Novel high-toughness low-expansion zinc-based wear-resistant alloy and preparation method thereof

Abstract

The invention discloses a novel high-toughness low-expansion zinc-based wear-resistant alloy and a preparation method thereof, and relates to the technical field of alloy materials. The preparation method comprises the following steps: heating an aluminum-copper intermediate alloy, an aluminum-cobalt intermediate alloy and metal aluminum in a smelting furnace to 750-850 DEG C, then adding metal zinc and galvanized activated ceramic powder, and reducing the temperature to 650-750 DEG C to obtain a molten alloy; then, the molten alloy is poured into a casting ladle, carbon powder is added, and stirring is conducted for 5-10 min; and finally, the molten alloy is poured into a mold at the temperature of 450-600 DEG C, then the mold is put into water at the temperature of 40-80 DEG C to be cooled, and the zinc-based wear-resistant alloy is obtained after casting molding. The zinc-based wear-resistant alloy prepared in the invention has excellent strength and toughness, also has excellent low-expansion characteristic and wear resistance, and is widely applied in the industrial fields of mechanical manufacturing and the like.

Description

Technical Field

[0001] The present application relates to the technical field of alloy materials, and in particular to a novel high-strength, high-toughness, low-expansion zinc-based wear-resistant alloy and a preparation method thereof. Background Art

[0002] Zinc-based alloys are widely used in the fields of machinery manufacturing and automobile industry due to their low cost, excellent casting performance and certain wear resistance, such as bearings, bushings, worm gears and other wear-resistant parts. However, traditional zinc-based alloys still have significant performance bottlenecks, such as:

[0003] Traditional zinc-based alloys usually have a high thermal expansion coefficient, which makes them prone to dimensional deformation in environments with large temperature fluctuations, limiting their application in fields such as precision instruments and high-temperature scenarios.

[0004] Traditional zinc-based alloys have low toughness and poor wear resistance, making it difficult to meet the needs of high-load working conditions.

[0005] In addition, due to the differences in physical and chemical properties between traditional zinc-based alloys and non-oxide ceramic particles or powders, their compatibility is often poor, making it difficult to form high-strength, toughness, low-expansion, and wear-resistant alloys with excellent performance that are composited with non-oxide ceramic particles or powders.

[0006] Chinese patent application publication number CN107447132A discloses a zinc-based alloy and its preparation method. The zinc-based alloy is a Zn-Al-Cu-Ba-Mg-La-Ce zinc-based alloy composed of 5.5-7.5% Al, 2.5-4.5% Cu, 3.5-5.5% Ba, 0.011-0.016% Mg, 0.13-0.17% La, 0.22-0.29% Ce, and the remainder Zn by weight. The patent application describes a process in which Ba is added to a Zn-Al-Cu-Mg molten metal, followed by LaBr3 and CeBr3 for a modification treatment, followed by a refining treatment with AlCl3 to produce a high-strength, wear-resistant Zn-Al-Cu-Ba-Mg-La-Ce zinc-based alloy.

[0007] However, the zinc-based alloy produced in the above patent application does not mention specific toughness and thermal expansion-related properties; it is not compounded with non-oxide ceramic materials and its wear resistance still has room for improvement. Summary of the Invention

[0008] To address the shortcomings of existing technologies, this application provides a novel high-strength, low-expansion zinc-based wear-resistant alloy and its preparation method. By combining metallic zinc, metallic aluminum, an aluminum-copper master alloy, an aluminum-cobalt master alloy, and a zinc-coated activated ceramic powder, a zinc-based wear-resistant alloy with excellent strength and toughness, low expansion properties, and wear resistance is obtained.

[0009] In order to achieve the above objectives, this application adopts the following technical solutions:

[0010] In the first aspect, the present application provides a novel high-strength, toughness, low-expansion zinc-based wear-resistant alloy, the raw material components of the zinc-based wear-resistant alloy include metallic zinc, metallic aluminum, aluminum-copper master alloy, aluminum-cobalt master alloy and galvanized activated ceramic powder; the galvanized activated ceramic powder is obtained by plasma activating non-oxide ceramic powder and then further galvanizing it by chemical plating; the non-oxide ceramic powder includes one or more of titanium carbide nitrogen, silicon carbide, tungsten carbide, titanium carbide and titanium nitride.

[0011] In a second aspect, the present application provides a method for preparing a novel high-strength, high-toughness, low-expansion zinc-based wear-resistant alloy, comprising the following steps:

[0012] After heating the aluminum-copper master alloy, the aluminum-cobalt master alloy and metallic aluminum to 750-850° C. in a furnace, metallic zinc and galvanized activated ceramic powder are added to the furnace, and the temperature is lowered to 650-750° C. to obtain a molten alloy;

[0013] Pour the molten alloy into the ladle, then add carbon powder and stir for 5 to 10 minutes;

[0014] Then, the molten alloy is poured into a mold with a temperature of 450-600° C., and the mold is placed in water with a temperature of 40-80° C. to cool. After casting and molding, the zinc-based wear-resistant alloy is obtained.

[0015] Beneficial technical effects:

[0016] In the zinc-based wear-resistant alloy prepared by the present application, the alloying effect of zinc, aluminum, copper and cobalt and the fine grain structure synergistically improve the strength and toughness of the alloy; the galvanized activated ceramic powder can bear the load and hinder the movement of dislocations, further strengthening the alloy matrix. Moreover, the galvanized activated ceramic powder has a good compatibility with zinc and other metal matrices. Through chemical plating and heat treatment, a gradient interface of "ceramic-zinc-other metal matrix" can be formed, which increases the bonding strength of each component, and galvanizing can avoid particle shedding and failure, further enhancing the strength and toughness of the alloy. In addition, the introduction of galvanized activated ceramic powder significantly reduces the overall thermal expansion coefficient of the alloy, making the obtained zinc-based alloy suitable for high temperature or temperature alternating environments. Moreover, the galvanized activated ceramic powder can act as a hard point to directly resist wear, and cooperate with metals such as cobalt and copper in the alloy to significantly improve the wear resistance of the obtained zinc-based wear-resistant alloy. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is a physical picture of the zinc-based wear-resistant alloy.

[0018] Figure 2 is a SEM image of the zinc-based wear-resistant alloy.

[0019] Figure 3 It is a schematic diagram of the preparation process of the zinc-based wear-resistant alloy. DETAILED DESCRIPTION

[0020] In order to make the technical problems, technical solutions, and beneficial effects to be solved by this application more clearly understood, the present application is further described in detail below with reference to the following examples. However, this should not be construed as limiting the scope of this application to the following examples. Without departing from the above-mentioned method concepts of this application, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of this application.

[0021] In this application, the terms used in this application are for the purpose of describing specific embodiments only and are not intended to be limiting of the application.

[0022] As used in this application, the singular forms "for," "or," "an," "any," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0023] In addition, the terms “first” and “second”, if used, are only used for descriptive purposes and should not be understood as indicating or implying relative importance.

[0024] In the first aspect, the present application provides a new type of high-strength, low-toughness, and low-expansion zinc-based wear-resistant alloy, the physical diagram of which is as follows: Figure 1 Its microscopic morphology is shown in Figure 2 The raw materials of the zinc-based wear-resistant alloy include metallic zinc, metallic aluminum, an aluminum-copper master alloy, an aluminum-cobalt master alloy, and galvanized activated ceramic powder. The galvanized activated ceramic powder is produced by plasma-activating non-oxide ceramic powder and then electrolessly galvanizing it. The non-oxide ceramic powder includes one or more of titanium carbide nitride, silicon carbide, tungsten carbide, titanium carbide, and titanium nitride.

[0025] In a possible implementation, the mass ratio of the metallic zinc, metallic aluminum, aluminum-copper master alloy, aluminum-cobalt master alloy and zinc-plated activated ceramic powder is (50-70): (15-30): (5-15): (1-5): (1-3).

[0026] In a possible implementation, in the aluminum-copper master alloy, the mass ratio of metallic copper to metallic aluminum is 50:50; and in the aluminum-cobalt master alloy, the amount of metallic cobalt is 10% of the amount of metallic aluminum.

[0027] In one possible implementation, the method for preparing the galvanized activated ceramic powder includes the following steps:

[0028] The non-oxide ceramic powder is pickled with an acid wash solution and ultrasonically cleaned with deionized water for 10 to 15 minutes, and then dried in a vacuum drying oven at 100 to 120° C. for 2 to 3 hours;

[0029] The dried ceramic powder is subjected to plasma activation treatment in an argon-hydrogen composite atmosphere at a power of 300 W for 15 to 20 minutes to obtain an activated ceramic powder;

[0030] The activated ceramic powder is mixed with the chemical plating solution in a volume ratio of 1:8, the plating parameters are controlled, and the deposition is performed for 40 to 60 minutes to obtain a ceramic powder semi-finished product;

[0031] The obtained ceramic powder semi-finished product is kept at 200-250° C. for 1-2 hours, and then kept at 350-400° C. for 0.5-1 hour to obtain heat-treated ceramic powder;

[0032] Then, under nitrogen protective atmosphere, the heat-treated ceramic powder is immersed in silicate passivation solution for 20-30 seconds, and finally ultrasonically cleaned with deionized water for 10-15 minutes and then dried in a vacuum drying oven at 100-120° C. for 1-2 hours to obtain the galvanized activated ceramic powder.

[0033] In one possible implementation, the pickling solution includes hydrofluoric acid, nitric acid, and water; the volume ratio of the hydrofluoric acid, nitric acid, and water is (5-10):(15-20):(70-80). The pickling solution with the above volume ratio is mainly used to remove oxides and other contaminants from the surface of ceramic powders and has applicability. The hydrofluoric acid is used to dissolve the silicon dioxide on the surface of silicon carbide, and the nitric acid is used to oxidize the metal oxides on the surface of other ceramic powders.

[0034] In one possible implementation, the volume percentage of hydrogen in the argon-hydrogen composite atmosphere is 10-15%. The hydrogen ions in the hydrogen plasma can reduce trace oxides that have not been completely washed off the ceramic surface, exposing fresh ceramic crystal surfaces, and more thoroughly activating the ceramic powder, thereby improving the effect of subsequent chemical plating.

[0035] In one possible implementation, the electroless plating solution comprises a zinc salt, a complexing agent, a reducing agent, and a stabilizer. The zinc salt comprises one or more of zinc sulfate, zinc chloride, and zinc acetate; the complexing agent comprises one or more of sodium citrate, EDTA, and potassium sodium tartrate; the reducing agent comprises one or more of sodium hypophosphite, sodium borohydride, and potassium borohydride; and the stabilizer comprises one or more of sodium tungstate, sodium molybdate, thiourea, 2-mercaptobenzothiazole, and 2,2'-bipyridine. The zinc salt provides zinc ions, which form a zinc coating on the surface of the ceramic powder through a reduction reaction. The complexing agent forms a stable complex with the zinc ions, controlling the concentration of free zinc ions and preventing spontaneous zinc deposition. The reducing agent undergoes an oxidation reaction on the surface of the activated ceramic powder, releasing electrons for zinc ion reduction. The stabilizer preferentially adsorbs on highly active sites, such as grain boundaries and defects, to inhibit localized over-deposition. The synergistic effect of these components in the electroless plating solution enables an efficient and stable electroless zinc plating process.

[0036] In one possible implementation, the zinc salt concentration ranges from 120 to 150 g / L; the complexing agent concentration ranges from 45 to 60 g / L; the reducing agent concentration ranges from 20 to 30 g / L; and the stabilizer concentration ranges from 1 to 5 ppm. The zinc salt concentration range ensures sufficient zinc ion concentration to avoid a decrease in the zinc plating rate due to diffusion limitations, while also preventing oversaturation of zinc ions that triggers dendrite growth and reduces coating density. The reducing agent concentration range ensures sufficient reducing power while preventing the side reaction of phosphide, which increases coating brittleness.

[0037] In one possible implementation, the plating parameters include pH=8.5±0.5, temperature 85±5° C., and stirring speed 250±50 rpm. Under the above plating parameters, the uniformity, density, and bonding strength of the zinc coating of the zinc-plated activated ceramic powder can be maximized.

[0038] In a second aspect, the present application provides a method for preparing a novel high-strength, low-toughness, and low-expansion zinc-based wear-resistant alloy, such as Figure 3 As shown, the following steps are included:

[0039] After heating the aluminum-copper master alloy, the aluminum-cobalt master alloy and metallic aluminum to 750-850° C. in a furnace, metallic zinc and galvanized activated ceramic powder are added to the furnace, and the temperature is lowered to 650-750° C. to obtain a molten alloy;

[0040] Pour the molten alloy into the ladle, then add carbon powder and stir for 5 to 10 minutes;

[0041] Then, the molten alloy is poured into a mold with a temperature of 450-600° C., and the mold is placed in water with a temperature of 40-80° C. to cool. After casting and molding, the zinc-based wear-resistant alloy is obtained.

[0042] In the above steps, carbon powder is added to reduce the oxidation of metallic zinc during the alloy production process.

[0043] In one possible implementation, the carbon powder is added in an amount of 0.05-0.1% of the metal zinc. This amount of carbon powder can prevent agglomeration and segregation in the zinc-based wear-resistant alloy, thereby preventing the formation of coarse carbides and reducing the toughness of the zinc-based wear-resistant alloy while ensuring the effect of resisting oxidation of the metal zinc.

[0044] The following will describe in detail a preparation method of a novel high-strength, high-toughness, low-expansion zinc-based wear-resistant alloy provided by the present application in combination with different embodiments.

[0045] Example 1:

[0046] like Figure 3 As shown, a method for preparing a novel high-strength, high-toughness, low-expansion zinc-based wear-resistant alloy comprises the following steps:

[0047] 1. Pickling the titanium carbide with an acid cleaning solution and ultrasonically cleaning it with deionized water for 10 minutes, and then drying it in a vacuum drying oven at 100°C for 2 hours; the acid cleaning solution includes hydrofluoric acid, nitric acid and water; the volume ratio of hydrofluoric acid, nitric acid and water is 5:15:80;

[0048] 2. Plasma activation treatment of the dried titanium nitride carbide was performed under an argon atmosphere and a power of 300 W for 15 minutes to obtain activated titanium nitride carbide;

[0049] 3. Mixing activated titanium nitride carbide with a chemical plating solution in a volume ratio of 1:8, and depositing for 40 minutes at a pH of 8.0, a temperature of 80° C., and a stirring rate of 200 rpm to obtain a titanium nitride carbide semi-finished product; the chemical plating solution comprises zinc sulfate (120 g / L), sodium citrate (45 g / L), sodium hypophosphite (20 g / L), and sodium tungstate (1 ppm);

[0050] 4. The obtained titanium nitride carbide semi-finished product is kept at 200° C. for 1 hour, and then kept at 350° C. for 0.5 hour to obtain heat-treated titanium nitride carbide;

[0051] 5. Then, under a nitrogen protective atmosphere, immerse the heat-treated titanium nitride carbide in a silicate passivation solution for 20 seconds, and finally ultrasonically clean the titanium nitride carbide with deionized water for 10 minutes and then dry it in a vacuum drying oven at 100° C. for 1 hour to obtain the zinc-coated titanium nitride carbide.

[0052] 6. After heating the aluminum-copper master alloy, the aluminum-cobalt master alloy and metallic aluminum to 750° C. in a furnace, metallic zinc and zinc-coated titanium carbide are added to the furnace, and the temperature is lowered to 650° C. to obtain a molten alloy;

[0053] The mass ratio of the metallic zinc, metallic aluminum, aluminum-copper master alloy, aluminum-cobalt master alloy and zinc-plated titanium carbide is 60:25:10:3:2;

[0054] 7. Pour the molten alloy into the ladle, then add carbon powder (the addition amount is 0.05% of the metallic zinc) and stir for 5 minutes;

[0055] 8. Pour the molten alloy into a mold at a temperature of 450° C., place the mold in 40° C. water for cooling, and obtain the zinc-based wear-resistant alloy after casting and molding.

[0056] Example 2:

[0057] like Figure 3 As shown, a method for preparing a novel high-strength, high-toughness, low-expansion zinc-based wear-resistant alloy comprises the following steps:

[0058] 1. The silicon carbide was pickled with an acid cleaning solution and ultrasonically cleaned with deionized water for 12 minutes, and then dried in a vacuum drying oven at 110° C. for 2.5 hours; the acid cleaning solution included hydrofluoric acid, nitric acid, and water; and the volume ratio of the hydrofluoric acid, nitric acid, and water was 6:16:78;

[0059] 2. Plasma activation treatment of the dried silicon carbide was performed under an argon atmosphere and a power of 300 W for 16 minutes to obtain activated silicon carbide;

[0060] 3. Mixing activated silicon carbide with a chemical plating solution in a volume ratio of 1:8, and depositing for 45 minutes at a pH of 8.5, a temperature of 85° C., and a stirring rate of 250 rpm to obtain a semi-finished silicon carbide product; the chemical plating solution comprises zinc chloride (130 g / L), EDTA (50 g / L), sodium borohydride (25 g / L), and sodium molybdate (2 ppm);

[0061] 4. The obtained silicon carbide semi-finished product is kept at 220° C. for 1.5 hours and then kept at 370° C. for 0.75 hours to obtain heat-treated silicon carbide;

[0062] 5. Then, under a nitrogen protective atmosphere, the heat-treated silicon carbide was immersed in a silicate passivation solution for 22 seconds, and finally ultrasonically cleaned with deionized water for 12 minutes and then dried in a vacuum drying oven at 110° C. for 1.2 hours to obtain the zinc-coated silicon carbide;

[0063] 6. After heating the aluminum-copper master alloy, the aluminum-cobalt master alloy, and metallic aluminum to 780°C in a furnace, metallic zinc and galvanized silicon carbide are added to the furnace, and the temperature is lowered to 670°C to obtain a molten alloy;

[0064] The mass ratio of the metallic zinc, metallic aluminum, aluminum-copper master alloy, aluminum-cobalt master alloy and galvanized silicon carbide is 70:15:7:5:3;

[0065] 7. Pour the molten alloy into the ladle, then add carbon powder (the addition amount is 0.06% of the metallic zinc) and stir for 6 minutes;

[0066] 8. Pour the molten alloy into a mold at a temperature of 500° C., place the mold in 50° C. water for cooling, and obtain the zinc-based wear-resistant alloy after casting and molding.

[0067] Example 3:

[0068] like Figure 3 As shown, a method for preparing a novel high-strength, high-toughness, low-expansion zinc-based wear-resistant alloy comprises the following steps:

[0069] 1. Pickle the tungsten carbide with an acid wash solution and ultrasonically clean it with deionized water for 13 minutes, and then dry it in a vacuum drying oven at 115°C for 2.8 hours; the acid wash solution includes hydrofluoric acid, nitric acid and water; the volume ratio of hydrofluoric acid, nitric acid and water is 7:17:76;

[0070] 2. The dried tungsten carbide was subjected to plasma activation treatment for 17 minutes under an argon atmosphere and a power of 300 W to obtain activated tungsten carbide;

[0071] 3. The activated tungsten carbide was mixed with the chemical plating solution in a volume ratio of 1:8, and the mixture was deposited for 50 min at pH = 9.0, temperature 90 ° C, and stirring rate 300 rpm to obtain a tungsten carbide semi-finished product; the chemical plating solution components included zinc acetate (140 g / L), potassium sodium tartrate (55 g / L), potassium borohydride (28 g / L) and thiourea (3 ppm);

[0072] 4. The obtained tungsten carbide semi-finished product is kept at 230°C for 1.8 hours, and then kept at 380°C for 0.8 hours to obtain heat-treated tungsten carbide;

[0073] 5. Then, under a nitrogen protective atmosphere, the heat-treated tungsten carbide was immersed in a silicate passivation solution for 24 seconds, and finally ultrasonically cleaned with deionized water for 13 minutes and then dried in a vacuum drying oven at 115° C. for 1.5 hours to obtain the zinc-coated tungsten carbide;

[0074] 6. After heating the aluminum-copper master alloy, aluminum-cobalt master alloy and metallic aluminum to 800°C in a furnace, metallic zinc and galvanized tungsten carbide are added to the furnace, and the temperature is lowered to 700°C to obtain a molten alloy;

[0075] The mass ratio of the metallic zinc, metallic aluminum, aluminum-copper master alloy, aluminum-cobalt master alloy and galvanized tungsten carbide is 55:25:15:4:1;

[0076] 7. Pour the molten alloy into the ladle, then add carbon powder (the addition amount is 0.07% of the metallic zinc) and stir for 7 minutes;

[0077] 8. Pour the molten alloy into a mold at a temperature of 550° C., place the mold in water at 60° C. to cool, and obtain the zinc-based wear-resistant alloy after casting.

[0078] Example 4:

[0079] like Figure 3 As shown, a method for preparing a novel high-strength, high-toughness, low-expansion zinc-based wear-resistant alloy comprises the following steps:

[0080] 1. The titanium carbide was pickled with an acid cleaning solution and ultrasonically cleaned with deionized water for 14 minutes, and then dried in a vacuum drying oven at 120° C. for 3 hours; the acid cleaning solution included hydrofluoric acid, nitric acid, and water; and the volume ratio of the hydrofluoric acid, nitric acid, and water was 8:18:74;

[0081] 2. The dried titanium carbide was subjected to plasma activation treatment in an argon atmosphere at a power of 300 W for 18 minutes to obtain activated titanium carbide;

[0082] 3. Mixing activated titanium carbide with an electroless plating solution in a volume ratio of 1:8, and depositing for 55 minutes at a pH of 8.5, a temperature of 85° C., and a stirring rate of 250 rpm to obtain a titanium carbide semi-finished product; the electroless plating solution comprises zinc sulfate (150 g / L), sodium citrate (60 g / L), sodium hypophosphite (30 g / L), and 2-mercaptobenzothiazole (4 ppm);

[0083] 4. The obtained titanium carbide semi-finished product is kept at 250° C. for 2 hours and then kept at 400° C. for 1 hour to obtain heat-treated titanium carbide;

[0084] 5. Then, under a nitrogen protective atmosphere, immersing the heat-treated titanium carbide in a silicate passivation solution for 26 seconds, and finally ultrasonically cleaning with deionized water for 14 minutes and drying in a vacuum drying oven at 120° C. for 1.8 hours to obtain the zinc-coated titanium carbide;

[0085] 6. After heating the aluminum-copper master alloy, the aluminum-cobalt master alloy and metallic aluminum to 820° C. in a furnace, metallic zinc and galvanized titanium carbide are added to the furnace, and the temperature is lowered to 720° C. to obtain a molten alloy;

[0086] The mass ratio of the metallic zinc, metallic aluminum, aluminum-copper master alloy, aluminum-cobalt master alloy and galvanized titanium carbide is 65:20:8:4:3;

[0087] 7. Pour the molten alloy into the ladle, then add carbon powder (the addition amount is 0.08% of the metallic zinc) and stir for 8 minutes;

[0088] 8. Pour the molten alloy into a mold at a temperature of 600° C., place the mold in water at 70° C. to cool, and obtain the zinc-based wear-resistant alloy after casting.

[0089] Example 5:

[0090] like Figure 3 As shown, a method for preparing a novel high-strength, high-toughness, low-expansion zinc-based wear-resistant alloy comprises the following steps:

[0091] 1. The titanium nitride was pickled with an acid cleaning solution and ultrasonically cleaned with deionized water for 15 minutes, and then dried in a vacuum drying oven at 105° C. for 2.2 hours; the acid cleaning solution comprised hydrofluoric acid, nitric acid, and water; and the volume ratio of the hydrofluoric acid, nitric acid, and water was 9:19:72;

[0092] 2. Plasma activation treatment of the dried titanium nitride was performed for 19 minutes under an argon atmosphere and a power of 300 W to obtain activated titanium nitride;

[0093] 3. Mixing activated titanium nitride with an electroless plating solution in a volume ratio of 1:8, and depositing for 58 minutes at a pH of 8.3, a temperature of 83° C., and a stirring rate of 230 rpm to obtain a titanium nitride semi-finished product; the electroless plating solution comprises zinc chloride (125 g / L), EDTA (48 g / L), sodium borohydride (22 g / L), and 2,2'-bipyridine (5 ppm);

[0094] 4. The obtained titanium nitride semi-finished product is kept at 210° C. for 1.2 hours and then kept at 360° C. for 0.6 hours to obtain heat-treated titanium nitride;

[0095] 5. Then, under a nitrogen protective atmosphere, the heat-treated titanium nitride was immersed in a silicate passivation solution for 28 seconds, and finally ultrasonically cleaned with deionized water for 15 minutes and then dried in a vacuum drying oven at 105° C. for 1.6 hours to obtain the galvanized titanium nitride;

[0096] 6. After heating the aluminum-copper master alloy, the aluminum-cobalt master alloy and metallic aluminum to 850° C. in a furnace, metallic zinc and galvanized titanium nitride are added to the furnace, and the temperature is lowered to 750° C. to obtain a molten alloy;

[0097] The mass ratio of the metallic zinc, metallic aluminum, aluminum-copper master alloy, aluminum-cobalt master alloy and galvanized titanium nitride is 55:22:15:5:3;

[0098] 7. Pour the molten alloy into the ladle, then add carbon powder (the addition amount is 0.09% of the metallic zinc) and stir for 9 minutes;

[0099] 8. Pour the molten alloy into a mold at a temperature of 580° C., place the mold in water at 80° C. to cool, and obtain the zinc-based wear-resistant alloy after casting.

[0100] Example 6:

[0101] like Figure 3 As shown, a method for preparing a novel high-strength, high-toughness, low-expansion zinc-based wear-resistant alloy comprises the following steps:

[0102] 1. The titanium carbide was pickled with an acid cleaning solution and ultrasonically cleaned with deionized water for 11 minutes, and then dried in a vacuum drying oven at 118°C for 2.7 hours; the acid cleaning solution included hydrofluoric acid, nitric acid, and water; and the volume ratio of the hydrofluoric acid, nitric acid, and water was 10:20:70;

[0103] 2. Plasma activation treatment of the dried titanium nitride carbide was performed under an argon atmosphere and a power of 300 W for 20 minutes to obtain activated titanium nitride carbide;

[0104] 3. Mixing activated titanium nitride carbide with an electroless plating solution in a volume ratio of 1:8, and depositing for 60 minutes at a pH of 8.7, a temperature of 87° C., and a stirring rate of 270 rpm to obtain a titanium nitride carbide semi-finished product; the electroless plating solution comprises zinc acetate (145 g / L), potassium sodium tartrate (58 g / L), potassium borohydride (29 g / L), and sodium tungstate (1.5 ppm);

[0105] 4. The obtained titanium nitride carbide semi-finished product is kept at 240° C. for 1.9 hours and then kept at 390° C. for 0.9 hours to obtain heat-treated titanium nitride carbide;

[0106] 5. Then, under a nitrogen protective atmosphere, the heat-treated titanium nitride carbide was immersed in a silicate passivation solution for 30 seconds, and finally ultrasonically cleaned with deionized water for 11 minutes and then dried in a vacuum drying oven at 118° C. for 2 hours to obtain the zinc-coated titanium nitride carbide;

[0107] 6. After heating the aluminum-copper master alloy, the aluminum-cobalt master alloy and metallic aluminum to 830° C. in a furnace, metallic zinc and galvanized titanium carbide are added to the furnace, and the temperature is lowered to 730° C. to obtain a molten alloy;

[0108] The mass ratio of the metallic zinc, metallic aluminum, aluminum-copper master alloy, aluminum-cobalt master alloy and zinc-plated titanium carbide is 63:20:12:3:2;

[0109] 7. Pour the molten alloy into the ladle, then add carbon powder (the addition amount is 0.1% of the metallic zinc) and stir for 10 minutes;

[0110] 8. Pour the molten alloy into a mold at a temperature of 520° C., place the mold in water at 55° C. to cool, and obtain the zinc-based wear-resistant alloy after casting.

[0111] Comparative Example 1:

[0112] A method for preparing a novel high-strength, high-toughness, low-expansion zinc-based wear-resistant alloy comprises the following steps:

[0113] 1. After heating the aluminum-copper master alloy, aluminum-cobalt master alloy and metal aluminum to 750°C in a furnace, add metal zinc and titanium carbide into the furnace and lower the temperature to 650°C to obtain a molten alloy;

[0114] The mass ratio of the metallic zinc, metallic aluminum, aluminum-copper master alloy, aluminum-cobalt master alloy and titanium nitride carbide is 60:25:10:3:2;

[0115] 2. Pour the molten alloy into the ladle, then add carbon powder (the addition amount is 0.05% of the metal zinc) and stir for 5 minutes;

[0116] 3. Pour the molten alloy into a mold at a temperature of 450° C., place the mold in 40° C. water for cooling, and obtain the zinc-based wear-resistant alloy after casting and molding.

[0117] Comparative Example 2:

[0118] A method for preparing a novel high-strength, high-toughness, low-expansion zinc-based wear-resistant alloy comprises the following steps:

[0119] 1. Pickle the tungsten carbide with an acid wash solution and ultrasonically clean it with deionized water for 13 minutes, and then dry it in a vacuum drying oven at 115°C for 2.8 hours; the acid wash solution includes hydrofluoric acid, nitric acid and water; the volume ratio of hydrofluoric acid, nitric acid and water is 7:17:76;

[0120] 2. The dried tungsten carbide was subjected to plasma activation treatment for 17 minutes under an argon atmosphere and a power of 300 W to obtain activated tungsten carbide;

[0121] 3. The activated tungsten carbide was mixed with the chemical plating solution in a volume ratio of 1:8, and the mixture was deposited for 50 min at pH = 9.0, temperature 90 ° C, and stirring rate 300 rpm to obtain a tungsten carbide semi-finished product; the chemical plating solution components included zinc acetate (140 g / L), potassium sodium tartrate (55 g / L), potassium borohydride (28 g / L) and thiourea (3 ppm);

[0122] 4. The obtained tungsten carbide semi-finished product is kept at 230°C for 1.8 hours, and then kept at 380°C for 0.8 hours to obtain heat-treated tungsten carbide;

[0123] 5. Then, under a nitrogen protective atmosphere, the heat-treated tungsten carbide was immersed in a silicate passivation solution for 24 seconds, and finally ultrasonically cleaned with deionized water for 13 minutes and then dried in a vacuum drying oven at 115° C. for 1.5 hours to obtain the zinc-coated tungsten carbide;

[0124] 6. After heating the metal aluminum to 800°C in a furnace, add metal zinc and galvanized tungsten carbide into the furnace and lower the temperature to 700°C to obtain a molten alloy;

[0125] The mass ratio of the metallic zinc, metallic aluminum and galvanized tungsten carbide is 70:29:1;

[0126] 7. Pour the molten alloy into the ladle, then add carbon powder (the addition amount is 0.07% of the metallic zinc) and stir for 7 minutes;

[0127] 8. Pour the molten alloy into a mold at a temperature of 550° C., place the mold in water at 60° C. to cool, and obtain the zinc-based wear-resistant alloy after casting.

[0128] Comparative Example 3:

[0129] A method for preparing a novel high-strength, high-toughness, low-expansion zinc-based wear-resistant alloy comprises the following steps:

[0130] 1. After heating the aluminum-copper master alloy, aluminum-cobalt master alloy and metallic aluminum to 830°C in a furnace, metallic zinc is added to the furnace and the temperature is lowered to 730°C to obtain a molten alloy;

[0131] The mass ratio of the metallic zinc, metallic aluminum, aluminum-copper master alloy and aluminum-cobalt master alloy is 65:20:12:3;

[0132] 2. Pour the molten alloy into the ladle, then add carbon powder (the addition amount is 0.1% of the metal zinc) and stir for 10 minutes;

[0133] 3. Pour the molten alloy into a mold at a temperature of 520° C., place the mold in water at 55° C. to cool, and obtain the zinc-based wear-resistant alloy after casting.

[0134] Performance testing:

[0135] The tensile strength of the prepared zinc-based wear-resistant alloy was tested with reference to GB / T 228.1-2021 to reflect the high strength performance of the prepared zinc-based wear-resistant alloy.

[0136] The Charpy pendulum impact test was carried out on the prepared zinc-based wear-resistant alloy with reference to GB / T 229-2020, and the test results were used to reflect the toughness of the prepared zinc-based wear-resistant alloy.

[0137] The thermal expansion coefficient of the prepared zinc-based wear-resistant alloy was tested with reference to ISO18099:2022 to reflect the low expansion characteristics of the prepared zinc-based wear-resistant alloy in the range of 30 to 420°C.

[0138] The prepared zinc-based wear-resistant alloy was subjected to a sliding wear test (200 r / min, 30 min) with reference to GB / T 12444-2006, and the wear quality test results were used to reflect the wear resistance of the prepared zinc-based wear-resistant alloy.

[0139] The results of the above tests are summarized in Table 1 below.

[0140] Table 1 Test results of zinc-based wear-resistant alloys prepared in Examples and Comparative Examples

[0141]

[0142] As can be seen from Table 1, all test data of the zinc-based wear-resistant alloys prepared in Examples 1 to 6 are better than those in Comparative Examples 1 to 3.

[0143] This is because, in the zinc-based wear-resistant alloys prepared in Examples 1 to 6, the alloying effect of zinc, aluminum, copper, and cobalt and the fine-grained structure synergistically improve the strength and toughness of the alloy; the galvanized activated ceramic powder can bear the load and hinder dislocation movement, further strengthening the alloy matrix. Moreover, the galvanized activated ceramic powder has good compatibility with zinc and other metal matrices. Through chemical plating and heat treatment, a gradient interface of "ceramic-zinc-other metal matrix" can be formed, which increases the bonding strength of each component, and galvanizing can avoid particle shedding and failure, further enhancing the strength and toughness of the alloy. In addition, the introduction of galvanized activated ceramic powder significantly reduces the overall thermal expansion coefficient of the alloy, making the obtained zinc-based alloy suitable for high temperature or temperature alternating environments. Moreover, the galvanized activated ceramic powder can act as a hard point to directly resist wear, and cooperate with metals such as cobalt and copper in the alloy to significantly improve the wear resistance of the obtained zinc-based wear-resistant alloy.

[0144] However, the titanium nitride carbide used in Comparative Example 1 is not galvanized, so its compatibility with zinc and other metal matrices is poor, and it cannot form a gradient interface of "ceramic-zinc-other metal matrix", which increases the bonding strength of each component and ultimately reduces the strength and toughness of the alloy obtained.

[0145] In Comparative Example 2, no aluminum-copper master alloy and aluminum-cobalt master alloy are used, so the alloying effect of zinc, aluminum, copper and cobalt and the synergy of fine grain structure cannot be produced in the obtained zinc-based wear-resistant alloy, and the strength and toughness of the obtained alloy are therefore not strong enough.

[0146] Comparative Example 3 does not use ceramic powder. On the one hand, it cannot form a gradient interface of "ceramic-zinc-other metal matrix", nor can it reduce the overall thermal expansion coefficient of the alloy. In addition, it cannot cooperate with metals such as cobalt and copper in the alloy to resist wear. Therefore, the performance of the zinc-based wear-resistant alloy obtained is very poor.

[0147] The above results show and describe the basic principles and main features of this application as well as the advantages of this application.

[0148] Those skilled in the art should understand that the present application is not limited to the above-described embodiments. The above-described embodiments and descriptions are merely illustrative of the principles of the present application. Various changes and improvements may be made to the present application without departing from the spirit and scope of the present application. Such changes and improvements are intended to fall within the scope of the present application. The scope of protection claimed in the present application is defined by the equivalents of the appended claims.

Claims

1. A new type of high strength, toughness and low expansion zinc-based wear-resistant alloy, characterized in that: The raw material components of the zinc-based wear-resistant alloy include metallic zinc, metallic aluminum, aluminum-copper master alloy, aluminum-cobalt master alloy and galvanized activated ceramic powder; the galvanized activated ceramic powder is obtained by plasma activating non-oxide ceramic powder and then further galvanizing it by chemical plating; the non-oxide ceramic powder includes one or more of titanium carbide, silicon carbide, tungsten carbide, titanium carbide and titanium nitride.

2. A novel high-strength, low-toughness zinc-based wear-resistant alloy according to claim 1, characterized in that: The mass ratio of the metallic zinc, metallic aluminum, aluminum-copper master alloy, aluminum-cobalt master alloy and zinc-plated activated ceramic powder is (50-70): (15-30): (5-15): (1-5): (1-3).

3. A novel high-strength, low-toughness zinc-based wear-resistant alloy according to claim 1, characterized in that: In the aluminum-copper master alloy, the mass ratio of metal copper to metal aluminum is 50:50; in the aluminum-cobalt master alloy, the amount of metal cobalt used is 10% of the amount of metal aluminum used.

4. A novel high-strength, low-toughness zinc-based wear-resistant alloy according to any one of claims 2 to 3, characterized in that: The preparation method of the galvanized activated ceramic powder comprises the following steps: The non-oxide ceramic powder is pickled with an acid wash solution and ultrasonically cleaned with deionized water for 10 to 15 minutes, and then dried in a vacuum drying oven at 100 to 120° C. for 2 to 3 hours; The dried ceramic powder is subjected to plasma activation treatment in an argon-hydrogen composite atmosphere at a power of 300 W for 15 to 20 minutes to obtain an activated ceramic powder; The activated ceramic powder is mixed with the chemical plating solution in a volume ratio of 1:8, the plating parameters are controlled, and the deposition is performed for 40 to 60 minutes to obtain a ceramic powder semi-finished product; The obtained ceramic powder semi-finished product is kept at 200-250° C. for 1-2 hours, and then kept at 350-400° C. for 0.5-1 hour to obtain heat-treated ceramic powder; Then, under nitrogen protective atmosphere, the heat-treated ceramic powder is immersed in silicate passivation solution for 20-30 seconds, and finally ultrasonically cleaned with deionized water for 10-15 minutes and then dried in a vacuum drying oven at 100-120° C. for 1-2 hours to obtain the galvanized activated ceramic powder.

5. A novel high-strength, low-toughness zinc-based wear-resistant alloy according to claim 4, characterized in that: The pickling solution includes hydrofluoric acid, nitric acid and water; the volume ratio of the hydrofluoric acid, nitric acid and water is (5-10): (15-20): (70-80); in the argon-hydrogen composite atmosphere, the volume proportion of hydrogen is 10-15%.

6. A novel high-strength, low-toughness zinc-based wear-resistant alloy according to claim 4, characterized in that: The chemical plating solution comprises zinc salt, a complexing agent, a reducing agent and a stabilizer; the zinc salt comprises one or more of zinc sulfate, zinc chloride and zinc acetate; the complexing agent comprises one or more of sodium citrate, EDTA and potassium sodium tartrate; the reducing agent comprises one or more of sodium hypophosphite, sodium borohydride and potassium borohydride; the stabilizer comprises one or more of sodium tungstate, sodium molybdate, thiourea, 2-mercaptobenzothiazole and 2,2'-bipyridine.

7. A novel high-strength, low-toughness zinc-based wear-resistant alloy according to claim 6, characterized in that: The concentration range of the zinc salt is 120-150 g / L; the concentration range of the complexing agent is 45-60 g / L; the concentration range of the reducing agent is 20-30 g / L; and the concentration range of the stabilizer is 1-5 ppm.

8. The novel high-strength, low-toughness zinc-based wear-resistant alloy according to claim 4, characterized in that: The plating parameters include pH=8.5±0.5, temperature 85±5° C., and stirring speed 250±50 rpm.

9. The method for preparing the novel high-strength, high-toughness, low-expansion zinc-based wear-resistant alloy according to any one of claims 5 to 8, characterized in that: The steps include: After heating the aluminum-copper master alloy, the aluminum-cobalt master alloy and metallic aluminum to 750-850° C. in a furnace, metallic zinc and galvanized activated ceramic powder are added to the furnace, and the temperature is lowered to 650-750° C. to obtain a molten alloy; Pour the molten alloy into the ladle, then add carbon powder and stir for 5 to 10 minutes; The molten alloy is then poured into a mold with a temperature of 450-600° C., the mold is placed in water at 40-80° C. for cooling, and the zinc-based wear-resistant alloy is obtained after casting and molding.

10. The method for preparing the novel high-strength, high-toughness, low-expansion zinc-based wear-resistant alloy according to claim 9, characterized in that: The added amount of the carbon powder is 0.05-0.1% of the metallic zinc.

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