrosion resistance test results were as follows: there were obvious rust marks at the scribing points and the coating peeling degree was moderate. The reason for this was that the hydrophobic modified graphene had good low surface energy after being modified by silane, so the corrosion resistance decreased after it was removed.

[0032] Comparative Example 3: The hydrophobic modified graphene and anti-aging modified carbon fiber were removed, while the rest remained the same as in Example 1. Experimental data showed that, compared to Example 1, the corrosion resistance test results were as follows: more rust was observed at the scribing points, and the coating peeling was more severe; the gloss retention rate decreased to 68%. The reason for this is that, based on Comparative Example 2, Comparative Example 3 further removed the anti-aging modified carbon fiber, resulting in a significant decrease in the coating's anti-aging performance and gloss retention rate. Secondly, the anti-aging modified carbon fiber can synergistically provide a corrosion-resistant surface with other fillers, so its removal reduces corrosion resistance.

[0033] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process method article or apparatus.

[0034] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A processing technology for wear-resistant and corrosion-resistant tungsten carbide material, characterized in that: Includes the following steps: Step 1: Mix epoxy resin and ethyl acetate, heat, stir evenly, then add dibutyltin dilaurate, dichlorodimethylsilane and triethylamine in sequence, continue the reaction, and after the reaction is completed, centrifuge, wash and distill under reduced pressure to obtain modified epoxy resin. Step 2: Mix modified epoxy resin, epoxy resin, hydrophobic modified graphene, anti-aging modified carbon fiber, modified alumina, curing agent, defoamer, leveling agent and wetting and dispersing agent, stir and disperse to obtain anti-corrosion coating; apply the anti-corrosion coating evenly to the surface of tungsten carbide substrate, cure to obtain finished product; The preparation process of anti-aging modified carbon fiber is as follows: Step S1: Mix carbon fiber and acetone for Soxhlet extraction, reflux for 20-25 hours, then wash and dry the fiber to obtain pretreated carbon fiber. The pretreated carbon fiber and hydrogen peroxide solution are then mixed and stirred for 10-12 hours. After the reaction is completed, the carbon fiber is washed with water and dried to obtain activated carbon fiber. Step S2: Mix activated carbon fibers with anhydrous ethanol, then add 3-mercaptopropyltriethoxysilane, ultrasonically disperse for 20-30 min, add hydrochloric acid solution, adjust the pH of the solution to 4-5, react at 70-75℃ for 6-7 h, after the reaction is completed, wash with alcohol and dry to obtain modified carbon fibers. Step S3: Add 2,4-dihydroxybenzophenone and triethylamine to tetrahydrofuran, stir to dissolve, and then add acryloyl chloride solution dropwise at 0-2℃. Continue the reaction for 6-8 hours. After the reaction is completed, wash, recrystallize and dry to obtain the modified benzophenone anti-aging agent. Step S4: Mix modified carbon fiber, modified benzophenone anti-aging agent, α,α-dimethoxy-α-phenylacetophenone, and chloroform, and react under ultraviolet light for 30-40 minutes. After the reaction is completed, wash and dry to obtain anti-aging modified carbon fiber. In step S1, the concentration of hydrogen peroxide solution is 25-28 wt%; in step S2, the reaction mass ratio of activated carbon fiber and 3-mercaptopropyltriethoxysilane is 2:(0.8-1.0); in step S3, the reaction molar ratio of 2,4-dihydroxybenzophenone and acryloyl chloride is 1:(1.3-1.4); in step S4, the reaction mass ratio of modified carbon fiber and modified benzophenone-based anti-aging agent is 1:(0.03-0.05).

2. The processing technology of a wear-resistant and corrosion-resistant tungsten carbide material according to claim 1, characterized in that: The modified epoxy resin is obtained by stirring and reacting at 50-55℃ for 2-3 hours; the finished product is obtained by curing at 70-80℃ for 3-4 hours; the mass ratio of epoxy resin to dichlorodimethylsilane is 1:(0.13-0.15); the coating thickness is 20-25μm.

3. The processing technology of a wear-resistant and corrosion-resistant tungsten carbide material according to claim 1, characterized in that: In step two, the composition of the anti-corrosion coating is as follows (by weight): 20-30 parts modified epoxy resin, 30-40 parts epoxy resin, 2-3 parts hydrophobic modified graphene, 10-12 parts anti-aging modified carbon fiber, 10-15 parts modified alumina, 8-12 parts curing agent, 1-2 parts wetting and dispersing agent, 1-2 parts defoamer, and 0.5-0.8 parts leveling agent; the curing agent is polyamide.

4. The processing technology of a wear-resistant and corrosion-resistant tungsten carbide material according to claim 3, characterized in that: The preparation process of hydrophobic modified graphene is as follows: graphene oxide is added to a mixed solution of anhydrous ethanol and deionized water, and after being ultrasonically dispersed evenly, γ-aminopropyltriethoxysilane and perfluorooctyltriethoxysilane are added. The mixture is stirred at 40-45℃ for 7-8 hours. After the reaction is completed, the graphene is filtered, washed with water, washed with alcohol, and dried to obtain hydrophobic modified graphene.

5. The processing technology of a wear-resistant and corrosion-resistant tungsten carbide material according to claim 4, characterized in that: The mass ratio of graphene oxide, γ-aminopropyltriethoxysilane, and perfluorooctyltriethoxysilane is 1:(0.20-0.25):(0.4-0.5).

6. The processing technology of a wear-resistant and corrosion-resistant tungsten carbide material according to claim 3, characterized in that: The preparation process of modified alumina is as follows: γ-aminopropyltriethoxysilane is added to a mixed solution of anhydrous ethanol and deionized water, stirred for 15-20 min, and then alumina powder is added. The temperature is raised to 60-65℃ and stirred for 4-5 h. After the reaction is completed, the alumina is obtained by filtration, washing and drying.

7. The processing technology of a wear-resistant and corrosion-resistant tungsten carbide material according to claim 6, characterized in that: The mass ratio of alumina powder to γ-aminopropyltriethoxysilane is 1:(0.02-0.03).

8. A wear-resistant and corrosion-resistant tungsten carbide material, characterized in that, It is processed according to any one of the processing techniques described in claims 1-7.

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