A method for producing a selenium alloyed steel

Abstract

The present application relates to the technical field of alloy steel, and particularly relates to a preparation method of selenium-added alloy steel, which comprises the following steps: sequentially performing solid solution treatment and ion nitriding treatment on a semi-finished product of the selenium-added alloy steel after component design; adopting a combination of micro-arc oxidation and ultrasonic-assisted ionic liquid electroplating to prepare a composite film layer with corrosion resistance, wear resistance, friction reduction and antibacterial property on the surface of the nitrided selenium-added alloy steel; controlling the process parameters of the micro-arc oxidation to form uniform nanometer holes on the surface of the nitrided selenium-added alloy steel; then adopting ultrasonic-assisted ionic liquid electroplating to perform sealing treatment on the nanometer holes formed by the micro-arc oxidation, so as to construct a gradient hardness layer; and selecting choline chloride-glycol ionic liquid as an electroplating solution solvent for ultrasonic-assisted ionic liquid electroplating, wherein the selenium-added alloy steel after the micro-arc oxidation treatment is put into an electroplating solution containing composite nanometer molybdenum disulfide to construct a copper-cobalt-nickel layer doped with composite nanometer molybdenum disulfide on the surface.

Description

Technical Field

[0001] This invention relates to the field of alloy steel technology, specifically a method for preparing selenium-added alloy steel. Background Technology

[0002] As a trace element, selenium can improve the processing performance of steel, and is therefore often used in the steel industry. It plays a positive role in improving the strength, ductility, and corrosion resistance of alloy steel. For example, selenium can enhance the interstitial atomic bonding force in alloy steel or help carbon in steel alloys diffuse into ferrite, thereby increasing the hardness of alloy steel. At the same time, selenium can also prevent hot cracking and resist oxidation.

[0003] In practical applications, wear and corrosion of selenium-added alloy steel are hot research topics. Researching how to improve the wear resistance and corrosion resistance of selenium-added alloy steel has practical significance and economic value. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing selenium-added alloy steel to solve the problems in the prior art.

[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0006] A method for preparing selenium-added alloy steel includes the following steps:

[0007] S1: The alloy raw materials are melted in a vacuum induction furnace and then cast into shape to obtain a semi-finished selenium-added alloy steel.

[0008] S2: The semi-finished selenium-added alloy steel is subjected to solution treatment, cleaning, drying, and sanding in sequence, followed by ion nitriding treatment, polishing, alkaline washing, acid washing, ultrasonic water washing, and drying to obtain nitrided selenium-added alloy steel.

[0009] S3: Micro-arc oxidation treatment is performed on selenium-nitrided alloy steel, followed by cleaning and drying to obtain pretreated selenium-nitrided alloy steel;

[0010] S4: Prepare an electroplating solution containing composite nano-molybdenum disulfide, place the pretreated selenium-added alloy steel into the electroplating solution, perform ultrasonic-assisted electroplating treatment, and dry to obtain a selenium-added alloy steel.

[0011] Furthermore, by mass percentage, the composition of the alloy raw materials is as follows: manganese 29-30%, aluminum 9.4-9.6%, molybdenum 0.4-0.5%, silicon 0.9-1%, carbon 1-1.1%, selenium 0.3%, with the balance being iron.

[0012] Furthermore, the working conditions for solution treatment are: holding at 950℃ for 60 minutes.

[0013] Furthermore, the working conditions for ion nitriding treatment are as follows: it is carried out in a glow discharge ion nitriding furnace, using pure ammonia gas, and held at 550℃ for 15 hours to maintain an ammonia decomposition rate of 600 mL / h. Then, the temperature is increased to 570℃ at a rate of 20℃ / h and held for 30 hours to maintain an ammonia decomposition rate of 750 mL / h. The furnace is then cooled to 250℃ and removed from the furnace by oil cooling.

[0014] Furthermore, the working conditions for micro-arc oxidation are as follows: a bipolar pulse power supply is used, the current is 0.3A, the pulse frequency is 500Hz, and the oxidation time is 10min; the electrolyte for micro-arc oxidation is: deionized water as solvent, containing 40g / L sodium hexametaphosphate and 10g / L sodium silicate, and the temperature is 28-30℃.

[0015] Furthermore, the operating conditions for ultrasonic-assisted electroplating are: current density 3.8-4.2 mA / cm². 2 The time is 50-60 minutes, the temperature is 65℃, and the ultrasonic power is 250W.

[0016] Furthermore, the electroplating solution is composed of: choline chloride-ethylene glycol ionic liquid as solvent, containing 86 g / L nickel chloride hexahydrate, 46 g / L cobalt chloride hexahydrate, 21 g / L nickel sulfamate, 15 g / L copper chloride dihydrate, and (5-7) g / L composite nano molybdenum disulfide; wherein the choline chloride-ethylene glycol ionic liquid is obtained by compounding choline chloride and ethylene glycol in a molar ratio of 1:2.

[0017] Furthermore, the preparation of composite nano-molybdenum disulfide includes the following steps:

[0018] (1) Mix ammonium molybdate tetrahydrate and deionized water, add template KIT-6, sonicate for 5-10 min, stir for 8-10 h, filter and dry, add thiourea, grind, transfer to nitrogen atmosphere, keep warm at 500℃ for 4 h, cool to 18-25℃, add NaOH aqueous solution and keep warm for 18-20 h, wash with water, filter and dry to obtain porous nano molybdenum disulfide; mix porous nano molybdenum disulfide aqueous solution and silver nitrate aqueous solution, sonicate for 10-15 min, centrifuge, wash and freeze dry to obtain silver-loaded nano molybdenum disulfide;

[0019] (2) Mix cobalt nitrate hexahydrate and methanol, add a mixture of 2-methylimidazole and methanol, stir, seal, and let stand at 18-25℃ for 22-24h. Centrifuge, wash, and dry to obtain ZIF-67. Mix ZIF-67 and ethanol, add silver-loaded molybdenum disulfide nanoparticles, stir for 30-40min, transfer to a reaction vessel, keep warm at 180℃ for 10-12h, wash, and dry to obtain modified molybdenum disulfide nanoparticles.

[0020] (3) Mix the composite corrosion inhibitor and ethanol, add the modified nano molybdenum disulfide, stir ultrasonically for 1-2 hours, transfer to a vacuum environment, stir ultrasonically for 20-30 minutes, wash and dry to obtain composite nano molybdenum disulfide.

[0021] Furthermore, the composite corrosion inhibitor is obtained by compounding polyaspartic acid, sodium gluconate, and benzotriazole in a mass ratio of 1:2:3.

[0022] Furthermore, the preparation of template KIT-6 includes the following steps: P123, deionized water, and hydrochloric acid solution are stirred at 32-37℃ for 3-4 hours, n-butanol is added, and stirring is continued for 1-2 hours, sodium silicate solution is added, and stirring is continued for 22-24 hours, transferred to a reaction vessel, kept at 104-106℃ for 22-24 hours, cooled, filtered, washed, dried, calcined at 550℃ for 2 hours, and ground to obtain template KIT-6.

[0023] Compared with the prior art, the beneficial effects of the present invention are:

[0024] This invention provides a method for preparing selenium-added alloy steel. Through process and composition design, antibacterial selenium-added alloy steel with high strength, strong wear resistance, and good corrosion resistance is prepared, thereby extending the service life of selenium-added alloy steel.

[0025] This invention involves sequentially performing solution treatment and ion nitriding treatment on selenium-enriched alloy steel semi-finished products after composition design, thereby significantly improving the mechanical strength of selenium-enriched alloy steel.

[0026] A composite film layer with corrosion resistance, wear resistance, friction reduction, and antibacterial properties was prepared on the surface of selenium-nitrided alloy steel by combining micro-arc oxidation with ultrasonic-assisted ionic liquid electroplating, thereby improving the various properties of selenium-nitrided alloy steel. By controlling the process parameters of micro-arc oxidation, uniform nanopores were formed on the surface of selenium-nitrided alloy steel. Then, ultrasonic-assisted ionic liquid electroplating was used to seal the nanopores formed by micro-arc oxidation, thereby constructing a gradient hardness layer and improving the rust resistance and corrosion resistance of selenium-nitrided alloy steel.

[0027] To meet current green production requirements, this invention uses choline chloride-ethylene glycol ionic liquid as the solvent for ultrasonic-assisted ionic liquid electroplating. In this invention, selenium-enriched alloy steel treated with micro-arc oxidation is placed in an electroplating solution containing composite nano-molybdenum disulfide, constructing a copper-cobalt-nickel layer doped with composite nano-molybdenum disulfide on its surface, thereby significantly improving the wear resistance and corrosion resistance of the selenium-enriched alloy steel. The composite nano-molybdenum disulfide is synthesized in situ using the mesoporous material KIT-6 as a template via nano-casting, resulting in a porous and ordered molybdenum disulfide structure. Then, Ag is adsorbed through electrostatic adsorption. + Loading Ag onto porous molybdenum disulfide nanoparticles to construct a photothermal synergistic Ag +An antibacterial nanoplatform is used to further improve the corrosion resistance of composite nano-molybdenum disulfide. This involves combining silver-loaded nano-molybdenum disulfide with ZIF-67, which has a unique pore structure and a large surface area. This composite nano-container serves as a composite corrosion inhibitor. The corrosion inhibitor is a compound of polyaspartic acid with excellent biodegradability, sodium gluconate, and benzotriazole. This synergistic effect enhances the corrosion resistance of selenium-added alloy steel, thereby constructing a durable, corrosion-resistant, and broad-spectrum antibacterial film that extends the service life of the selenium-added alloy steel. Detailed Implementation

[0028] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0029] It should be noted that if the embodiments of the present invention involve directional indicators such as up, down, left, right, front, and back, these directional indicators are only used to explain the relative positional relationship and movement of components in a specific posture. If the specific posture changes, the directional indicators will also change accordingly. Furthermore, the technical solutions of the various embodiments can be combined with each other, but this must be based on the ability of those skilled in the art to implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be considered that such a combination of technical solutions does not exist and is not within the scope of protection claimed by the present invention.

[0030] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are only used to explain the present invention and are not intended to limit the present invention.

[0031] Example 1: A method for preparing selenium-added alloy steel, comprising the following steps:

[0032] S1: The alloy raw materials are melted in a vacuum induction furnace and then cast into shape to obtain a semi-finished selenium-added alloy steel.

[0033] The alloy raw materials are composed of the following by mass percentage: manganese 29.5%, aluminum 9.5%, molybdenum 0.45%, silicon 0.95%, carbon 1.05%, selenium 0.3%, with the balance being iron;

[0034] S2: The semi-finished selenium-added alloy steel is subjected to solution treatment, cleaning, drying, and sanding in sequence, followed by ion nitriding treatment, polishing, alkaline washing, acid washing, ultrasonic water washing, and drying to obtain nitrided selenium-added alloy steel.

[0035] The working conditions for the solution treatment are: holding at 950℃ for 60 min; the working conditions for the ion nitriding treatment are: carried out in a glow discharge ion nitriding furnace, using pure ammonia gas, holding at 550℃ for 15 h, maintaining an ammonia decomposition rate of 600 mL / h, then increasing the temperature at 20℃ / h to 570℃ and holding for 30 h, maintaining an ammonia decomposition rate of 750 mL / h, cooling to 250℃ with glow discharge, and then removing from the furnace and oil-cooling.

[0036] S3: Micro-arc oxidation treatment is performed on selenium-nitrided alloy steel, followed by cleaning and drying to obtain pretreated selenium-nitrided alloy steel;

[0037] The working conditions for micro-arc oxidation are as follows: a bipolar pulse power supply is used, the current is 0.3A, the pulse frequency is 500Hz, and the oxidation time is 15min; the electrolyte for micro-arc oxidation is: deionized water as solvent, containing 40g / L sodium hexametaphosphate and 10g / L sodium silicate, and the temperature is 28℃.

[0038] S4: Prepare an electroplating solution containing composite nano-molybdenum disulfide, place the pretreated selenium-added alloy steel into the electroplating solution, perform ultrasonic-assisted electroplating treatment, and dry to obtain a selenium-added alloy steel.

[0039] The operating conditions for ultrasonic-assisted electroplating are: current density 3.8 mA / cm². 2 The time was 60 minutes, the temperature was 65℃, and the ultrasonic power was 250W.

[0040] Electroplating solution: Deionized water is used as solvent, containing 86 g / L nickel chloride hexahydrate, 46 g / L cobalt chloride hexahydrate, 21 g / L nickel sulfamate, 15 g / L copper chloride dihydrate, and 5 g / L composite nano molybdenum disulfide; the choline chloride-ethylene glycol ionic liquid is obtained by mixing choline chloride and ethylene glycol in a molar ratio of 1:2.

[0041] The preparation of the composite nano-molybdenum disulfide includes the following steps:

[0042] (1) Mix 1.3g ammonium molybdate tetrahydrate and 4mL deionized water, add 0.8g template KIT-6, sonicate for 5min, stir for 8h, filter and dry, add 0.1g thiourea, grind, transfer to nitrogen atmosphere, keep warm at 500℃ for 4h, cool to 18℃, add 2mol / L NaOH aqueous solution and keep warm for 18h, wash with water, filter and dry to obtain porous nano molybdenum disulfide; mix 10mL 1mg / mL porous nano molybdenum disulfide aqueous solution and 10mL 1mg / mL silver nitrate aqueous solution, centrifuge, wash and freeze dry to obtain silver-loaded nano molybdenum disulfide;

[0043] (2) Mix 1.5g cobalt nitrate hexahydrate and 100mL methanol, add 1.6g 2-methylimidazole and 100mL methanol, stir, seal, stand at 18℃ for 24h, centrifuge, wash and dry to obtain ZIF-67; mix 0.2g ZIF-67 and 50mL ethanol, add 0.5g silver-loaded molybdenum disulfide nanoparticles, stir for 30min, transfer to a reaction vessel, keep warm at 180℃ for 10h, wash and dry to obtain modified molybdenum disulfide nanoparticles;

[0044] (3) Mix 6g of composite corrosion inhibitor and 100mL of ethanol, add 0.7g of modified nano molybdenum disulfide, stir ultrasonically for 1h, transfer to a vacuum environment, stir ultrasonically for 20min, wash and dry to obtain composite nano molybdenum disulfide.

[0045] The composite corrosion inhibitor is obtained by compounding polyaspartic acid, sodium gluconate and benzotriazole in a mass ratio of 1:2:3;

[0046] The preparation of template KIT-6 includes the following steps: 2g P123, 72g deionized water, and 4g of 37% hydrochloric acid solution are stirred at 32℃ for 4h, 2g n-butanol is added, and stirring is continued for 1h, 4.2g of 30% sodium silicate solution is added, and stirring is continued for 22h, then transferred to a reaction vessel and kept at 104℃ for 24h, cooled, filtered, washed, dried, calcined at 550℃ for 2h, and ground to obtain template KIT-6.

[0047] Example 2: A method for preparing selenium-added alloy steel, comprising the following steps:

[0048] S1: The alloy raw materials are melted in a vacuum induction furnace and then cast into shape to obtain a semi-finished selenium-added alloy steel.

[0049] The alloy raw materials are composed of the following by mass percentage: manganese 29.5%, aluminum 9.5%, molybdenum 0.45%, silicon 0.95%, carbon 1.01%, selenium 0.3%, with the balance being iron;

[0050] S2: The semi-finished selenium-added alloy steel is subjected to solution treatment, cleaning, drying, and sanding in sequence, followed by ion nitriding treatment, polishing, alkaline washing, acid washing, ultrasonic water washing, and drying to obtain nitrided selenium-added alloy steel.

[0051] The working conditions for the solution treatment are: holding at 950℃ for 60 min; the working conditions for the ion nitriding treatment are: carried out in a glow discharge ion nitriding furnace, using pure ammonia gas, holding at 550℃ for 15 h, maintaining an ammonia decomposition rate of 600 mL / h, then increasing the temperature at 20℃ / h to 570℃ and holding for 30 h, maintaining an ammonia decomposition rate of 750 mL / h, cooling to 250℃ with glow discharge, and then removing from the furnace and oil-cooling.

[0052] S3: Micro-arc oxidation treatment is performed on selenium-nitrided alloy steel, followed by cleaning and drying to obtain pretreated selenium-nitrided alloy steel;

[0053] The working conditions for micro-arc oxidation are as follows: a bipolar pulse power supply is used, the current is 0.3A, the pulse frequency is 500Hz, and the oxidation time is 15min; the electrolyte for micro-arc oxidation is deionized water as the solvent, containing 40g / L sodium hexametaphosphate and 10g / L sodium silicate, and the temperature is 29℃.

[0054] S4: Prepare an electroplating solution containing composite nano-molybdenum disulfide, place the pretreated selenium-added alloy steel into the electroplating solution, perform ultrasonic-assisted electroplating treatment, and dry to obtain a selenium-added alloy steel.

[0055] The working conditions for ultrasonic-assisted electroplating are: current density 4 mA / cm². 2 The time was 55 minutes, the temperature was 65℃, and the ultrasonic power was 250W.

[0056] Electroplating solution: Deionized water is used as solvent, containing 86 g / L nickel chloride hexahydrate, 46 g / L cobalt chloride hexahydrate, 21 g / L nickel sulfamate, 15 g / L copper chloride dihydrate, and 6 g / L composite nano molybdenum disulfide; the choline chloride-ethylene glycol ionic liquid is obtained by mixing choline chloride and ethylene glycol in a molar ratio of 1:2.

[0057] The preparation of the composite nano-molybdenum disulfide includes the following steps:

[0058] (1) Mix 1.3g ammonium molybdate tetrahydrate and 4mL deionized water, add 0.8g template KIT-6, sonicate for 8min, stir for 9h, filter and dry, add 0.1g thiourea, grind, transfer to nitrogen atmosphere, keep warm at 500℃ for 4h, cool to 20℃, add 2mol / L NaOH aqueous solution and keep warm for 19h, wash with water, filter and dry to obtain porous nano molybdenum disulfide; mix 10mL 1mg / mL porous nano molybdenum disulfide aqueous solution and 10mL 1mg / mL silver nitrate aqueous solution, centrifuge, wash and freeze dry to obtain silver-loaded nano molybdenum disulfide;

[0059] (2) Mix 1.5g cobalt nitrate hexahydrate and 100mL methanol, add 1.6g 2-methylimidazole and 100mL methanol, stir, seal, stand at 20℃ for 23h, centrifuge, wash and dry to obtain ZIF-67; mix 0.2g ZIF-67 and 50mL ethanol, add 0.5g silver-loaded nano-molybdenum disulfide, stir for 35min, transfer to a reaction vessel, keep warm at 180℃ for 11h, wash and dry to obtain modified nano-molybdenum disulfide;

[0060] (3) Mix 6g of composite corrosion inhibitor and 100mL of ethanol, add 0.7g of modified nano molybdenum disulfide, stir ultrasonically for 1.5h, transfer to a vacuum environment, stir ultrasonically for 25min, wash and dry to obtain composite nano molybdenum disulfide.

[0061] The composite corrosion inhibitor is obtained by compounding polyaspartic acid, sodium gluconate and benzotriazole in a mass ratio of 1:2:3;

[0062] The preparation of template KIT-6 includes the following steps: 2g P123, 72g deionized water, and 4g of 37% hydrochloric acid solution were stirred at 35°C for 3.5h, 2g n-butanol was added, and stirring was continued for 1.5h, 4.2g of 30% sodium silicate solution was added, and stirring was continued for 23h, transferred to a reaction vessel, kept at 105°C for 23h, cooled, filtered, washed, dried, calcined at 550°C for 2h, and ground to obtain template KIT-6.

[0063] Example 3: A method for preparing selenium-added alloy steel, comprising the following steps:

[0064] S1: The alloy raw materials are melted in a vacuum induction furnace and then cast into shape to obtain a semi-finished selenium-added alloy steel.

[0065] The alloy raw materials are composed of the following by mass percentage: manganese 29.5%, aluminum 9.5%, molybdenum 0.45%, silicon 0.95%, carbon 1.05%, selenium 0.3%, with the balance being iron;

[0066] S2: The semi-finished selenium-added alloy steel is subjected to solution treatment, cleaning, drying, and sanding in sequence, followed by ion nitriding treatment, polishing, alkaline washing, acid washing, ultrasonic water washing, and drying to obtain nitrided selenium-added alloy steel.

[0067] The working conditions for the solution treatment are: holding at 950℃ for 60 min; the working conditions for the ion nitriding treatment are: carried out in a glow discharge ion nitriding furnace, using pure ammonia gas, holding at 550℃ for 15 h, maintaining an ammonia decomposition rate of 600 mL / h, then increasing the temperature at 20℃ / h to 570℃ and holding for 30 h, maintaining an ammonia decomposition rate of 750 mL / h, cooling to 250℃ with glow discharge, and then removing from the furnace and oil-cooling.

[0068] S3: Micro-arc oxidation treatment is performed on selenium-nitrided alloy steel, followed by cleaning and drying to obtain pretreated selenium-nitrided alloy steel;

[0069] The working conditions for micro-arc oxidation are as follows: a bipolar pulse power supply is used, the current is 0.3A, the pulse frequency is 500Hz, and the oxidation time is 15min; the electrolyte for micro-arc oxidation is: deionized water as solvent, containing 40g / L sodium hexametaphosphate and 10g / L sodium silicate, and the temperature is 30℃.

[0070] S4: Prepare an electroplating solution containing composite nano-molybdenum disulfide, place the pretreated selenium-added alloy steel into the electroplating solution, perform ultrasonic-assisted electroplating treatment, and dry to obtain a selenium-added alloy steel.

[0071] The operating conditions for ultrasonic-assisted electroplating are: current density 4.2 mA / cm². 2 The time was 50 minutes, the temperature was 65℃, and the ultrasonic power was 250W.

[0072] Electroplating solution: Deionized water is used as solvent, containing 86 g / L nickel chloride hexahydrate, 46 g / L cobalt chloride hexahydrate, 21 g / L nickel sulfamate, 15 g / L copper chloride dihydrate, and 7 g / L composite nano molybdenum disulfide; the choline chloride-ethylene glycol ionic liquid is obtained by mixing choline chloride and ethylene glycol in a molar ratio of 1:2.

[0073] The preparation of the composite nano-molybdenum disulfide includes the following steps:

[0074] (1) Mix 1.3g ammonium molybdate tetrahydrate and 4mL deionized water, add 0.8g template KIT-6, sonicate for 10min, stir for 8h, filter and dry, add 0.1g thiourea, grind, transfer to nitrogen atmosphere, keep warm at 500℃ for 4h, cool to 25℃, add 2mol / L NaOH aqueous solution and keep warm for 20h, wash with water, filter and dry to obtain porous nano molybdenum disulfide; mix 10mL 1mg / mL porous nano molybdenum disulfide aqueous solution and 10mL 1mg / mL silver nitrate aqueous solution, centrifuge, wash and freeze dry to obtain silver-loaded nano molybdenum disulfide;

[0075] (2) Mix 1.5g cobalt nitrate hexahydrate and 100mL methanol, add 1.6g 2-methylimidazole and 100mL methanol, stir, seal, stand at 25℃ for 22h, centrifuge, wash and dry to obtain ZIF-67; mix 0.2g ZIF-67 and 50mL ethanol, add 0.5g silver-loaded molybdenum disulfide nanoparticles, stir for 40min, transfer to a reaction vessel, keep warm at 180℃ for 12h, wash and dry to obtain modified molybdenum disulfide nanoparticles;

[0076] (3) Mix 6g of composite corrosion inhibitor and 100mL of ethanol, add 0.7g of modified nano molybdenum disulfide, stir ultrasonically for 2h, transfer to a vacuum environment, stir ultrasonically for 30min, wash and dry to obtain composite nano molybdenum disulfide.

[0077] The composite corrosion inhibitor is obtained by compounding polyaspartic acid, sodium gluconate and benzotriazole in a mass ratio of 1:2:3;

[0078] The preparation of template KIT-6 includes the following steps: 2g P123, 72g deionized water, and 4g of 37% hydrochloric acid solution were stirred at 37°C for 3h, 2g n-butanol was added, and stirring was continued for 2h, 4.2g of 30% sodium silicate solution was added, and stirring was continued for 24h, the mixture was transferred to a reaction vessel, kept at 106°C for 22h, cooled, filtered, washed, dried, calcined at 550°C for 2h, and ground to obtain template KIT-6.

[0079] Comparative Example 1: Using Example 3 as the control group, the composite nano-molybdenum disulfide was replaced with silver-loaded nano-molybdenum disulfide, while other processes were normal.

[0080] Comparative Example 2: Using Example 3 as the control group, composite nano molybdenum disulfide (XH-MoS2-100: Shanghai Xiaohuang Nanotechnology Co., Ltd.) was used to replace the composite nano molybdenum disulfide, and other processes were normal.

[0081] Source of raw materials used (for illustrative purposes only):

[0082] P123A392125: (Alpha) Zhengzhou Alpha Chemical Co., Ltd.; Sodium hexametaphosphate S108858, nickel chloride hexahydrate N112126, cobalt chloride hexahydrate C116457, nickel aminosulfonate N102822, copper chloride dihydrate C111680, choline chloride C108896, ethylene glycol E103319, ammonium molybdate tetrahydrate A294843, thiourea T112512, cobalt nitrate hexahydrate C112729, 2-methylimidazolium M104839, polyaspartic acid P303238, sodium gluconate S432829, benzotriazole B101002: Aladdin reagent; sodium silicate, NaOH, silver nitrate, methanol, ethanol, hydrochloric acid, n-butanol, analytical grade, commercially available.

[0083] Performance testing: The alloys prepared in the examples and comparative examples were tested;

[0084] Antibacterial activity: Staphylococcus aureus was used as the test strain, and the plate method was employed.

[0085] Wear resistance: The test was conducted using a vertical universal friction and wear tester with GCr15 as the wear material. The turntable speed was 110 r / min, the load was 12 N, and the time was 20 min. The sample was kept at 200℃ for 2 h and then cooled to 25℃ for wear resistance testing. The wear resistance was characterized by the weight ΔG of the worn sample, where ΔG = G0 - G1 (G0 - weight before wear, G1 - weight after wear).

[0086] Corrosion resistance: The sample was kept at 200℃ for 12h, then cooled to 25℃ for corrosion resistance testing. It was placed in a salt spray chamber at 37.5℃, with a sodium chloride concentration of 60g / L and a pH of 6.8. After 1200h, it was observed whether rust or other phenomena appeared. If no rust or other phenomena appeared, it was considered qualified. The results are shown in Table 1.

[0087] Table 1

[0088]

[0089] This invention provides a method for preparing selenium-added alloy steel. Through process and composition design, antibacterial selenium-added alloy steel with high strength, strong wear resistance, and good corrosion resistance is prepared, thereby extending the service life of selenium-added alloy steel.

[0090] Comparing Example 3 with Comparative Examples 1 and 2, it can be seen that, in order to meet the current requirements of green production, the present invention uses choline chloride-ethylene glycol ionic liquid as the electroplating solution solvent for ultrasonic-assisted ionic liquid electroplating. In the present invention, selenium-added alloy steel after micro-arc oxidation treatment is placed in an electroplating solution containing composite nano-molybdenum disulfide, and a copper-cobalt-nickel layer doped with composite nano-molybdenum disulfide is constructed on its surface, thereby significantly improving the wear resistance and corrosion resistance of the selenium-added alloy steel. Among them, the composite nano-molybdenum disulfide uses the mesoporous material KIT-6 as a template to synthesize a porous and ordered molybdenum disulfide structure in situ through nano-casting, and then Ag is adsorbed through electrostatic adsorption. + Loading Ag onto porous molybdenum disulfide nanoparticles to construct a photothermal synergistic Ag + To further improve the corrosion resistance of composite nano-molybdenum disulfide, an antibacterial nanoplatform is developed. This involves combining silver-loaded nano-molybdenum disulfide with a unique porous structure and a large surface area of ​​ZIF-67, and then using a metal framework as a composite corrosion inhibitor in the nano-container. This results in a durable, corrosion-resistant, and broad-spectrum antibacterial film that extends the service life of selenium-added alloy steel.

[0091] The above description is merely an embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural transformations made using the present invention's specification under the inventive concept of the present invention, or direct / indirect applications in other related technical fields, are included within the patent protection scope of the present invention.

Claims

1. A method for preparing selenium-added alloy steel, characterized in that, Includes the following steps: S1: The alloy raw materials are melted in a vacuum induction furnace and then cast into shape to obtain a semi-finished selenium-added alloy steel. S2: The semi-finished selenium-added alloy steel is subjected to solution treatment, cleaning, drying, and sanding in sequence, followed by ion nitriding treatment, polishing, alkaline washing, acid washing, ultrasonic water washing, and drying to obtain nitrided selenium-added alloy steel. S3: Micro-arc oxidation treatment is performed on selenium-nitrided alloy steel, followed by cleaning and drying to obtain pretreated selenium-nitrided alloy steel; S4: Prepare an electroplating solution containing composite nano-molybdenum disulfide, place the pretreated selenium-added alloy steel into the electroplating solution, perform ultrasonic-assisted electroplating treatment, and dry to obtain a selenium-added alloy steel. The electroplating solution is composed of choline chloride-ethylene glycol ionic liquid as solvent, containing 86 g / L nickel chloride hexahydrate, 46 g / L cobalt chloride hexahydrate, 21 g / L nickel sulfamate, 15 g / L copper chloride dihydrate, and 5-7 g / L composite nano molybdenum disulfide; wherein the choline chloride-ethylene glycol ionic liquid is obtained by mixing choline chloride and ethylene glycol in a molar ratio of 1:

2. The preparation of the composite nano-molybdenum disulfide includes the following steps: (1) Mix ammonium molybdate tetrahydrate and deionized water, add template KIT-6, sonicate for 5-10 min, stir for 8-10 h, filter and dry, add thiourea, grind, transfer to nitrogen atmosphere, keep warm at 500℃ for 4 h, cool to 18-25℃, add NaOH aqueous solution and keep warm for 18-20 h, wash with water, filter and dry to obtain porous nano molybdenum disulfide; mix porous nano molybdenum disulfide aqueous solution and silver nitrate aqueous solution, sonicate for 10-15 min, centrifuge, wash and freeze dry to obtain silver-loaded nano molybdenum disulfide; (2) Mix cobalt nitrate hexahydrate and methanol, add a mixture of 2-methylimidazole and methanol, stir, seal, and let stand at 18-25℃ for 22-24h. Centrifuge, wash, and dry to obtain ZIF-67. Mix ZIF-67 and ethanol, add silver-loaded molybdenum disulfide nanoparticles, stir for 30-40min, transfer to a reaction vessel, keep warm at 180℃ for 10-12h, wash, and dry to obtain modified molybdenum disulfide nanoparticles. (3) Mix the composite corrosion inhibitor and ethanol, add the modified nano molybdenum disulfide, stir ultrasonically for 1-2 hours, transfer to a vacuum environment, stir ultrasonically for 20-30 minutes, wash and dry to obtain composite nano molybdenum disulfide.

2. The method for preparing selenium-added alloy steel according to claim 1, characterized in that, The alloy raw materials are composed of the following by mass percentage: manganese 29-30%, aluminum 9.4-9.6%, molybdenum 0.4-0.5%, silicon 0.9-1%, carbon 1-1.1%, selenium 0.3%, with the balance being iron.

3. The method for preparing selenium-added alloy steel according to claim 1, characterized in that, The working conditions for the solution treatment are: holding at 950℃ for 60 min; the working conditions for the ion nitriding treatment are: carried out in a glow discharge ion nitriding furnace, using pure ammonia gas, holding at 550℃ for 15 h, maintaining an ammonia decomposition rate of 600 mL / h, then raising the temperature to 570℃ at 20℃ / h and holding for 30 h, maintaining an ammonia decomposition rate of 750 mL / h, cooling to 250℃ with glow discharge, and then removing from the furnace and oil-cooling.

4. The method for preparing selenium-added alloy steel according to claim 1, characterized in that, The working conditions for micro-arc oxidation are as follows: a bipolar pulse power supply is used, the current is 0.3A, the pulse frequency is 500Hz, and the oxidation time is 10min; the electrolyte for micro-arc oxidation is deionized water as the solvent, containing 40g / L sodium hexametaphosphate and 10g / L sodium silicate, and the temperature is 28-30℃.

5. The method for preparing selenium-added alloy steel according to claim 1, characterized in that, The operating conditions for ultrasonic-assisted electroplating are: current density 3.8-4.2 mA / cm². 2 The time is 50-60 minutes, the temperature is 65℃, and the ultrasonic power is 250W.

6. The method for preparing selenium-added alloy steel according to claim 1, characterized in that, In the preparation of composite nano-molybdenum disulfide, the composite corrosion inhibitor is obtained by compounding polyaspartic acid, sodium gluconate and benzotriazole in a mass ratio of 1:2:

3.

7. The method for preparing selenium-added alloy steel according to claim 1, characterized in that, The preparation of template KIT-6 includes the following steps: P123, deionized water, and hydrochloric acid solution are stirred at 32-37℃ for 3-4 hours, n-butanol is added, and stirring is continued for 1-2 hours, sodium silicate solution is added, and stirring is continued for 22-24 hours, then transferred to a reaction vessel and kept at 104-106℃ for 22-24 hours, cooled, filtered, washed, dried, calcined at 550℃ for 2 hours, and ground to obtain template KIT-6.

8. A selenium-added alloy steel, characterized in that, It is prepared by the preparation method described in any one of claims 1-7.

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