High-temperature-resistant softening-resistant tellurium-copper alloy material and preparation method thereof

Abstract

The invention discloses a high-temperature-resistant softening-resistant tellurium-copper alloy material and a preparation method thereof, and relates to the technical field of alloy materials, and the tellurium-copper alloy material prepared by using tellurium, sulfur, zirconium, tin and copper as base materials has good high-temperature-resistant softening-resistant performance. Dopamine is used for modifying the surface of the tellurium-copper alloy material, a compact protection layer can be formed on the surface of the tellurium-copper alloy material, and the corrosion resistance of the alloy material is enhanced. Nickel is plated on the surface of the carbon nano tube, the nickel-plated carbon nano tube is more uniformly dispersed in a nickel-plated layer, the compatibility is more excellent, and the nickel layer is higher in density. And ferric chloride hexahydrate is added for further modification, tannic acid in the plating solution C can generate complex reaction, so that a complex is generated, the strength between the alloy material and a plating layer is enhanced, and the corrosion resistance of the alloy material is enhanced.

Description

Technical Field

[0001] The present invention relates to the technical field of alloy materials, in particular to a high-temperature resistant and softening-resistant tellurium-copper alloy material and a preparation method thereof. Background Art

[0002] Tellurium copper alloys are widely used in electronics, power generation, automotive, and other fields due to their excellent electrical and thermal conductivity. While traditional alloys offer good electrical conductivity and processing properties, they are prone to softening at high temperatures, causing material performance degradation and impacting the lifespan of equipment. Compared to traditional copper alloys, tellurium copper alloys maintain superior mechanical properties and softening resistance at higher temperatures. However, the softening resistance and corrosion resistance of existing tellurium copper alloys under extremely high temperature and acidic conditions still need to be improved.

[0003] In order to solve the above problems and improve the high temperature resistance, softening resistance and corrosion resistance of the tellurium copper alloy material, the present invention provides a high temperature resistant and softening resistance tellurium copper alloy material and a preparation method thereof. Summary of the Invention

[0004] The object of the present invention is to provide a high temperature resistant and softening resistant tellurium copper alloy material and a preparation method thereof, so as to solve the problems raised in the prior art.

[0005] To achieve the above object, the present invention provides the following technical solutions: A method for preparing a high-temperature resistant and softening-resistant tellurium-copper alloy material comprises the following steps: Step 1: Take tellurium, sulfur, zirconium, tin, and copper, melt, cast, pull, extrude, pickle, anneal, draw, and then perform aging treatment to obtain a tellurium copper alloy material; Step 2: taking a tellurium-copper alloy material, pickling, drying, activating, and drying to obtain a pretreated tellurium-copper alloy material; Step 3: taking the pretreated tellurium copper alloy material and placing it in a dopamine solution, immersing it for 22-26 hours, taking it out and drying it to obtain a modified tellurium copper alloy material; Step 4: placing the modified tellurium copper alloy material in plating solution B, electroplating at 88-90° C. for 30-35 minutes, taking out and drying to obtain tellurium copper alloy material A; The tellurium copper alloy material A is placed in a plating solution C, electroplated at 88-90° C. for 30-35 minutes, taken out, and dried to obtain a high-temperature resistant and softening-resistant tellurium copper alloy material.

[0006] More optimally, the tellurium-copper alloy material includes the following components, calculated by weight percentage: 0.3wt%-0.4wt% tellurium, 0.22wt%-0.28wt% sulfur, 0.50wt%-0.75wt% zirconium, 0.23wt%-0.40wt% tin, and the balance is copper.

[0007] More optimally, the plating solution B comprises the following ingredients: 24-27 g / L nickel sulfate hexahydrate, 20-22 g / L sodium hypophosphite monohydrate, 40-46 g / L sodium citrate, and the pH is adjusted to 8 using aqueous ammonia.

[0008] More optimally, the plating solution C comprises the following ingredients: 24-27 g / L nickel sulfate hexahydrate, 25-27 g / L sodium hypophosphite monohydrate, 1-2 g / L cage-type silsesquioxane-modified carbon nanotubes, and 25-30 mL / L tannic acid, and the pH is adjusted to 4.5 using aqueous ammonia.

[0009] More optimally, the method for preparing the cage-type silsesquioxane-modified carbon nanotubes comprises the following steps: S1: Take tetramethylammonium hydroxide, acetonitrile, deionized water, and propanol, stir evenly, add aminopropyltriethoxysilane dropwise, raise the temperature to 50-52°C, react for 10-14 hours, add tetrahydrofuran, precipitate, filter, wash, and dry to obtain amino cage silsesquioxane; S2: Take isopropanol and deionized water, stir evenly, add nickel-plated carbon nanotubes, add sodium hydroxide solution, adjust the pH to 13-14, stir for 4-5 hours, add amino-type cage-type silsesquioxane, heat to 50-55°C, react for 4-5 hours, add ferric chloride hexahydrate, react for 2-3 hours, centrifuge, wash, and dry to obtain cage-type silsesquioxane-modified carbon nanotubes.

[0010] More optimally, the method for preparing the nickel-plated carbon nanotubes is as follows: placing carbon nanotubes in plating solution A, nickel plating at 60-65° C. for 30-35 minutes, vacuuming, washing, and drying to obtain nickel-plated carbon nanotubes.

[0011] More optimally, the plating solution A includes the following components: plating solution A: 33-36 g / L nickel sulfate, 15-17 g / L trisodium citrate, 30-35 g / L sodium hypophosphite, and ammonia water is used to adjust the pH to 8.5.

[0012] More optimally, the dopamine solution preparation method is: take tris(hydroxymethyl)aminomethane and deionized water, stir evenly, add hydrochloric acid dropwise, adjust the pH value to 8.5, and obtain a buffer solution; take the buffer solution, add dopamine hydrochloride, and stir evenly to obtain a dopamine solution.

[0013] Compared with the prior art, the present invention has the following beneficial effects: The tellurium-copper alloy prepared using tellurium, sulfur, zirconium, tin, and copper as matrix materials exhibits excellent high-temperature resistance and softening resistance. Modifying the surface of the tellurium-copper alloy with dopamine forms a dense protective layer on the alloy surface, enhancing the alloy's corrosion resistance.

[0014] 2. The present invention first nickel-plates the surface of carbon nanotubes. This nickel-plated carbon nanotubes are more evenly dispersed within the nickel-plated layer, resulting in improved compatibility and a higher density of the nickel layer. The nickel-plated carbon nanotubes are then compounded with an amino-modified cage-type silsesquioxane to increase the specific surface area of the carbon nanotubes and the tortuosity of the surface through which corrosive substances enter the tellurium-copper alloy, making it more difficult for corrosive substances to invade and thus improving corrosion resistance. Further modification is achieved by adding ferric chloride hexahydrate, which reacts with the tannic acid in plating solution C to form a complex, strengthening the bond between the alloy and the coating and enhancing the corrosion resistance of the alloy.

[0015] 3. Pre-plating the modified tellurium copper alloy material in a plating solution B with a pH of 8. The plating solution B is alkaline. Avoid direct use of the acidic plating solution C for plating. The polydopamine film on the surface of the modified tellurium copper alloy material may be corroded by the acidic liquid and fail. Pre-plating the modified tellurium copper alloy material with the plating solution B can increase the hardness of the alloy. DETAILED DESCRIPTION

[0016] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0017] The sources and types of the substances involved in the present invention are not particularly limited, and illustratively include: carbon nanotubes: 10-20 nm, item number: 100252, which can be purchased from Xianfeng Nano.

[0018] Example 1: A method for preparing a high-temperature resistant and softening-resistant tellurium-copper alloy material, comprising the following steps: Step 1: Take tellurium, sulfur, zirconium, tin, and copper, melt, cast, pull, extrude, pickle, anneal, draw, and then perform aging treatment to obtain a tellurium-copper alloy material; Taking a tellurium-copper alloy material, pickling, drying, activating, and drying it to obtain a pretreated tellurium-copper alloy material; The tellurium-copper alloy material comprises the following components, calculated by weight percentage: 0.35 wt% tellurium, 0.26 wt% sulfur, 0.65 wt% zirconium, 0.30 wt% tin, and the balance copper; Step 2: Preparation of modified tellurium copper alloy material: Take 1.5 g of tris(hydroxymethyl)aminomethane and 100 mL of deionized water, stir evenly, add 0.1 mol / L hydrochloric acid dropwise, adjust the pH to 8.5, and obtain a buffer solution; take 200 mL of the buffer solution, add 1 g of dopamine hydrochloride, and stir evenly to obtain a dopamine solution; The pretreated tellurium-copper alloy material is placed in a dopamine solution and immersed for 24 hours, taken out, and dried to obtain a modified tellurium-copper alloy material; Step 3: Preparation of nickel-plated carbon nanotubes: The carbon nanotubes were placed in plating solution A and nickel plated at 62°C for 32 minutes, vacuumed, washed, and dried to obtain nickel-plated carbon nanotubes. Bath A: 34 g / L nickel sulfate, 16 g / L trisodium citrate, 33 g / L sodium hypophosphite, pH adjusted to 8.5 with ammonia; Step 4: Preparation of cage-type silsesquioxane-modified carbon nanotubes: Take 4 mL of tetramethylammonium hydroxide, 20 mL of acetonitrile, 200 mL of deionized water, and 80 mL of propanol, stir evenly, add 200 g of aminopropyltriethoxysilane dropwise, heat to 51 ° C, react for 11 hours, add 500 mL of tetrahydrofuran, precipitate, filter, wash, and dry to obtain amino cage silsesquioxane; Take 50 mL of isopropanol and 50 mL of deionized water, stir evenly, add 2 g of nickel-plated carbon nanotubes, add sodium hydroxide solution, adjust the pH to 13.5, stir for 4.5 hours, add 10 g of amino-type cage-type silsesquioxane, heat to 52 ° C, react for 4.5 hours, add 15 mL of ferric chloride hexahydrate, react for 2.5 hours, centrifuge, wash, and dry to obtain cage-type silsesquioxane-modified carbon nanotubes; Step 5: Preparation of high temperature resistant and softening resistant tellurium copper alloy material: The modified tellurium-copper alloy material is placed in plating solution B, electroplated at 89°C for 32 minutes, taken out and dried to obtain tellurium-copper alloy material A; The tellurium copper alloy material A is placed in the plating solution C, electroplated at 89°C for 32 minutes, taken out and dried to obtain a high temperature resistant and softening resistant tellurium copper alloy material; Bath B: 25 g / L nickel sulfate hexahydrate, 21 g / L sodium hypophosphite monohydrate, 43 g / L sodium citrate, pH adjusted to 8 with aqueous ammonia. Plating solution C: 26 g / L nickel sulfate hexahydrate, 26 g / L sodium hypophosphite monohydrate, 1.5 g / L cage-type silsesquioxane-modified carbon nanotubes, 28 mL / L tannic acid, and the pH was adjusted to 4.5 using aqueous ammonia.

[0019] Example 2: A method for preparing a high-temperature resistant and softening-resistant tellurium-copper alloy material, comprising the following steps: Step 1: Take tellurium, sulfur, zirconium, tin, and copper, melt, cast, pull, extrude, pickle, anneal, draw, and then perform aging treatment to obtain a tellurium-copper alloy material; Taking a tellurium-copper alloy material, pickling, drying, activating, and drying it to obtain a pretreated tellurium-copper alloy material; The tellurium-copper alloy material comprises the following components, calculated by weight percentage: 0.3 wt % tellurium, 0.22 wt % sulfur, 0.50 wt % zirconium, 0.23 wt % tin, and the balance copper; Step 2: Preparation of modified tellurium copper alloy material: Take 1.5 g of tris(hydroxymethyl)aminomethane and 100 mL of deionized water, stir evenly, add 0.1 mol / L hydrochloric acid dropwise, adjust the pH to 8.5, and obtain a buffer solution; take 200 mL of the buffer solution, add 1 g of dopamine hydrochloride, and stir evenly to obtain a dopamine solution; The pretreated tellurium-copper alloy material was placed in a dopamine solution and immersed for 22 hours, then taken out and dried to obtain a modified tellurium-copper alloy material; Step 3: Preparation of nickel-plated carbon nanotubes: The carbon nanotubes were placed in plating solution A, nickel plated at 60°C for 30 min, vacuumed, washed, and dried to obtain nickel-plated carbon nanotubes; Bath A: 33g / L nickel sulfate, 15g / L trisodium citrate, 30g / L sodium hypophosphite, pH adjusted to 8.5 with ammonia water; Step 4: Preparation of cage-type silsesquioxane-modified carbon nanotubes: Take 4 mL of tetramethylammonium hydroxide, 20 mL of acetonitrile, 200 mL of deionized water, and 80 mL of propanol, stir evenly, add 200 g of aminopropyltriethoxysilane dropwise, heat to 50 ° C, react for 10 hours, add 500 mL of tetrahydrofuran, precipitate, filter, wash, and dry to obtain amino cage silsesquioxane; Take 50 mL of isopropanol and 50 mL of deionized water, stir evenly, add 2 g of nickel-plated carbon nanotubes, add sodium hydroxide solution, adjust the pH to 13, stir for 4 h, add 10 g of amino-type cage-type silsesquioxane, heat to 50 ° C, react for 4 h, add 15 mL of ferric chloride hexahydrate, react for 2 h, centrifuge, wash, and dry to obtain cage-type silsesquioxane-modified carbon nanotubes; Step 5: Preparation of high temperature resistant and softening resistant tellurium copper alloy material: The modified tellurium-copper alloy material is placed in plating solution B, electroplated at 88°C for 30 minutes, taken out and dried to obtain tellurium-copper alloy material A; The tellurium copper alloy material A is placed in the plating solution C, electroplated at 88°C for 30 minutes, taken out and dried to obtain a high temperature resistant and softening resistant tellurium copper alloy material; Bath B: 24 g / L nickel sulfate hexahydrate, 20 g / L sodium hypophosphite monohydrate, 40 g / L sodium citrate, pH adjusted to 8 with aqueous ammonia. Plating solution C: 24 g / L nickel sulfate hexahydrate, 25 g / L sodium hypophosphite monohydrate, 1 g / L cage-type silsesquioxane-modified carbon nanotubes, 25 mL / L tannic acid, and the pH was adjusted to 4.5 using aqueous ammonia.

[0020] Example 3: A method for preparing a high-temperature resistant and softening-resistant tellurium-copper alloy material, comprising the following steps: Step 1: Take tellurium, sulfur, zirconium, tin, and copper, melt, cast, pull, extrude, pickle, anneal, draw, and then perform aging treatment to obtain a tellurium-copper alloy material; Taking a tellurium-copper alloy material, pickling, drying, activating, and drying it to obtain a pretreated tellurium-copper alloy material; The tellurium-copper alloy material comprises the following components, calculated by weight percentage: 0.4 wt % tellurium, 0.28 wt % sulfur, 0.75 wt % zirconium, 0.40 wt % tin, and the balance copper; Step 2: Preparation of modified tellurium copper alloy material: Take 1.5 g of tris(hydroxymethyl)aminomethane and 100 mL of deionized water, stir evenly, add 0.1 mol / L hydrochloric acid dropwise, adjust the pH to 8.5, and obtain a buffer solution; take 200 mL of the buffer solution, add 1 g of dopamine hydrochloride, and stir evenly to obtain a dopamine solution; The pretreated tellurium-copper alloy material is placed in a dopamine solution and immersed for 26 hours, taken out, and dried to obtain a modified tellurium-copper alloy material; Step 3: Preparation of nickel-plated carbon nanotubes: The carbon nanotubes were placed in plating solution A and nickel plated at 65°C for 35 minutes, vacuum-treated, washed, and dried to obtain nickel-plated carbon nanotubes. Bath A: 36 g / L nickel sulfate, 17 g / L trisodium citrate, 35 g / L sodium hypophosphite, pH adjusted to 8.5 with ammonia; Step 4: Preparation of cage-type silsesquioxane-modified carbon nanotubes: Take 4 mL of tetramethylammonium hydroxide, 20 mL of acetonitrile, 200 mL of deionized water, and 80 mL of propanol, stir evenly, add 200 g of aminopropyltriethoxysilane dropwise, heat to 52 ° C, react for 14 h, add 500 mL of tetrahydrofuran, precipitate, filter, wash, and dry to obtain amino cage silsesquioxane; Take 50 mL of isopropanol and 50 mL of deionized water, stir evenly, add 2 g of nickel-plated carbon nanotubes, add sodium hydroxide solution, adjust the pH to 14, stir for 5 h, add 10 g of amino-type cage-type silsesquioxane, heat to 55 ° C, react for 5 h, add 15 mL of ferric chloride hexahydrate, react for 3 h, centrifuge, wash, and dry to obtain cage-type silsesquioxane-modified carbon nanotubes; Step 5: Preparation of high temperature resistant and softening resistant tellurium copper alloy material: The modified tellurium-copper alloy material is placed in plating solution B, electroplated at 90° C. for 35 minutes, taken out, and dried to obtain tellurium-copper alloy material A; The tellurium-copper alloy material A is placed in a plating solution C, electroplated at 90°C for 35 minutes, taken out, and dried to obtain a high-temperature resistant and softening-resistant tellurium-copper alloy material; Bath B: 27 g / L nickel sulfate hexahydrate, 22 g / L sodium hypophosphite monohydrate, 46 g / L sodium citrate, pH adjusted to 8 with ammonia. Plating solution C: 27 g / L nickel sulfate hexahydrate, 27 g / L sodium hypophosphite monohydrate, 2 g / L cage-type silsesquioxane-modified carbon nanotubes, 30 mL / L tannic acid, and the pH was adjusted to 4.5 using aqueous ammonia.

[0021] Comparative Example 1: No nickel plating was performed on the surface of the carbon nanotubes, and the rest was the same as in Example 1: Step 1: Take tellurium, sulfur, zirconium, tin, and copper, melt, cast, pull, extrude, pickle, anneal, draw, and then perform aging treatment to obtain a tellurium-copper alloy material; Taking a tellurium-copper alloy material, pickling, drying, activating, and drying it to obtain a pretreated tellurium-copper alloy material; The tellurium-copper alloy material comprises the following components, calculated by weight percentage: 0.35 wt% tellurium, 0.26 wt% sulfur, 0.65 wt% zirconium, 0.30 wt% tin, and the balance copper; Step 2: Preparation of modified tellurium copper alloy material: Take 1.5 g of tris(hydroxymethyl)aminomethane and 100 mL of deionized water, stir evenly, add 0.1 mol / L hydrochloric acid dropwise, adjust the pH to 8.5, and obtain a buffer solution; take 200 mL of the buffer solution, add 1 g of dopamine hydrochloride, and stir evenly to obtain a dopamine solution; The pretreated tellurium-copper alloy material is placed in a dopamine solution and immersed for 24 hours, taken out, and dried to obtain a modified tellurium-copper alloy material; Step 3: Preparation of cage-type silsesquioxane-modified carbon nanotubes: Take 4 mL of tetramethylammonium hydroxide, 20 mL of acetonitrile, 200 mL of deionized water, and 80 mL of propanol, stir evenly, add 200 g of aminopropyltriethoxysilane dropwise, heat to 51 ° C, react for 11 hours, add 500 mL of tetrahydrofuran, precipitate, filter, wash, and dry to obtain amino cage silsesquioxane; Take 50 mL of isopropanol and 50 mL of deionized water, stir evenly, add 2 g of carbon nanotubes, add sodium hydroxide solution, adjust the pH to 13.5, stir for 4.5 hours, add 10 g of amino-type cage-type silsesquioxane, heat to 52 ° C, react for 4.5 hours, add 15 mL of ferric chloride hexahydrate, react for 2.5 hours, centrifuge, wash, and dry to obtain cage-type silsesquioxane-modified carbon nanotubes; Step 4: Preparation of high temperature resistant and softening resistant tellurium copper alloy material: The modified tellurium-copper alloy material is placed in plating solution B, electroplated at 89°C for 32 minutes, taken out and dried to obtain tellurium-copper alloy material A; The tellurium copper alloy material A is placed in the plating solution C, electroplated at 89°C for 32 minutes, taken out and dried to obtain a high temperature resistant and softening resistant tellurium copper alloy material; Bath B: 25 g / L nickel sulfate hexahydrate, 21 g / L sodium hypophosphite monohydrate, 43 g / L sodium citrate, pH adjusted to 8 with aqueous ammonia. Plating solution C: 26 g / L nickel sulfate hexahydrate, 26 g / L sodium hypophosphite monohydrate, 1.5 g / L cage-type silsesquioxane-modified carbon nanotubes, 28 mL / L tannic acid, and the pH was adjusted to 4.5 using aqueous ammonia.

[0022] Comparative Example 2: No amino-type cage silsesquioxane was added, and the rest was the same as Example 1: Step 1: Take tellurium, sulfur, zirconium, tin, and copper, melt, cast, pull, extrude, pickle, anneal, draw, and then perform aging treatment to obtain a tellurium-copper alloy material; Taking a tellurium-copper alloy material, pickling, drying, activating, and drying it to obtain a pretreated tellurium-copper alloy material; The tellurium-copper alloy material comprises the following components, calculated by weight percentage: 0.35 wt% tellurium, 0.26 wt% sulfur, 0.65 wt% zirconium, 0.30 wt% tin, and the balance copper; Step 2: Preparation of modified tellurium copper alloy material: Take 1.5 g of tris(hydroxymethyl)aminomethane and 100 mL of deionized water, stir evenly, add 0.1 mol / L hydrochloric acid dropwise, adjust the pH to 8.5, and obtain a buffer solution; take 200 mL of the buffer solution, add 1 g of dopamine hydrochloride, and stir evenly to obtain a dopamine solution; The pretreated tellurium-copper alloy material is placed in a dopamine solution and immersed for 24 hours, taken out, and dried to obtain a modified tellurium-copper alloy material; Step 3: Preparation of nickel-plated carbon nanotubes: The carbon nanotubes were placed in plating solution A and nickel plated at 62°C for 32 minutes, vacuumed, washed, and dried to obtain nickel-plated carbon nanotubes. Bath A: 34 g / L nickel sulfate, 16 g / L trisodium citrate, 33 g / L sodium hypophosphite, pH adjusted to 8.5 with ammonia; Step 4: Preparation of modified carbon nanotubes: Take 50 mL of isopropanol and 50 mL of deionized water, stir evenly, add 2 g of nickel-plated carbon nanotubes, add sodium hydroxide solution, adjust the pH to 13.5, stir for 4.5 hours, add 15 mL of ferric chloride hexahydrate, heat to 52°C, react for 2.5 hours, centrifuge, wash, and dry to obtain modified carbon nanotubes; Step 5: Preparation of high temperature resistant and softening resistant tellurium copper alloy material: The modified tellurium-copper alloy material is placed in plating solution B, electroplated at 89°C for 32 minutes, taken out and dried to obtain tellurium-copper alloy material A; The tellurium copper alloy material A is placed in the plating solution C, electroplated at 89°C for 32 minutes, taken out and dried to obtain a high temperature resistant and softening resistant tellurium copper alloy material; Bath B: 25 g / L nickel sulfate hexahydrate, 21 g / L sodium hypophosphite monohydrate, 43 g / L sodium citrate, pH adjusted to 8 with aqueous ammonia. Plating solution C: 26 g / L nickel sulfate hexahydrate, 26 g / L sodium hypophosphite monohydrate, 1.5 g / L modified carbon nanotubes, 28 mL / L tannic acid, and the pH was adjusted to 4.5 using aqueous ammonia.

[0023] Comparative Example 3: No ferric chloride hexahydrate was added, and the rest was the same as in Example 1: Step 1: Take tellurium, sulfur, zirconium, tin, and copper, melt, cast, pull, extrude, pickle, anneal, draw, and then perform aging treatment to obtain a tellurium-copper alloy material; Taking a tellurium-copper alloy material, pickling, drying, activating, and drying it to obtain a pretreated tellurium-copper alloy material; The tellurium-copper alloy material comprises the following components, calculated by weight percentage: 0.35 wt% tellurium, 0.26 wt% sulfur, 0.65 wt% zirconium, 0.30 wt% tin, and the balance copper; Step 2: Preparation of modified tellurium copper alloy material: Take 1.5 g of tris(hydroxymethyl)aminomethane and 100 mL of deionized water, stir evenly, add 0.1 mol / L hydrochloric acid dropwise, adjust the pH to 8.5, and obtain a buffer solution; take 200 mL of the buffer solution, add 1 g of dopamine hydrochloride, and stir evenly to obtain a dopamine solution; The pretreated tellurium-copper alloy material is placed in a dopamine solution and immersed for 24 hours, taken out, and dried to obtain a modified tellurium-copper alloy material; Step 3: Preparation of nickel-plated carbon nanotubes: The carbon nanotubes were placed in plating solution A and nickel plated at 62°C for 32 minutes, vacuumed, washed, and dried to obtain nickel-plated carbon nanotubes. Bath A: 34 g / L nickel sulfate, 16 g / L trisodium citrate, 33 g / L sodium hypophosphite, pH adjusted to 8.5 with ammonia; Step 4: Preparation of cage-type silsesquioxane-modified carbon nanotubes: Take 4 mL of tetramethylammonium hydroxide, 20 mL of acetonitrile, 200 mL of deionized water, and 80 mL of propanol, stir evenly, add 200 g of aminopropyltriethoxysilane dropwise, heat to 51 ° C, react for 11 hours, add 500 mL of tetrahydrofuran, precipitate, filter, wash, and dry to obtain amino cage silsesquioxane; Take 50 mL of isopropanol and 50 mL of deionized water, stir evenly, add 2 g of nickel-plated carbon nanotubes, add sodium hydroxide solution, adjust the pH to 13.5, stir for 4.5 hours, add 10 g of amino-type cage-type silsesquioxane, heat to 52 ° C, react for 4.5 hours, centrifuge, wash, and dry to obtain cage-type silsesquioxane-modified carbon nanotubes; Step 5: Preparation of high temperature resistant and softening resistant tellurium copper alloy material: The modified tellurium-copper alloy material is placed in plating solution B, electroplated at 89°C for 32 minutes, taken out and dried to obtain tellurium-copper alloy material A; The tellurium copper alloy material A is placed in the plating solution C, electroplated at 89°C for 32 minutes, taken out and dried to obtain a high temperature resistant and softening resistant tellurium copper alloy material; Bath B: 25 g / L nickel sulfate hexahydrate, 21 g / L sodium hypophosphite monohydrate, 43 g / L sodium citrate, pH adjusted to 8 with aqueous ammonia. Plating solution C: 26 g / L nickel sulfate hexahydrate, 26 g / L sodium hypophosphite monohydrate, 1.5 g / L cage-type silsesquioxane-modified carbon nanotubes, 28 mL / L tannic acid, and the pH was adjusted to 4.5 using aqueous ammonia.

[0024] Comparative Example 4: No plating solution B was added, and the rest was the same as in Example 1: Step 1: Take tellurium, sulfur, zirconium, tin, and copper, melt, cast, pull, extrude, pickle, anneal, draw, and then perform aging treatment to obtain a tellurium-copper alloy material; Taking a tellurium-copper alloy material, pickling, drying, activating, and drying it to obtain a pretreated tellurium-copper alloy material; The tellurium-copper alloy material comprises the following components, calculated by weight percentage: 0.35 wt% tellurium, 0.26 wt% sulfur, 0.65 wt% zirconium, 0.30 wt% tin, and the balance copper; Step 2: Preparation of modified tellurium copper alloy material: Take 1.5 g of tris(hydroxymethyl)aminomethane and 100 mL of deionized water, stir evenly, add 0.1 mol / L hydrochloric acid dropwise, adjust the pH to 8.5, and obtain a buffer solution; take 200 mL of the buffer solution, add 1 g of dopamine hydrochloride, and stir evenly to obtain a dopamine solution; The pretreated tellurium-copper alloy material is placed in a dopamine solution and immersed for 24 hours, taken out, and dried to obtain a modified tellurium-copper alloy material; Step 3: Preparation of nickel-plated carbon nanotubes: The carbon nanotubes were placed in plating solution A and nickel plated at 62°C for 32 minutes, vacuumed, washed, and dried to obtain nickel-plated carbon nanotubes. Bath A: 34 g / L nickel sulfate, 16 g / L trisodium citrate, 33 g / L sodium hypophosphite, pH adjusted to 8.5 with ammonia; Step 4: Preparation of cage-type silsesquioxane-modified carbon nanotubes: Take 4 mL of tetramethylammonium hydroxide, 20 mL of acetonitrile, 200 mL of deionized water, and 80 mL of propanol, stir evenly, add 200 g of aminopropyltriethoxysilane dropwise, heat to 51 ° C, react for 11 hours, add 500 mL of tetrahydrofuran, precipitate, filter, wash, and dry to obtain amino cage silsesquioxane; Take 50 mL of isopropanol and 50 mL of deionized water, stir evenly, add 2 g of nickel-plated carbon nanotubes, add sodium hydroxide solution, adjust the pH to 13.5, stir for 4.5 hours, add 10 g of amino-type cage-type silsesquioxane, heat to 52 ° C, react for 4.5 hours, add 15 mL of ferric chloride hexahydrate, react for 2.5 hours, centrifuge, wash, and dry to obtain cage-type silsesquioxane-modified carbon nanotubes; Step 5: Preparation of high temperature resistant and softening resistant tellurium copper alloy material: The modified tellurium-copper alloy material is placed in plating solution C, electroplated at 89° C. for 32 minutes, taken out, and dried to obtain a high-temperature resistant and softening-resistant tellurium-copper alloy material; Plating solution C: 26 g / L nickel sulfate hexahydrate, 26 g / L sodium hypophosphite monohydrate, 1.5 g / L cage-type silsesquioxane-modified carbon nanotubes, 28 mL / L tannic acid, and the pH was adjusted to 4.5 using aqueous ammonia.

[0025] experiment: The high-temperature resistant and softening-resistant tellurium-copper alloy materials prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were subjected to performance tests. The high-temperature resistant and softening-resistant tellurium-copper alloy materials were heated at a certain temperature using a box-type resistance furnace. The hardness change before and after the test was measured. When the hardness dropped by 20%, this temperature was the softening temperature of the high-temperature resistant and softening-resistant tellurium-copper alloy material. The high-temperature resistant and softening-resistant tellurium-copper alloy material was placed in a sodium chloride solution with a concentration of 3.5wt% and a temperature of 25°C for 7 days, then removed and weighed. The corrosion rate was calculated. The data obtained are shown in Table 1 below: Table 1

[0026] Conclusion: From the comparison of the data in the table, it can be seen that in Comparative Example 1, nickel is not plated on the surface of the carbon nanotubes, the corrosion rate increases, and the corrosion resistance decreases. In Comparative Example 2, no amino-type cage-type silsesquioxane is added, and corrosive substances easily enter the surface of the tellurium copper alloy material, resulting in a decrease in corrosion resistance. In Comparative Example 3, ferric chloride hexahydrate is not added, and a complex reaction cannot be formed, resulting in a decrease in the corrosion resistance of the alloy. In Comparative Example 4, no plating solution B is added, and the corrosion resistance decreases. In Examples 1-3 of the present invention, nickel is first plated on the surface of the carbon nanotubes. After nickel plating, the carbon nanotubes are more evenly dispersed in the nickel-plated layer, have better compatibility, and have a higher density of the nickel layer, thereby improving the corrosion resistance of the alloy material. The nickel-plated carbon nanotubes are then compounded with amino-type cage-type silsesquioxane, making it more difficult for corrosive substances to invade, thereby improving corrosion resistance. Further modification by adding ferric chloride hexahydrate can produce a complex reaction with the tannic acid in plating solution C, thereby generating a complex compound, strengthening the strength between the alloy material and the coating, and thus enhancing the corrosion resistance of the alloy material.

[0027] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations that come within the meaning and range of equivalents of the claims be embraced therein.

Claims

1. A method for preparing a high-temperature resistant and softening-resistant tellurium-copper alloy material, characterized by: The following steps are involved: Step 1: Take tellurium, sulfur, zirconium, tin, and copper, melt, cast, pull, extrude, pickle, anneal, draw, and then perform aging treatment to obtain a tellurium copper alloy material; Step 2: taking a tellurium-copper alloy material, pickling, drying, activating, and drying to obtain a pretreated tellurium-copper alloy material; Step 3: taking the pretreated tellurium copper alloy material and placing it in a dopamine solution, immersing it for 22-26 hours, taking it out and drying it to obtain a modified tellurium copper alloy material; Step 4: placing the modified tellurium copper alloy material in plating solution B, electroplating at 88-90° C. for 30-35 minutes, taking out and drying to obtain tellurium copper alloy material A; The tellurium copper alloy material A is placed in a plating solution C, electroplated at 88-90° C. for 30-35 minutes, taken out, and dried to obtain a high-temperature resistant and softening-resistant tellurium copper alloy material.

2. The method for preparing a high-temperature resistant and softening-resistant tellurium-copper alloy material according to claim 1, characterized in that: The tellurium-copper alloy material includes the following components, calculated by weight percentage: 0.3wt%-0.4wt% tellurium, 0.22wt%-0.28wt% sulfur, 0.50wt%-0.75wt% zirconium, 0.23wt%-0.40wt% tin, and the balance copper.

3. The method for preparing a high-temperature resistant and softening-resistant tellurium-copper alloy material according to claim 1, characterized in that: The plating solution B includes the following components: 24-27 g / L nickel sulfate hexahydrate, 20-22 g / L sodium hypophosphite monohydrate, and 40-46 g / L sodium citrate, and the pH is adjusted to 8 using ammonia water.

4. The method for preparing a high-temperature resistant and softening-resistant tellurium-copper alloy material according to claim 1, characterized in that: The plating solution C includes the following components: 24-27 g / L nickel sulfate hexahydrate, 25-27 g / L sodium hypophosphite monohydrate, 1-2 g / L cage-type silsesquioxane-modified carbon nanotubes, and 25-30 mL / L tannic acid, and the pH is adjusted to 4.5 using ammonia water.

5. The method for preparing a high-temperature resistant and softening-resistant tellurium-copper alloy material according to claim 4, characterized in that: The preparation method of the cage-type silsesquioxane-modified carbon nanotubes is as follows: The following steps are involved: S1: Take tetramethylammonium hydroxide, acetonitrile, deionized water, and propanol, stir evenly, add aminopropyltriethoxysilane dropwise, raise the temperature to 50-52°C, react for 10-14 hours, add tetrahydrofuran, precipitate, filter, wash, and dry to obtain amino cage silsesquioxane; S2: Take isopropanol and deionized water, stir evenly, add nickel-plated carbon nanotubes, add sodium hydroxide solution, adjust the pH to 13-14, stir for 4-5 hours, add amino-type cage-type silsesquioxane, heat to 50-55°C, react for 4-5 hours, add ferric chloride hexahydrate, react for 2-3 hours, centrifuge, wash, and dry to obtain cage-type silsesquioxane-modified carbon nanotubes.

6. The method for preparing a high-temperature resistant and softening-resistant tellurium-copper alloy material according to claim 5, characterized in that: The preparation method of the nickel-plated carbon nanotubes comprises: placing carbon nanotubes in a plating solution A, plating nickel at 60-65° C. for 30-35 minutes, vacuuming, washing, and drying to obtain nickel-plated carbon nanotubes.

7. The method for preparing a high-temperature resistant and softening-resistant tellurium-copper alloy material according to claim 6, characterized in that: The plating solution A includes the following components: plating solution A: 33-36 g / L nickel sulfate, 15-17 g / L trisodium citrate, 30-35 g / L sodium hypophosphite, and ammonia water is used to adjust the pH to 8.

5.

8. The method for preparing a high-temperature resistant and softening-resistant tellurium-copper alloy material according to claim 1, characterized in that: The dopamine solution preparation method comprises the following steps: taking tris(hydroxymethyl)aminomethane and deionized water, stirring evenly, adding hydrochloric acid dropwise, and adjusting the pH value to 8.5 to obtain a buffer solution; taking the buffer solution, adding dopamine hydrochloride, and stirring evenly to obtain a dopamine solution.

9. A high-temperature resistant and softening-resistant tellurium-copper alloy material prepared according to the method for preparing a high-temperature resistant and softening-resistant tellurium-copper alloy material according to any one of claims 1 to 8.

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