Preparation method of selenium-added alloy steel

Abstract

The invention relates to the technical field of alloy steel, in particular to a preparation method of selenium-added alloy steel, which comprises the following steps: sequentially carrying out solution treatment and ion nitriding treatment on a selenium-added alloy steel semi-finished product subjected to component design, and preparing the selenium-added alloy steel by adopting a mode of combining micro-arc oxidation and ultrasonic-assisted ionic liquid electroplating. A corrosion-resistant, wear-resistant, antifriction and antibacterial composite film layer is prepared on the surface of the nitrided selenium-added alloy steel, uniform nano holes are formed in the surface of the nitrided selenium-added alloy steel by controlling technological parameters of micro-arc oxidation, and then the nano holes formed by micro-arc oxidation are sealed by adopting an ultrasonic-assisted ionic liquid electroplating mode, so that the nitrided selenium-added alloy steel is obtained. Constructing a gradient hardness layer; choline chloride-ethylene glycol ionic liquid is selected as an electroplating solution solvent for ultrasonic-assisted ionic liquid electroplating, selenium-added alloy steel subjected to micro-arc oxidation treatment is put into an electroplating solution containing composite nano molybdenum disulfide, and a composite nano molybdenum disulfide doped copper-cobalt-nickel layer is constructed on the surface of the selenium-added alloy steel.

Description

Technical Field

[0001] The present invention relates to the technical field of alloy steel, and specifically to a preparation method of selenium-added alloy steel. Background Art

[0002] As a trace element, selenium can improve the processing performance of steel, and is thus often applied to the steel industry. It plays a positive role in improving the properties of alloy steel such as strength, ductility, and corrosion resistance. For example, selenium can enhance the binding force of interstitial atoms in alloy steel or help carbon in the steel alloy diffuse into ferrite, thereby achieving the effect of increasing the hardness of alloy steel. At the same time, selenium can also prevent hot cracking and oxidation.

[0003] In practical applications, the wear and corrosion of selenium-added alloy steel are hot research issues. Studying 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 the present invention is to provide a preparation method of selenium-added alloy steel to solve the problems in the prior art.

[0005] To solve the above technical problems, the present invention provides the following technical solutions:

[0006] A preparation method of selenium-added alloy steel includes the following steps:

[0007] S1: Melting alloy raw materials using a vacuum induction furnace, casting and molding to obtain a semi-finished product of selenium-added alloy steel;

[0008] S2: Sequentially performing solution treatment, cleaning, drying, sanding on the semi-finished product of selenium-added alloy steel, then performing ion nitriding treatment, polishing, alkali washing, acid washing, ultrasonic water washing, and drying to obtain nitrided selenium-added alloy steel;

[0009] S3: Performing micro-arc oxidation treatment on the nitrided selenium-added alloy steel, cleaning and drying to obtain pre-treated selenium-added alloy steel;

[0010] S4: Preparing an electroplating solution containing composite nano-molybdenum disulfide, putting the pre-treated selenium-added alloy steel into the electroplating solution, performing ultrasonic-assisted electroplating treatment, and drying to obtain a kind of selenium-added alloy steel.

[0011] Further, 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%, and the balance is iron.

[0012] Further, the working conditions of the solution treatment are: holding at 950°C for 60 min.

[0013] Furthermore, the working conditions for ion nitriding treatment are as follows: It is carried out in a glow ion nitriding furnace, with pure ammonia gas used as the atmosphere. It is kept at 550 °C for 15 h, with the ammonia decomposition rate maintained at 600 mL / h. Then, it is heated at a rate of 20 °C / h to 570 °C and kept at this temperature for 30 h, with the ammonia decomposition rate maintained at 750 mL / h. It is cooled with glow to 250 °C and then taken out of the furnace and cooled in oil.

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

[0015] Furthermore, the working conditions for ultrasonic-assisted electroplating treatment are as follows: The current density is 3.8 - 4.2 mA / cm 2 , the time is 50 - 60 min, the temperature is 65 °C, and the ultrasonic power is 250 W.

[0016] Furthermore, the composition of the electroplating solution is as follows: Using choline chloride - ethylene glycol ionic liquid as the 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; among them, the choline chloride - ethylene glycol ionic liquid is obtained by mixing choline chloride and ethylene glycol in a molar ratio of 1:2.

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

[0018] (1) Mix ammonium molybdate tetrahydrate and deionized water, add the template KIT-6, perform ultrasonic treatment for 5 - 10 min, stir for 8 - 10 h, filter and dry, add thiourea, grind, transfer to a nitrogen atmosphere, keep at 500 °C for 4 h, cool to 18 - 25 °C, add an aqueous NaOH solution and keep at this temperature for 18 - 20 h, wash, filter by suction, and dry to obtain porous nano-molybdenum disulfide; Mix the aqueous solution of porous nano-molybdenum disulfide and the aqueous solution of silver nitrate, perform ultrasonic mixing 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 and seal, let it stand at 18 - 25 °C for 22 - 24 h, centrifuge, wash, and dry to obtain ZIF-67; Mix ZIF-67 and ethanol, add silver-loaded nano-molybdenum disulfide, stir for 30 - 40 min, transfer to a reaction kettle, keep at 180 °C for 10 - 12 h, wash, and dry to obtain modified nano-molybdenum disulfide;

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

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

[0022] Further, the preparation of the template KIT-6 includes the following steps: Stir P123, deionized water, and hydrochloric acid solution at 32 - 37 °C for 3 - 4 h, add n-butanol, continue stirring for 1 - 2 h, add sodium silicate solution, continue stirring for 22 - 24 h, transfer to a reaction kettle, keep warm at 104 - 106 °C for 22 - 24 h, cool, filter by suction, wash, dry, calcine at 550 °C for 2 h, and grind to obtain the template KIT-6.

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

[0024] The present invention provides a preparation method of selenium-added alloy steel. Through process and composition design, an antibacterial selenium-added alloy steel with high strength, strong wear resistance, and good corrosion resistance is prepared, thereby prolonging the service life of the selenium-added alloy steel.

[0025] The present invention successively performs solution treatment and ion nitriding treatment on the semi-finished product of the selenium-added alloy steel after composition design, thereby greatly improving the mechanical strength of the selenium-added alloy steel.

[0026] By combining micro-arc oxidation and ultrasonic-assisted ionic liquid electroplating, a composite film layer with corrosion resistance, wear resistance and antifriction, and antibacterial properties is prepared on the surface of the nitrided selenium-added alloy steel, thereby improving various properties of the selenium-added alloy steel; by controlling the process parameters of micro-arc oxidation, uniform nano-pores are formed on the surface of the nitrided selenium-added alloy steel, and then the nano-pores formed by micro-arc oxidation are sealed by ultrasonic-assisted ionic liquid electroplating, thereby constructing a gradient hardness layer and improving the rust resistance and corrosion resistance of the selenium-added alloy steel.

[0027] To meet the requirements of existing green production, choline chloride-ethylene glycol ionic liquid is selected as the electroplating solution solvent for ultrasonic-assisted ionic liquid electroplating in the present invention. In the present invention, the selenium-added alloy steel after micro-arc oxidation treatment is put into the 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 greatly 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, and porous ordered molybdenum disulfide is in-situ synthesized by the nano-casting method, and then Ag + is loaded on the porous nano-molybdenum disulfide by electrostatic adsorption to construct a photo-thermal synergistic Ag +An antibacterial nano - platform. To further improve the corrosion resistance of composite nano - molybdenum disulfide, silver - loaded nano - molybdenum disulfide is combined with ZIF - 67 with a unique pore structure and large surface area, and then used as a nano - container for a composite corrosion inhibitor. The composite corrosion inhibitor is obtained by compounding polyaspartic acid with excellent biodegradability with sodium gluconate and benzotriazole, synergistically enhancing the corrosion resistance of selenium - added alloy steel, thereby constructing a film layer with long - lasting corrosion resistance and broad - spectrum antibacterial properties, and extending the service life of selenium - added alloy steel. Detailed implementation manners

[0028] The following will describe clearly and completely the technical solutions in the present invention in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than 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 making creative efforts fall within the protection scope of the present invention.

[0029] It should be noted that if there are directional indications such as up, down, left, right, front, and back in the embodiments of the present invention, the directional indications are only used to explain the relative positional relationship and movement conditions between components in a specific posture. If the specific posture changes, the directional indications will also change accordingly. In addition, the technical solutions between various embodiments can be combined with each other, but it must be based on the fact that those of ordinary skill in the art can implement it. When the combination of technical solutions results in contradictions or cannot be implemented, it should be considered that such a combination of technical solutions does not exist and is not within the protection scope required by the present invention.

[0030] The following further elaborates on the technical solutions of the present invention in conjunction with specific embodiments. It should be understood that the following embodiments are only used to explain the present invention and are not used to limit the present invention.

[0031] Example 1: A preparation method of selenium - added alloy steel includes the following steps:

[0032] S1: Melting alloy raw materials using a vacuum induction furnace, casting and molding to obtain a semi - finished selenium - added alloy steel;

[0033] By mass percentage, the composition of the alloy raw materials is as follows: manganese 29.5%, aluminum 9.5%, molybdenum 0.45%, silicon 0.95%, carbon 1.05%, selenium 0.3%, and the balance is iron;

[0034] S2: Sequentially performing solution treatment, cleaning, drying, grinding on the semi - finished selenium - added alloy steel, and then performing ion nitriding treatment, polishing, alkali washing, acid washing, ultrasonic water washing, and drying to obtain nitrided selenium - added alloy steel;

[0035] The working conditions of the solution treatment are as follows: holding at 950 °C for 60 min; the working conditions of the ion nitriding treatment are as follows: carried out in a glow ion nitriding furnace, the atmosphere used is pure ammonia gas, holding at 550 °C for 15 h, maintaining the ammonia decomposition rate at 600 mL / h, then heating up to 570 °C at a rate of 20 °C / h and holding for 30 h, maintaining the ammonia decomposition rate at 750 mL / h, cooling with glow to 250 °C, and taking out of the furnace and cooling in oil;

[0036] S3: Perform micro-arc oxidation treatment on the nitrided selenium-added alloy steel, clean and dry it to obtain the pretreated selenium-added alloy steel;

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

[0038] S4: Prepare an electroplating solution containing composite nano-molybdenum disulfide, put the pretreated selenium-added alloy steel into the electroplating solution, carry out ultrasonic-assisted electroplating treatment, and dry it to obtain a kind of selenium-added alloy steel;

[0039] The working conditions of the ultrasonic-assisted electroplating treatment are: the current density is 3.8 mA / cm 2 , the time is 60 min, the temperature is 65 °C, and the ultrasonic power is 250 W;

[0040] The electroplating solution: using deionized water as the solvent, which contains 86 g / L of nickel chloride hexahydrate, 46 g / L of cobalt chloride hexahydrate, 21 g / L of nickel sulfamate, 15 g / L of copper chloride dihydrate, and 5 g / L of composite nano-molybdenum disulfide; among them, 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 1.3 g of ammonium molybdate tetrahydrate and 4 mL of deionized water, add 0.8 g of template KIT-6, perform ultrasonic treatment for 5 min, stir for 8 h, filter and dry, add 0.1 g of thiourea, grind, transfer to a nitrogen atmosphere, hold at 500 °C for 4 h, cool down to 18 °C, add 2 mol / L NaOH aqueous solution and hold for 18 h, wash with water, filter by suction and dry to obtain porous nano-molybdenum disulfide; mix 10 mL of 1 mg / mL porous nano-molybdenum disulfide aqueous solution and 10 mL of 1 mg / mL silver nitrate aqueous solution, centrifuge, wash, and freeze-dry to obtain silver-loaded nano-molybdenum disulfide;

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

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

[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 the template KIT-6 includes the following steps: Mix 2 g of P123, 72 g of deionized water, and 4 g of hydrochloric acid solution with a mass concentration of 37%, stir at 32 °C for 4 h, add 2 g of n-butanol, continue stirring for 1 h, add 4.2 g of sodium silicate solution with a mass concentration of 30%, continue stirring for 22 h, transfer to a reaction kettle, keep warm at 104 °C for 24 h, cool, filter by suction, wash, and dry, calcine at 550 °C for 2 h, and grind to obtain the template KIT-6.

[0047] Example 2: A preparation method of selenium-added alloy steel, including the following steps:

[0048] S1: Melting alloy raw materials using a vacuum induction furnace, casting to obtain a selenium-added alloy steel semi-finished product;

[0049] By mass percentage, the composition of the alloy raw materials is as follows: manganese 29.5%, aluminum 9.5%, molybdenum 0.45%, silicon 0.95%, carbon 1.01%, selenium 0.3%, and the balance is iron;

[0050] S2: Sequentially perform solution treatment on the selenium-added alloy steel semi-finished product, clean, dry, grind, then perform ion nitriding treatment, polish, alkali wash, acid wash, ultrasonic water wash, and dry to obtain nitrided selenium-added alloy steel;

[0051] The working conditions of the solution treatment are: keep warm at 950 °C for 60 min; the working conditions of the ion nitriding treatment are: carried out in a glow ion nitriding furnace, the atmosphere used is pure ammonia gas, keep warm at 550 °C for 15 h, keep the ammonia decomposition rate at 600 mL / h, then heat up to 570 °C at a rate of 20 °C / h and keep warm for 30 h, keep the ammonia decomposition rate at 750 mL / h, cool with glow to 250 °C, and take out and cool in oil;

[0052] S3: Perform micro-arc oxidation treatment on the nitrided selenium-added alloy steel, wash and dry it to obtain the pretreated selenium-added alloy steel;

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

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

[0055] The working conditions of the ultrasonic-assisted electroplating treatment are: The current density is 4 mA / cm 2 , the time is 55 min, the temperature is 65 °C, and the ultrasonic power is 250 W;

[0056] The electroplating solution: Using deionized water as the 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; Among them, 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 1.3 g of ammonium molybdate tetrahydrate and 4 mL of deionized water, add 0.8 g of template KIT-6, perform ultrasonic treatment for 8 min, stir for 9 h, filter and dry, add 0.1 g of thiourea, grind, transfer to a nitrogen atmosphere, keep warm at 500 °C for 4 h, cool down to 20 °C, add 2 mol / L NaOH aqueous solution and keep warm for 19 h, wash, filter by suction and dry to obtain porous nano-molybdenum disulfide; Mix 10 mL of 1 mg / mL porous nano-molybdenum disulfide aqueous solution and 10 mL of 1 mg / mL silver nitrate aqueous solution, centrifuge, wash and freeze-dry to obtain silver-loaded nano-molybdenum disulfide;

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

[0060] (3) Mix 6 g of the composite corrosion inhibitor and 100 mL of ethanol, add 0.7 g of modified nano-molybdenum disulfide, stir ultrasonically for 1.5 h, transfer to a vacuum environment, stir ultrasonically for 25 min, 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: Mix 2 g of P123, 72 g of deionized water, and 4 g of hydrochloric acid solution with a mass concentration of 37%, stir at 35 °C for 3.5 h, add 2 g of n-butanol, continue stirring for 1.5 h, add 4.2 g of sodium silicate solution with a mass concentration of 30%, continue stirring for 23 h, transfer to a reaction kettle, keep warm at 105 °C for 23 h, cool, filter, wash, and dry, calcine at 550 °C for 2 h, and grind to obtain template KIT-6.

[0063] Example 3: A preparation method of selenium-added alloy steel, including the following steps:

[0064] S1: Melting alloy raw materials using a vacuum induction furnace, casting and molding to obtain a selenium-added alloy steel semi-finished product;

[0065] By mass percentage, the composition of the alloy raw materials is as follows: manganese 29.5%, aluminum 9.5%, molybdenum 0.45%, silicon 0.95%, carbon 1.05%, selenium 0.3%, and the balance is iron;

[0066] S2: Sequentially perform solution treatment on the selenium-added alloy steel semi-finished product, clean, dry, and sandblast, then perform ion nitriding treatment, polish, alkali wash, acid wash, ultrasonic water wash, and dry to obtain nitrided selenium-added alloy steel;

[0067] The working conditions of the solution treatment are: keep warm at 950 °C for 60 min; the working conditions of the ion nitriding treatment are: carried out in a glow ion nitriding furnace, the atmosphere used is pure ammonia gas, keep warm at 550 °C for 15 h, keep the ammonia decomposition rate at 600 mL / h, then heat up to 570 °C at a rate of 20 °C / h and keep warm for 30 h, keep the ammonia decomposition rate at 750 mL / h, cool with glow to 250 °C, and take out the furnace for oil cooling;

[0068] S3: Perform micro-arc oxidation treatment on the nitrided selenium-added alloy steel, clean and dry to obtain pre-treated selenium-added alloy steel;

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

[0070] S4: Prepare an electroplating solution containing composite nano-molybdenum disulfide. Place the pre-treated selenium-added alloy steel into the electroplating solution and conduct ultrasonic-assisted electroplating treatment. After drying, a kind of selenium-added alloy steel is obtained;

[0071] The working conditions of the ultrasonic-assisted electroplating treatment are: current density 4.2 mA / cm 2 , time is 50 min, temperature is 65 °C, and ultrasonic power is 250 W;

[0072] The electroplating solution: uses deionized water as the solvent, and contains 86 g / L nickel chloride hexahydrate, 46 g / L cobalt chloride hexahydrate, 21 g / L nickel sulfamate, 15 g / L copper chloride dihydrate, 7 g / L composite nano-molybdenum disulfide; among them, 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 said composite nano-molybdenum disulfide includes the following steps:

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

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

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

[0077] The composite corrosion inhibitor is obtained by mixing 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: 2 g of P123, 72 g of deionized water, and 4 g of hydrochloric acid solution with a mass concentration of 37% are stirred at 37 °C for 3 h. Then 2 g of n-butanol is added and stirring continues for 2 h. Next, 4.2 g of sodium silicate solution with a mass concentration of 30% is added and stirring continues for 24 h. The mixture is transferred to a reaction kettle, kept at 106 °C for 22 h, cooled, filtered by suction, washed, dried, calcined at 550 °C for 2 h, and ground to obtain Template KIT-6.

[0079] Comparative Example 1: Taking Example 3 as the control group, silver-loaded nano-molybdenum disulfide is used to replace the composite nano-molybdenum disulfide, and other processes are normal.

[0080] Comparative Example 2: Taking Example 3 as the control group, nano-molybdenum disulfide (XH-MoS2-100: Shanghai Xiaohuang Nano Technology Co., Ltd.) is used to replace the composite nano-molybdenum disulfide, and other processes are normal.

[0081] Sources of raw materials used (only as a demonstration example):

[0082] P123 A392125: (Alpha) Zhengzhou Alpha Chemical Co., Ltd.; sodium hexametaphosphate S108858, nickel chloride hexahydrate N112126, cobalt chloride hexahydrate C116457, nickel sulfamate N102822, copper chloride dihydrate C111680, choline chloride C108896, ethylene glycol E103319, ammonium molybdate tetrahydrate A294843, thiourea T112512, cobalt nitrate hexahydrate C112729, 2-methylimidazole M104839, polyaspartic acid P303238, sodium gluconate S432829, benzotriazole B101002: Aladdin reagents; sodium silicate, NaOH, silver nitrate, methanol, ethanol, hydrochloric acid, n-butanol, of analytical grade, purchased from the market.

[0083] Performance test: The alloys prepared in the examples and comparative examples are tested;

[0084] Antibacterial property: Using Staphylococcus aureus as the test strain, the plate method is adopted for testing;

[0085] Wear resistance: Tested using a vertical universal friction and wear testing machine, with GCr15 as the counter-material, the rotating speed of the turntable is 110 r / min, the load is 12 N, the time is 20 min, the sample is kept at 200 °C for 2 h, and then cooled to 25 °C for wear resistance testing. It is characterized by the worn weight ΔG of the sample, where ΔG = G0 - G1 (G0 - weight before wear, G1 - weight after wear);

[0086] Corrosion resistance: Keep the specimen at 200 °C for 12 h, cool it down to 25 °C for corrosion resistance test, put it into a salt spray chamber with a temperature of 37.5 °C, a sodium chloride concentration of 60 g / L, and a pH of 6.8, and observe whether there are rust and other phenomena after 1200 h. If there is none, it is qualified; the results are shown in Table 1.

[0087] Table 1

[0088]

[0089] The present invention provides a preparation method of selenium-added alloy steel. Through process and composition design, an antibacterial selenium-added alloy steel with high strength, strong wear resistance and good corrosion resistance is prepared, thereby prolonging the service life of the selenium-added alloy steel.

[0090] Comparing Example 3 with Comparative Example 1 and Comparative Example 2, it can be seen that in order to meet the requirements of existing green production, choline chloride-ethylene glycol ionic liquid is selected as the electroplating solution solvent for ultrasonic-assisted ionic liquid electroplating in the present invention. In the present invention, the selenium-added alloy steel after micro-arc oxidation treatment is put into 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 greatly improving the wear resistance and corrosion resistance of the selenium-added alloy steel; among them, the composite nano-molybdenum disulfide uses mesoporous material KIT-6 as a template, and porous and ordered molybdenum disulfide is in-situ synthesized by the nano-casting method, and then Ag + is loaded on the porous nano-molybdenum disulfide to construct a nano-platform with photothermal synergistic Ag + antibacterial property. To further improve the corrosion resistance of the composite nano-molybdenum disulfide, the silver-loaded nano-molybdenum disulfide is combined with ZIF-67 with a unique pore structure and a large surface area, and then the metal framework is used as a nano-container for the composite corrosion inhibitor, thereby constructing a film layer with long-lasting corrosion resistance and broad-spectrum antibacterial property, and prolonging the service life of the selenium-added alloy steel.

[0091] The above are only the embodiments of the present invention, and do not limit the patent scope of the present invention accordingly. All equivalent structural transformations made using the description of the present invention under the inventive concept of the present invention, or direct / indirect applications in other related technical fields are included in the patent protection scope of the present invention.

Claims

1. A method for preparing selenium-added alloy steel, characterized in that, It includes the following steps: S1: Melting alloy raw materials in a vacuum induction furnace, casting and molding to obtain a semi-finished selenium-added alloy steel; S2: Successively performing solution treatment, cleaning, drying, sanding on the semi-finished selenium-added alloy steel, then performing ion nitriding treatment, polishing, alkali washing, acid washing, ultrasonic water washing, and drying to obtain nitrided selenium-added alloy steel; S3: Performing micro-arc oxidation treatment on the nitrided selenium-added alloy steel, cleaning and drying to obtain pretreated selenium-added alloy steel; S4: Preparing an electroplating solution containing composite nano-molybdenum disulfide, putting the pretreated selenium-added alloy steel into the electroplating solution, performing ultrasonic-assisted electroplating treatment, and drying to obtain a kind of selenium-added alloy steel.

2. The preparation method of a selenium-added alloy steel according to claim 1, wherein 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%, and the balance is iron.

3. The preparation method of a selenium-added alloy steel according to claim 1, characterized in that, The working conditions of the solution treatment are: keeping warm at 950 °C for 60 min; the working conditions of the ion nitriding treatment are: carried out in a glow ion nitriding furnace, the atmosphere used is pure ammonia gas, keeping warm at 550 °C for 15 h, maintaining the ammonia decomposition rate at 600 mL / h, then heating up to 570 °C at a rate of 20 °C / h and keeping warm for 30 h, maintaining the ammonia decomposition rate at 750 mL / h, cooling with glow to 250 °C, and taking out of the furnace and cooling in oil.

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

5. The preparation method of a selenium-added alloy steel according to claim 1, characterized in that, The working conditions for ultrasonic-assisted electroplating treatment are: current density 3.8 - 4.2 mA / cm 2 , time 50 - 60 min, temperature 65 °C, ultrasonic power 250 W.

6. The preparation method of a selenium-added alloy steel according to claim 1, characterized in that, The composition of the electroplating solution is: using choline chloride-ethylene glycol ionic liquid as the 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, (5 - 7) g / L composite nano-molybdenum disulfide; the choline chloride-ethylene glycol ionic liquid is prepared by compounding choline chloride and ethylene glycol in a molar ratio of 1:

2.

7. The preparation method of a selenium-added alloy steel according to claim 1, wherein, The preparation of the composite nano-molybdenum disulfide includes the following steps: (1) Mixing ammonium molybdate tetrahydrate and deionized water, adding template KIT-6, performing ultrasonic treatment for 5 - 10 min, stirring for 8 - 10 h, filtering and drying, adding thiourea, grinding, transferring to a nitrogen atmosphere, keeping warm at 500 °C for 4 h, cooling to 18 - 25 °C, adding an aqueous NaOH solution and keeping warm for 18 - 20 h, washing with water, filtering by suction, and drying to obtain porous nano-molybdenum disulfide; mixing the aqueous solution of porous nano-molybdenum disulfide and the aqueous solution of silver nitrate, performing ultrasonic mixing for 10 - 15 min, centrifuging, washing, and freeze-drying to obtain silver-loaded nano-molybdenum disulfide; (2) Mixing cobalt nitrate hexahydrate and methanol, adding a mixture of 2-methylimidazole and methanol, stirring and sealing, standing at 18 - 25 °C for 22 - 24 h, centrifuging, washing, and drying to obtain ZIF-67; mixing ZIF-67 and ethanol, adding silver-loaded nano-molybdenum disulfide, stirring for 30 - 40 min, transferring to a reaction kettle, keeping warm at 180 °C for 10 - 12 h, washing and drying to obtain modified nano-molybdenum disulfide; (3) Mix the composite corrosion inhibitor and ethanol, add modified nano-molybdenum disulfide, stir ultrasonically for 1 - 2 h, transfer to a vacuum environment, stir ultrasonically for 20 - 30 min, wash and dry to obtain composite nano-molybdenum disulfide.

8. The preparation method of a selenium-added alloy steel according to claim 7, characterized in that, The composite corrosion inhibitor is prepared by compounding polyaspartic acid, sodium gluconate, and benzotriazole in a mass ratio of 1:2:

3.

9. The preparation method of a selenium-added alloy steel according to claim 7, characterized in that, The preparation of the template KIT-6 includes the following steps: Stir P123, deionized water, and hydrochloric acid solution at 32 - 37 °C for 3 - 4 h, add n-butanol, continue stirring for 1 - 2 h, add sodium silicate solution, continue stirring for 22 - 24 h, transfer to a reaction kettle, keep warm at 104 - 106 °C for 22 - 24 h, cool, filter by suction, wash, dry, calcine at 550 °C for 2 h, and grind to obtain the template KIT-6.

10. A selenium-added alloy steel, characterized in that, Prepared by the preparation method described in any one of claims 1 - 9.

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