Preparation method of high-strength and high-wear-resistance tungsten carbide hydrophobic layer on surface of steel material

Abstract

The application discloses a preparation method of a high-strength and high-wear-resistance tungsten carbide hydrophobic layer on a steel material surface, and comprises the following steps: 1) obtaining a steel material with a carburized layer on the surface by pre-carburization; 2) preparing a tungsten layer and an iron layer on the surface of the carburized steel material in sequence, and adding aminated polystyrene microspheres in the process of preparing the iron layer so that a large number of aminated polystyrene microspheres are distributed at the interface between the tungsten layer and the iron layer; 3) performing carburization treatment, decomposing the aminated polystyrene microspheres at high temperature, converting the tungsten layer into a tungsten carbide layer, and forming a rough interface between the tungsten carbide layer and the iron layer; and 4) removing the iron layer and modifying the surface with a low-surface-energy substance, so as to finally obtain a rough tungsten carbide layer and a hydrophobic layer on the surface of the rough tungsten carbide layer. The hydrophobic layer prepared by the method has high strength and hardness, excellent wear resistance, strong film-substrate adhesion, good hydrophobicity and corrosion resistance, is simple to operate, has strong applicability and high production efficiency.

Description

Technical Field

[0001] The invention belongs to the technical field of metal material surface treatment, and particularly relates to a method for preparing a high-strength and high-wear-resistant tungsten carbide hydrophobic layer on the surface of a steel material. Background Art

[0002] Steel is widely used in industry due to its excellent comprehensive mechanical properties. However, in certain specific applications, steel requires a combination of surface hardness, wear resistance, and corrosion resistance. Preparing a ceramic layer on the surface of steel is an effective way to improve surface hardness, wear resistance, and corrosion resistance. However, due to the poor hydrophobicity of the ceramic layer, it is susceptible to corrosion damage when exposed to long-term wetting with environmental liquids. Therefore, it is necessary to improve the surface hydrophobicity to slow the corrosion rate and improve corrosion resistance.

[0003] Research on the self-cleaning effect of lotus leaves has found that the nanoscale roughness and low surface energy of the waxy substance on the lotus leaf surface make it superhydrophobic. Inspired by this, researchers at home and abroad have improved surface hydrophobicity by constructing rough surfaces and preparing hydrophobic substances with low surface energy on them.

[0004] Methods for preparing surface roughness structures include etching, sol-gel, chemical vapor deposition, and spraying. Methods such as laser etching and plasma etching are complex, costly, and cannot be prepared quickly and on a large scale; the sol-gel method is complex, time-consuming, and difficult to control the surface structure; the roughness of thin films prepared by chemical vapor deposition is difficult to control; the substrate prepared by spraying has poor adhesion to the rough film, and the rough structure of the solid surface is easily destroyed. Therefore, there is an urgent need to prepare a coating on the surface of steel materials that has high hardness, high adhesion, high wear resistance, high hydrophobicity, and high corrosion resistance. Summary of the Invention

[0005] The purpose of the present invention is to provide a method for preparing a tungsten carbide hydrophobic layer with high hardness and high wear resistance on the surface of a steel material, thereby solving the problems of rough surface structure of the hydrophobic film, poor mechanical properties and poor durability in the prior art.

[0006] The technical solution adopted by the present invention is a method for preparing a high-strength and high-wear-resistant tungsten carbide hydrophobic layer on the surface of steel materials, which specifically includes the following steps:

[0007] Step 1: Carburize the steel material after surface pretreatment to form a carburized layer on the surface of the steel material;

[0008] Step 2: preparing a tungsten layer on the surface of the carburized layer by a thin film preparation process;

[0009] Step 3: The surface of the tungsten layer is electroplated using an electroplating solution containing amino-modified polystyrene microspheres to form an iron-amino-modified polystyrene microsphere layer;

[0010] Step 4: the iron-amino polystyrene microspheres layer and tungsten layer are subjected to carburizing treatment to obtain a tungsten carbide layer with a rough structure at the interface and an iron layer;

[0011] Step 5: the iron layer obtained in step 4 is etched clean with a chemical solution to obtain a tungsten carbide layer with a rough surface;

[0012] Step 6: the tungsten carbide layer with a rough surface is soaked in a low-surface-energy substance solution for 1-2 hours for surface modification, and a high-strength and high-wear-resistance tungsten carbide hydrophobic layer is obtained after drying.

[0013] The application also has the characteristics that:

[0014] The steel material in step 1 includes carbon steel and alloy steel, and the surface is pre-treated by sanding the surface with sandpaper until the surface oil stains and oxides are removed and the surface roughness is reduced. The pre-carburizing temperature ranges from 800 DEG C to 950 DEG C, and the pre-carburizing method is one of gas carburizing, solid carburizing, vacuum carburizing or plasma carburizing. The mass fraction of carbon element in the carburized layer on the surface of the steel material ranges from 0.8% to 2.0%;

[0015] The film preparation process in step 2 is one of ion plating, sputtering plating and chemical vapor deposition, and the thickness of the tungsten layer prepared ranges from 5 μm to 20 μm;

[0016] The specific method of electroplating treatment in step 3 is that the steel material with a tungsten layer is used as a cathode, pure iron is used as an anode, a ferrous chloride solution is used as an electroplating solution, and an amino polystyrene microsphere solution is added to the ferrous chloride solution. The thickness of the iron layer ranges from 15 μm to 30 μm.

[0017] The mass concentration of the ferrous chloride solution ranges from 300 g / L to 350 g / L, the pH value ranges from 1.3 to 1.5, the temperature ranges from 75 DEG C to 80 DEG C, and the current density ranges from 0.01 A / cm 2 -0.1 A / cm 2 .

[0018] The volume of the amino polystyrene microsphere solution added to 100 mL of the electroplating solution ranges from 2 mL to 4 mL, the solid content in the amino polystyrene microsphere solution is 25 mg / mL, and the average diameter of the amino polystyrene microspheres ranges from 5 μm to 10 μm.

[0019] The temperature range of the carburizing treatment in step 4 is 900 DEG C-1100 DEG C;

[0020] The chemical solution in step 5 is one of a hydrochloric acid solution, a sulfuric acid solution, or a nitric acid solution, wherein the mass fraction of hydrochloric acid in the hydrochloric acid solution is in the range of 15%-25%, the mass fraction of sulfuric acid in the sulfuric acid solution is in the range of 40%-70%, and the mass fraction of nitric acid in the nitric acid solution is in the range of 30%-50%;

[0021] The low surface energy substance solution in step 6 is any one of a perfluorodecyltriethoxysilane solution, a 1H,1H,2H,2H perfluorodecyltrihexyloxysilane ethanol solution, and a (3,3,3 trifluoropropyl) methyldimethoxysilane solution, and the mass fraction of the low surface energy substance in the low surface energy substance solution is in the range of 3%-5%.

[0022] The beneficial effects of the present invention are:

[0023] (1) The rough surface tungsten carbide layer prepared by the present invention has high strength and hardness, good wear resistance, and is formed by carburizing. The tungsten carbide is precipitated in situ, has high density, and high grain boundary strength. During the carburizing process, elements interdiffusion occurs between the tungsten layer and the substrate, forming a metallurgical bonding interface, and the film-base bonding strength is high;

[0024] (2) Compared with other surface technologies for preparing rough structures: Compared with the etching method, the present invention has lower costs and can be prepared quickly and on a large area; compared with the sol-gel method, the process is simple and easy to operate; compared with the chemical vapor deposition method, the surface structure prepared by the present invention has high roughness and good controllability; compared with the spraying method, it has high density, high ceramic volume fraction, high hardness, and good membrane-base bonding strength;

[0025] (3) The present invention can adjust the concentration of amino polystyrene balls added to the electroplating solution, the pH value of the electroplating solution, the current density and other parameters to control the surface roughness structure, thereby achieving the regulation of the surface structure;

[0026] (4) The present invention has small requirements on the shape of the workpiece, has strong applicability, and can process all surfaces of the metal substrate at the same time, with high production efficiency;

[0027] (5) The method for preparing the coating of the present invention is simple in process, easy to operate, and has strong applicability. The prepared rough structure hydrophobic layer has a stable structure, excellent wear resistance and high corrosion resistance, and has a good hydrophobic effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is a flow chart of the method for preparing a high-strength and high-wear-resistant tungsten carbide hydrophobic layer on the surface of steel materials of the present invention;

[0029] Figure 2 This is a partial enlarged view of a flow chart of the method for preparing a high-strength and high-wear-resistant tungsten carbide hydrophobic layer on the surface of a steel material of the present invention;

[0030] Figure 3 These are two partial enlarged views of the process flow of the method for preparing a high-strength and high-wear-resistant tungsten carbide hydrophobic layer on the surface of a steel material of the present invention;

[0031] Figure 4 Schematic diagram of the surface roughness structure of the hydrophobic layer prepared by the present invention. DETAILED DESCRIPTION

[0032] The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

[0033] The method for preparing a high-strength and high-wear-resistant tungsten carbide hydrophobic layer on the surface of a steel material of the present invention is as follows: Figure 1 As shown, please follow the steps below:

[0034] Step 1: Select a steel material as a substrate and polish its surface with sandpaper to remove surface oil and oxides and reduce surface roughness; then pre-carburize it at a temperature range of 800°C to 950°C using one of gas carburizing, solid carburizing, vacuum carburizing, and plasma carburizing to obtain a steel material having a carburized layer, wherein the mass fraction of carbon in the carburized layer ranges from 0.8% to 2.0%;

[0035] Step 2: preparing a tungsten layer on the surface of the steel material having the carburized layer by a thin film preparation process, wherein the thickness of the tungsten layer ranges from 5 μm to 20 μm. The thin film preparation process is one of ion plating, sputtering plating, and chemical vapor deposition. Preferably, magnetron sputtering is selected;

[0036] Step 3: Electroplating an iron layer on the surface of the steel material having a surface tungsten layer. Specifically, a ferrous chloride electrolyte with a mass concentration range of 300-350 g / L and a pH range of 1.3-1.5 is prepared, and a volume fraction range of 2 mL-4 mL of an amino polystyrene microsphere solution with a solid content of 25 mg / mL is added to every 100 mL of the electroplating solution. The average diameter of the amino polystyrene microspheres is in the range of 5 μm-10 μm. The steel material obtained in step 2 is used as the cathode and pure iron is used as the anode. The current density range is 0.01 A / cm 2 -0.1A / cm 2 The electroplating temperature is 75-80℃, and the thickness of the electroplated iron layer is 15μm-30μm. After electroplating, a steel material with an iron layer, amino polystyrene microspheres and a tungsten layer is obtained. Figure 2 As shown, a large number of amino-modified polystyrene microspheres are distributed at the interface between the tungsten layer and the iron layer;

[0037] Step 4: If Figure 3As shown, the steel material with an iron layer, amino polystyrene microspheres, and a tungsten layer on the surface obtained in step 3 is carburized at a temperature range of 900°C to 1100°C using a carburizing method selected from gas carburizing, solid carburizing, vacuum carburizing, and plasma carburizing. During the carburizing process, the amino polystyrene microspheres decompose, and the tungsten layer is converted into a tungsten carbide layer, with a rough interface formed between the tungsten carbide layer and the iron layer. After carburizing, an iron layer and a tungsten carbide layer with a rough interface are obtained.

[0038] Step 5: etching the surface iron layer of step 4 with a chemical solution, wherein the chemical solution is one of a hydrochloric acid solution, a sulfuric acid solution, or a nitric acid solution, wherein the mass fraction of hydrochloric acid in the hydrochloric acid solution is in a range of 15%-25%, the mass fraction of sulfuric acid in the sulfuric acid solution is in a range of 40%-70%, and the mass fraction of nitric acid in the nitric acid solution is in a range of 30%-50%, thereby obtaining a tungsten carbide layer with a rough surface;

[0039] Step 6: Soak the steel material with the roughened tungsten carbide layer obtained in step 5 for 1-2 hours in any one of a perfluorodecyltriethoxysilane solution, a 1H,1H,2H,2H-perfluorodecyltrihexyloxysilane ethanol solution, and a (3,3,3-trifluoropropyl)methyldimethoxysilane solution, wherein the mass fraction of the solute in the solution is in the range of 3%-5%. Remove and dry to obtain a high-strength and wear-resistant tungsten carbide hydrophobic layer.

[0040] In the preparation method of the high-strength and high-wear-resistant tungsten carbide hydrophobic layer on the surface of the steel material of the present invention: the role of step 1 is to enable the steel material matrix to serve as a carbon source in the subsequent carburizing process, providing carbon atoms for the tungsten layer, thereby achieving the effect of bidirectional carburizing; the role of the electroplated iron layer in step 3 is that iron can serve as a carburizing medium, which has the advantages that: on the one hand, the solid solubility of carbon in iron is relatively high, and on the other hand, the iron layer can act as a buffer, thereby avoiding the problem of loose and porous ceramic layer caused by excessive carbon potential; the principle of forming the surface rough structure is that after the amino polystyrene microspheres are decomposed at high temperature, pores are formed in the iron layer (especially at the interface between the iron layer and the tungsten layer), and then during the high-temperature carburizing process, the tungsten element diffuses on the inner surface of the pores of the iron layer, so that an iron-tungsten solid solution zone is formed in the area attached to the inner pore wall. The tungsten in the solid solution zone reacts with carbon to convert the pore wall area into tungsten carbide, forming a micron-sized tungsten carbide rough structure (primary rough structure), and at the same time, the tungsten carbide grows perpendicular to the inner pore wall, forming a micron or nanometer-scale dendritic rough structure (secondary rough structure). Therefore, after the rear surface iron layer is removed in step 5, a tungsten carbide surface with a hierarchical rough structure is obtained.

[0041] The rough surface tungsten carbide layer prepared by the present invention has high strength and hardness, and good wear resistance. The tungsten carbide ceramic layer is formed by carburizing. The tungsten carbide is precipitated in situ, is dense, has a high volume fraction of tungsten carbide, and grows internally, so the hardness is high and the membrane-base bonding strength is good. It has no harsh requirements on the workpiece and has strong applicability. It can be quickly prepared on all metal surfaces over a large area at the same time, and has high production efficiency. The surface roughness structure can be controlled by adjusting the concentration of amino polystyrene microspheres added to the electroplating solution, the pH value of the electroplating solution, the current density and other parameters, thereby achieving different hydrophobic membrane performance requirements.

[0042] Example 1:

[0043] The method for preparing a high-strength and high-wear-resistant tungsten carbide hydrophobic layer on the surface of a steel material of the present invention is specifically implemented according to the following steps:

[0044] Step 1: Carburize the steel material after surface pretreatment to form a carburized layer on the surface of the steel material;

[0045] The steel material in step 1 is 45 steel, and the surface pretreatment is to polish the surface of the steel material with sandpaper until the surface oil and oxides are removed. The pre-carburizing temperature is 800° C., and the mass fraction of carbon element in the carburized layer is 2.0%;

[0046] Step 2: preparing a tungsten layer on the surface of the carburized layer in step 1 by a thin film preparation process;

[0047] In step 2, the thin film preparation process is chemical vapor deposition, and the thickness of the tungsten layer is 15 μm;

[0048] Step 3: Electroplating an iron layer on the surface of the tungsten layer in step 2, wherein the electroplating solution contains amino-modified polystyrene microspheres to form an iron-amino-modified polystyrene microsphere layer;

[0049] The specific method of electroplating in step 3 is as follows: the steel material with tungsten layer is used as cathode, pure iron is used as anode, the electroplating solution is ferrous chloride solution, the mass concentration of ferrous chloride solution is 300g / L, the pH value is 1.3, the temperature is 75℃, and the current density is 0.01A / cm 2 A solution containing 5 μm-diameter amino polystyrene microspheres was added to the ferrous chloride solution. 2 mL of the 5 μm-diameter amino polystyrene microsphere solution was added to every 100 mL of the electroplating solution. The solid content of the amino polystyrene microsphere solution was 25 mg / mL. An iron-amino polystyrene microsphere layer was obtained. The iron layer had a thickness of 15 μm. Aminated polystyrene microspheres were distributed at the interface between the tungsten layer and the iron layer.

[0050] Step 4: Carburizing the iron-amino polystyrene microsphere layer and the tungsten layer. During the carburizing process, the amino polystyrene microspheres decompose, and the tungsten layer is converted into a tungsten carbide layer. A rough interface is formed between the tungsten carbide layer and the iron layer, thereby obtaining an iron layer and a tungsten carbide layer having a rough interface.

[0051] The temperature range of the carburizing treatment in step 4 is 900°C and the time is 30h;

[0052] Step 5: Use a chemical solution to corrode the iron layer with a rough structure at the interface and the iron layer on the surface of the tungsten carbide layer to obtain a tungsten carbide layer with a rough surface;

[0053] The chemical solution in step 5 is a hydrochloric acid solution, and the mass fraction of hydrochloric acid in the hydrochloric acid solution is 15%;

[0054] Step 6: Soak the tungsten carbide layer with a rough surface in step 5 in a low surface energy substance solution for 1 hour to perform surface modification, and obtain a high-strength and high-wear-resistant tungsten carbide hydrophobic layer after drying;

[0055] The low surface energy substance solution in step 6 is a (3,3,3-trifluoropropyl)methyldimethoxysilane solution, and the mass fraction of the (3,3,3-trifluoropropyl)methyldimethoxysilane solution is 3%.

[0056] Example 2:

[0057] The method for preparing a high-strength and high-wear-resistant tungsten carbide hydrophobic layer on the surface of a steel material of the present invention is specifically implemented according to the following steps:

[0058] Step 1: Carburize the steel material after surface pretreatment to form a carburized layer on the surface of the steel material;

[0059] The steel material in step 1 is T10 steel, and the surface pretreatment is to polish the surface of the steel material with sandpaper until the surface oil and oxides are removed. The pre-carburizing temperature is 950° C., and the mass fraction of carbon element in the carburized layer is 0.8%;

[0060] Step 2: preparing a tungsten layer on the surface of the carburized layer in step 1 by a thin film preparation process, wherein the thin film preparation process in step 2 is ion plating, and the thickness of the tungsten layer is 10 μm;

[0061] Step 3: Electroplating an iron layer on the surface of the tungsten layer in step 2, wherein the electroplating solution contains amino-modified polystyrene microspheres to form an iron-amino-modified polystyrene microsphere layer;

[0062] The specific method of electroplating in step 3 is as follows: the steel material with tungsten layer is used as cathode, pure iron is used as anode, the electroplating solution is ferrous chloride solution, the mass concentration of ferrous chloride solution is 320g / L, the pH value is 1.4, the temperature is 77℃, and the current density is 0.1A / cm2 A solution containing 6 μm-diameter amino polystyrene microspheres was added to the ferrous chloride solution. 2.5 mL of the 6 μm-diameter amino polystyrene microsphere solution was added to every 100 mL of the electroplating solution. The solid content of the amino polystyrene microsphere solution was 25 mg / mL. An iron-amino polystyrene microsphere layer was obtained. The iron layer had a thickness of 30 μm. Aminated polystyrene microspheres were distributed at the interface between the tungsten layer and the iron layer.

[0063] Step 4: Carburizing the iron-amino polystyrene microsphere layer and the tungsten layer. During the carburizing process, the amino polystyrene microspheres decompose, and the tungsten layer is converted into a tungsten carbide layer. A rough interface is formed between the tungsten carbide layer and the iron layer, thereby obtaining an iron layer and a tungsten carbide layer having a rough interface.

[0064] The temperature range of the carburizing treatment in step 4 is 1000°C and the time is 15h;

[0065] Step 5: Use a chemical solution to corrode the iron layer with a rough structure at the interface and the iron layer on the surface of the tungsten carbide layer to obtain a tungsten carbide layer with a rough surface;

[0066] The chemical solution in step 5 is a hydrochloric acid solution, and the mass fraction of hydrochloric acid in the hydrochloric acid solution is 20%;

[0067] Step 6: Soak the tungsten carbide layer with a rough surface in step 5 in a low surface energy substance solution for 1.5 hours to perform surface modification, and obtain a high-strength and high-wear-resistant tungsten carbide hydrophobic layer after drying;

[0068] The low surface energy substance solution in step 6 is an ethanol solution of 1H,1H,2H,2H-perfluorodecyltrihexyloxysilane, and the mass fraction of the ethanol solution of 1H,1H,2H,2H-perfluorodecyltrihexyloxysilane is 4%.

[0069] Example 3:

[0070] The method for preparing a high-strength and high-wear-resistant tungsten carbide hydrophobic layer on the surface of a steel material of the present invention is specifically implemented according to the following steps:

[0071] Step 1: Carburize the steel material after surface pretreatment to form a carburized layer on the surface of the steel material;

[0072] The steel material in step 1 is 45 steel, and the surface pretreatment is to polish the surface of the steel material with sandpaper until the surface oil and oxides are removed. The pre-carburizing temperature is 850° C., and the mass fraction of carbon element in the carburized layer is 1.2%;

[0073] Step 2: preparing a tungsten layer on the surface of the carburized layer in step 1 by a thin film preparation process;

[0074] The thin film preparation process in step 2 is sputtering, and the thickness of the tungsten layer is 12 μm;

[0075] Step 3: Electroplating an iron layer on the surface of the tungsten layer in step 2, wherein the electroplating solution contains amino-modified polystyrene microspheres to form an iron-amino-modified polystyrene microsphere layer;

[0076] The specific method of electroplating in step 3 is as follows: the steel material with tungsten layer is used as cathode, pure iron is used as anode, the electroplating solution is ferrous chloride solution, the mass concentration of ferrous chloride solution is 350g / L, the pH value is 1.5, the temperature is 80℃, and the current density is 0.04A / cm 2 A solution containing 7 μm-diameter amino polystyrene microspheres was added to the ferrous chloride solution. 4 mL of the 7 μm-diameter amino polystyrene microsphere solution was added to every 100 mL of the electroplating solution. The solid content of the amino polystyrene microsphere solution was 25 mg / mL. An iron-amino polystyrene microsphere layer was obtained. The iron layer had a thickness of 25 μm. Aminated polystyrene microspheres were distributed at the interface between the tungsten layer and the iron layer.

[0077] Step 4: Carburizing the iron-amino polystyrene microsphere layer and the tungsten layer. During the carburizing process, the amino polystyrene microspheres decompose, and the tungsten layer is converted into a tungsten carbide layer. A rough interface is formed between the tungsten carbide layer and the iron layer, thereby obtaining an iron layer and a tungsten carbide layer having a rough interface.

[0078] The temperature range of the carburizing treatment in step 4 is 1100°C and the time is 5 hours;

[0079] Step 5: Use a chemical solution to corrode the iron layer with a rough structure at the interface and the iron layer on the surface of the tungsten carbide layer to obtain a tungsten carbide layer with a rough surface;

[0080] The chemical solution in step 5 is a hydrochloric acid solution, and the mass fraction of hydrochloric acid in the hydrochloric acid solution is 20%;

[0081] Step 6: Soak the tungsten carbide layer with a rough surface in step 5 in a low surface energy substance solution for 2 hours to perform surface modification, and obtain a high-strength and high-wear-resistant tungsten carbide hydrophobic layer after drying;

[0082] The low surface energy substance solution in step 6 is a perfluorodecyltriethoxysilane solution, and the mass fraction of the perfluorodecyltriethoxysilane solution is 5%.

[0083] Example 4:

[0084] The method for preparing a high-strength and high-wear-resistant tungsten carbide hydrophobic layer on the surface of a steel material of the present invention is specifically implemented according to the following steps:

[0085] Step 1: Carburize the steel material after surface pretreatment to form a carburized layer on the surface of the steel material;

[0086] The steel material in step 1 is T10 steel, and the surface pretreatment is to polish the surface of the steel material with sandpaper until the surface oil and oxides are removed. The pre-carburizing temperature is 825°C, and the carbon mass fraction of the carburized layer is 1.4%;

[0087] Step 2: preparing a tungsten layer on the surface of the carburized layer in step 1 by a thin film preparation process;

[0088] In step 2, the thin film preparation process is magnetron sputtering, and the thickness of the tungsten layer is 5 μm;

[0089] Step 3: Electroplating an iron layer on the surface of the tungsten layer in step 2, wherein the electroplating solution contains amino-modified polystyrene microspheres to form an iron-amino-modified polystyrene microsphere layer;

[0090] The specific method of electroplating in step 3 is as follows: the steel material with tungsten layer is used as cathode, pure iron is used as anode, the electroplating solution is ferrous chloride solution, the mass concentration of ferrous chloride solution is 300g / L, the pH value is 1.3, the temperature is 75℃, and the current is 0.06A / cm 2 , and add a solution containing 8 μm-diameter amino polystyrene microspheres to the ferrous chloride solution, add 2 mL of the 8 μm-diameter amino polystyrene microsphere solution to every 100 mL of the electroplating solution, the solid content of the amino polystyrene microsphere solution is 25 mg / mL, the iron-amino polystyrene microsphere layer, the iron layer thickness is 15 μm, and amino polystyrene microspheres are distributed at the interface between the tungsten layer and the iron layer;

[0091] Step 4: Carburizing the iron-amino polystyrene microsphere layer and the tungsten layer. During the carburizing process, the amino polystyrene microspheres decompose, and the tungsten layer is converted into a tungsten carbide layer. A rough interface is formed between the tungsten carbide layer and the iron layer, thereby obtaining an iron layer and a tungsten carbide layer having a rough interface.

[0092] The temperature range of the carburizing treatment in step 4 is 900°C and the time is 10h;

[0093] Step 5: Use a chemical solution to corrode the iron layer with a rough structure at the interface and the iron layer on the surface of the tungsten carbide layer to obtain a tungsten carbide layer with a rough surface;

[0094] The chemical solution in step 5 is a sulfuric acid solution, and the mass fraction of sulfuric acid in the sulfuric acid solution is 40%;

[0095] Step 6: Soak the tungsten carbide layer with a rough surface in step 5 in a low surface energy substance solution for 1.5 hours to perform surface modification, and obtain a high-strength and high-wear-resistant tungsten carbide hydrophobic layer after drying;

[0096] The low surface energy substance solution in step 6 is a (3,3,3-trifluoropropyl)methyldimethoxysilane solution, and the mass fraction of the (3,3,3-trifluoropropyl)methyldimethoxysilane solution is 5%.

[0097] Example 5:

[0098] The method for preparing a high-strength and high-wear-resistant tungsten carbide hydrophobic layer on the surface of a steel material of the present invention is specifically implemented according to the following steps:

[0099] Step 1: Carburize the steel material after surface pretreatment to form a carburized layer on the surface of the steel material;

[0100] The steel material in step 1 is T10 steel, and the surface pretreatment is to polish the surface of the steel material with sandpaper until the surface oil and oxides are removed. The pre-carburizing temperature is 925°C, and the carbon mass fraction of the carburized layer is 1.6%;

[0101] Step 2: preparing a tungsten layer on the surface of the carburized layer in step 1 by a thin film preparation process, wherein the thin film preparation process in step 2 is chemical vapor deposition, and the thickness of the tungsten layer is 20 μm;

[0102] Step 3: Electroplating an iron layer on the surface of the tungsten layer in step 2, wherein the electroplating solution contains amino-modified polystyrene microspheres to form an iron-amino-modified polystyrene microsphere layer;

[0103] The specific method of electroplating in step 3 is as follows: the steel material with tungsten layer is used as cathode, pure iron is used as anode, the electroplating solution is ferrous chloride solution, the mass concentration of ferrous chloride solution is 300g / L, the pH value is 1.5, the temperature is 75℃, and the current is 0.08A / cm 2 A solution containing amino-modified polystyrene microspheres with a diameter of 9 μm was added to the ferrous chloride solution. 3 mL of the amino-modified polystyrene microsphere solution with a diameter of 9 μm was added to every 100 mL of the electroplating solution. The solid content of the amino-modified polystyrene microsphere solution was 25 mg / mL. An iron-amino-modified polystyrene microsphere layer was obtained. The iron layer had a thickness of 20 μm. Aminated polystyrene microspheres were distributed at the interface between the tungsten layer and the iron layer.

[0104] Step 4: Carburizing the iron-amino polystyrene microsphere layer and the tungsten layer. During the carburizing process, the amino polystyrene microspheres decompose, and the tungsten layer is converted into a tungsten carbide layer. A rough interface is formed between the tungsten carbide layer and the iron layer, thereby obtaining an iron layer and a tungsten carbide layer having a rough interface.

[0105] The temperature range of the carburizing treatment in step 4 is 1100°C and the time is 10 hours;

[0106] Step 5: Use a chemical solution to corrode the iron layer with a rough structure at the interface and the iron layer on the surface of the tungsten carbide layer to obtain a tungsten carbide layer with a rough surface;

[0107] The chemical solution in step 5 is a sulfuric acid solution, and the mass fraction of sulfuric acid in the sulfuric acid solution is 70%;

[0108] Step 6: Soak the tungsten carbide layer with a rough surface in step 5 in a low surface energy substance solution for 1 hour to perform surface modification, and obtain a high-strength and high-wear-resistant tungsten carbide hydrophobic layer after drying;

[0109] The low surface energy substance solution in step 6 is a (3,3,3-trifluoropropyl)methyldimethoxysilane solution, and the mass fraction of the (3,3,3-trifluoropropyl)methyldimethoxysilane solution is 4%.

[0110] Example 6:

[0111] The method for preparing a high-strength and high-wear-resistant tungsten carbide hydrophobic layer on the surface of a steel material of the present invention is specifically implemented according to the following steps:

[0112] Step 1: Carburize the steel material after surface pretreatment to form a carburized layer on the surface of the steel material;

[0113] The steel material in step 1 is 45 steel, and the surface pretreatment is to polish the surface of the steel material with sandpaper until the surface oil and oxides are removed. The pre-carburizing temperature is 1000° C., and the mass fraction of carbon in the carburized layer is 1.8%;

[0114] Step 2: preparing a tungsten layer on the surface of the carburized layer in step 1 by a thin film preparation process. The thin film preparation process in step 2 is magnetron sputtering. The thickness of the tungsten layer of the steel material with the tungsten layer is 8 μm.

[0115] Step 3: electroplating the steel material having the tungsten layer obtained in step 2 to obtain a steel material having an iron layer, amino-modified polystyrene microspheres and a tungsten layer;

[0116] The specific method of electroplating in step 3 is as follows: the steel material with tungsten layer is used as cathode, pure iron is used as anode, the electroplating solution is ferrous chloride solution, the mass concentration of ferrous chloride solution is 300g / L, the pH value is 1.3, the temperature is 80℃, and the current is 0.1A / cm 2 , and add a solution containing amino polystyrene microspheres with a diameter of 10 μm to the ferrous chloride solution, add 2 mL of the amino polystyrene microsphere solution with a diameter of 10 μm to every 100 mL of the electroplating solution, the solid content of the amino polystyrene microsphere solution is 25 mg / mL, the iron-amino polystyrene microsphere layer, the iron layer thickness is 30 μm, and amino polystyrene microspheres are distributed at the interface between the tungsten layer and the iron layer;

[0117] Step 4: Carburizing the iron-amino polystyrene microsphere layer and the tungsten layer. During the carburizing process, the amino polystyrene microspheres decompose, and the tungsten layer is converted into a tungsten carbide layer. A rough interface is formed between the tungsten carbide layer and the iron layer, thereby obtaining an iron layer and a tungsten carbide layer having a rough interface.

[0118] The temperature range of the carburizing treatment in step 4 is 1000°C and the time is 10h;

[0119] Step 5: Use a chemical solution to corrode the iron layer with a rough structure at the interface and the iron layer on the surface of the tungsten carbide layer to obtain a tungsten carbide layer with a rough surface;

[0120] The chemical solution in step 5 is a nitric acid solution, and the mass fraction of sulfuric acid in the nitric acid solution is 30%;

[0121] Step 6: Soak the tungsten carbide layer with a rough surface in step 5 in a low surface energy substance solution for 1.5 hours to perform surface modification, and obtain a high-strength and high-wear-resistant tungsten carbide hydrophobic layer after drying;

[0122] The low surface energy substance solution in step 6 is a (3,3,3-trifluoropropyl)methyldimethoxysilane solution, and the mass fraction of the (3,3,3-trifluoropropyl)methyldimethoxysilane solution is 3%.

[0123] Performance testing:

[0124] (1) Hardness: The microhardness of the above cases was measured by Vickers microhardness test. The load was 50 g, the indenter was a conical indenter, and the holding time was 10 s.

[0125] (2) Contact angle: The contact angle of the sample surface was measured using a contact angle meter with a droplet volume of 5 L;

[0126] The high-strength and high-wear-resistant tungsten carbide hydrophobic layers prepared in Examples 1-6 were subjected to relevant performance tests, and the test results are shown in the following table:

[0127] Item Surface hardness Contact angle (°) Example 1 2800 HV 162 Example 2 2500 HV 158 Example 3 2600 HV 156 Example 4 2000 HV 153 Example 5 2900 HV 160 Example 6 2200 HV 152

[0128] The surface roughness produced by the method for preparing a high-strength, highly wear-resistant tungsten carbide hydrophobic layer on the surface of steel materials has excellent mechanical properties. Its surface hardness can reach an average of 2900 HV, demonstrating excellent wear resistance. Contact angle measurements with a contact angle meter show that the prepared tungsten carbide hydrophobic layer exhibits a water contact angle greater than 150°, demonstrating excellent hydrophobic properties.

Claims

1. A method for preparing a high-strength and high-wear-resistant tungsten carbide hydrophobic layer on the surface of steel materials, characterized in that: Please follow the steps below to implement: Step 1: Carburize the steel material after surface pretreatment to form a carburized layer on the surface of the steel material; Step 2: preparing a tungsten layer on the surface of the carburized layer by a thin film preparation process; Step 3: electroplating the surface of the tungsten layer using an electroplating solution containing amino-modified polystyrene microspheres to form an iron-amino-modified polystyrene microsphere layer; Step 4: Carburizing the iron-amino polystyrene microsphere layer and the tungsten layer to obtain an iron layer and a tungsten carbide layer with a rough structure at the interface; Step 5: Use a chemical solution to corrode the iron layer obtained in step 4 to obtain a tungsten carbide layer with a rough surface; Step 6: Soak the tungsten carbide layer with a rough surface in a low surface energy substance solution for 1 hour to 2 hours to perform surface modification, and obtain a high-strength and high-wear-resistant tungsten carbide hydrophobic layer after drying.

2. The method for preparing a high-strength and high-wear-resistant tungsten carbide hydrophobic layer on a steel material surface according to claim 1, wherein The steel material in step 1 includes carbon steel or alloy steel, and the surface pretreatment is to polish the surface of the metal substrate with sandpaper until the oil and oxide on the surface of the metal substrate are removed. The pre-carburizing temperature range is 900°C-1100°C, and the pre-carburizing method is one of gas carburizing, solid carburizing, vacuum carburizing or plasma carburizing. After pre-carburizing, the mass fraction of carbon element in the carburized layer on the surface of the steel material is in the range of 0.8%-2.0%.

3. The method for preparing the high-strength and high-wear-resistant tungsten carbide hydrophobic layer on the surface of steel material according to claim 1, wherein The thin film preparation process in step 2 is one of ion plating, sputtering plating, and chemical vapor deposition, and the thickness of the tungsten layer is 5 μm-20 μm.

4. The method for preparing a high-strength and high-wear-resistant tungsten carbide hydrophobic layer on the surface of steel material according to claim 1, wherein The specific method of the electroplating treatment in step 3 is: the steel material with the tungsten layer is used as the cathode, pure iron is used as the anode, the electroplating solution is a ferrous chloride solution, and a solution containing amino-containing polystyrene microspheres is added to the ferrous chloride solution, and the thickness of the electroplated iron layer ranges from 15 μm to 30 μm.

5. The method for preparing a high-strength and high-wear-resistant tungsten carbide hydrophobic layer on the surface of steel material according to claim 4, characterized in that: The mass concentration of the ferrous chloride solution is in the range of 300 g / L-350 g / L, the pH value is in the range of 1.3-1.5, the temperature is in the range of 75° C.-80° C., and the current density is in the range of 0.01-0.1 A / cm 2 .

6. The method for preparing a high-strength and high-wear-resistant tungsten carbide hydrophobic layer on the surface of a steel material according to claim 4, wherein: The volume of the amino polystyrene microsphere solution added per 100 mL of the electroplating solution is in the range of 2 mL to 4 mL, the solid content of the amino polystyrene microsphere solution is 25 mg / mL, and the average diameter of the amino polystyrene microspheres is in the range of 5 μm to 10 μm.

7. The method for preparing a high-strength and high-wear-resistant tungsten carbide hydrophobic layer on the surface of a steel material according to claim 1, characterized in that: The temperature range of the carburizing treatment in step 4 is 900° C.-1100° C., and the time is 5 h-30 h.

8. The method for preparing a high-strength and high-wear-resistant tungsten carbide hydrophobic layer on the surface of a steel material according to claim 1, characterized in that: The chemical solution in step 5 is one of a hydrochloric acid solution, a sulfuric acid solution or a nitric acid solution, wherein the mass fraction of hydrochloric acid in the hydrochloric acid solution is 15%-25%, the mass fraction of sulfuric acid in the sulfuric acid solution is 40%-70%, and the mass fraction of nitric acid in the nitric acid solution is 30%-50%.

9. The method for preparing a high-strength and high-wear-resistant tungsten carbide hydrophobic layer on the surface of a steel material according to claim 1, characterized in that: The low surface energy substance solution in step 6 is any one of a perfluorodecyltriethoxysilane solution, a 1H,1H,2H,2H perfluorodecyltrihexyloxysilane ethanol solution, and a (3,3,3 trifluoropropyl) methyldimethoxysilane solution, and the mass fraction of the low surface energy substance in the low surface energy substance solution is 3%-5%.

Images