A high-strength alloy conductor and its preparation method

Abstract

This invention relates to the field of conductor materials, specifically to a high-strength alloy conductor and its preparation method. It addresses the problem that existing alloy conductor materials suffer from poor mechanical strength and conductivity, making them unsuitable for demanding applications. The preparation method uses Cu powder as the main raw material, adding Ag powder to impart excellent conductivity. Adding silver-loaded carbon nanotubes and nano-TiB2 particles significantly improves the conductor's mechanical properties and further enhances its conductivity. Furthermore, the use of a ball milling enhancer during the ball milling process refines the alloy grains, increasing the alloy's density and microstructure uniformity, further improving both the conductor's mechanical and conductivity properties. This high-strength alloy conductor exhibits excellent comprehensive performance and can be widely used in demanding conductive components in high-speed trains, aerospace, and new energy vehicles.

Description

Technical Field

[0001] This invention relates to the field of conductor materials, and more specifically to a high-strength alloy conductor and its preparation method. Background Technology

[0002] With the rapid development of modern technology, the performance requirements for conductor materials are increasing. Traditional conductor materials, such as pure copper and pure silver, although they have high conductivity, have low mechanical strength, making them difficult to meet the needs of some demanding applications.

[0003] To improve the performance of conductor materials, other elements are added to them through alloying. However, existing alloy conductor materials often lead to a significant decrease in conductivity while improving mechanical strength, making it difficult to achieve a good balance between mechanical strength and conductivity. Therefore, developing a high-strength alloy conductor and its preparation method is of significant practical importance. Summary of the Invention

[0004] In order to overcome the above-mentioned technical problems, the present invention aims to provide a high-strength alloy conductor and its preparation method, which solves the problem that the existing alloy conductor materials have poor mechanical strength and conductivity, and are difficult to meet the application requirements in some high-demand applications.

[0005] The objective of this invention can be achieved through the following technical solutions:

[0006] A high-strength alloy conductor comprises the following components in parts by weight:

[0007] 92.5-95.8 parts Cu powder, 3.0-5.0 parts Ag powder, 1.1-4.5 parts silver-loaded carbon nanotubes, 0.5-1.2 parts Cr powder, 0.2-0.5 parts ZrO2 powder, 0.05-0.15 parts rare earth elements, 0.3-0.8 parts nano TiB2 particles, 1-6 parts ball milling reinforcing agent, and 220-250 parts ethanol solution;

[0008] The silver-loaded carbon nanotubes are prepared by the following steps:

[0009] Step a1: Add concentrated nitric acid and concentrated sulfuric acid to a three-necked flask equipped with a stirrer and thermometer. Stir the reaction at 25-30℃ and 200-300 r / min for 3-5 min. Then add carbon nanotubes and continue stirring for 10-20 min. Then raise the temperature to 95-100℃ and continue stirring for 3-5 h. After the reaction is complete, cool the reaction product to room temperature, then centrifuge. Wash the precipitate with distilled water 3-5 times, then place it in a vacuum drying oven and dry it at 70-75℃ for 1-2 h to obtain acidified carbon nanotubes.

[0010] Step a2: Add stannous chloride and hydrochloric acid solution to a three-necked flask equipped with a stirrer and thermometer. Stir the reaction at 25-30℃ and 200-300 r / min for 10-20 min. Then add acidified carbon nanotubes and continue stirring for 2-4 h. After the reaction is complete, centrifuge the reaction product and wash the precipitate 3-5 times with distilled water. Then place it in a vacuum drying oven and dry it at 70-75℃ for 1-2 h to obtain sensitized carbon nanotubes.

[0011] Step a3: Add silver nitrate, concentrated ammonia, sodium hydroxide, polyvinylpyrrolidone, and deionized water to a three-necked flask equipped with a stirrer and thermometer. Stir the reaction at 25-30℃ and 200-300 r / min for 20-30 min. Then add sensitized carbon nanotubes and continue stirring for 20-30 min. Next, add glucose solution and continue stirring for 2-4 h. After the reaction is complete, centrifuge the reaction product and wash the precipitate 3-5 times with distilled water. Then place it in a vacuum drying oven and dry it at 50-55℃ for 2-3 h to obtain silver-loaded carbon nanotubes.

[0012] As a further aspect of the present invention: the ratio of concentrated nitric acid, concentrated sulfuric acid and carbon nanotubes used in step a1 is 30-35 mL: 30-35 mL: 2 g.

[0013] As a further aspect of the present invention: the mass fraction of the concentrated nitric acid in step a1 is 67%; the mass fraction of the concentrated sulfuric acid is 98%; and the carbon nanotube is a high-purity multi-walled carbon nanotube (TNMO).

[0014] As a further aspect of the present invention: the ratio of stannous chloride, hydrochloric acid solution and acidified carbon nanotubes used in step a2 is 0.8-1.6g: 100-120mL: 2g.

[0015] As a further aspect of the present invention: the molar concentration of the hydrochloric acid solution in step a2 is 1-1.2 mol / L.

[0016] As a further aspect of the present invention: the ratio of silver nitrate, concentrated ammonia, sodium hydroxide, polyvinylpyrrolidone, deionized water, sensitized carbon nanotubes and glucose solution used in step a3 is 2-3g: 5-7mL: 0.2-0.4g: 0.1-0.3g: 80-90mL: 3g: 80-90mL.

[0017] As a further aspect of the present invention: the concentrated ammonia in step a3 has a mass fraction of 25-27%; the polyvinylpyrrolidone is PVP K30; the glucose solution is a solution prepared by mixing glucose, sodium tartrate, deionized water and anhydrous ethanol in a ratio of 7-9g: 0.5-0.6g: 90-100mL: 10-12mL.

[0018] As a further aspect of the present invention: the ball milling reinforcing agent is prepared by the following steps:

[0019] 3-Chloropropyltriethoxysilane, triethanolamine, potassium carbonate, potassium iodide, and anhydrous acetone were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred for 20-30 minutes at a temperature of 0-5℃ and a stirring rate of 200-300 r / min. Then, the temperature was raised to 80-85℃ and the stirring was continued for 10-12 hours. After the reaction was completed, the reaction product was cooled to room temperature, then vacuum filtered, and the solvent was removed by rotary evaporation of the filtrate to obtain the ball milling reinforcing agent.

[0020] As a further aspect of the present invention, the ratio of the amounts of 3-chloropropyltriethoxysilane, triethanolamine, potassium carbonate, potassium iodide and anhydrous acetone is 10 mmol: 10 mmol: 11-13 mmol: 0.05-0.07 g: 60-70 mL.

[0021] As a further aspect of the present invention: a method for preparing a high-strength alloy conductor, comprising the following steps:

[0022] Step 1: Weigh out the following components by weight: 92.5-95.8 parts Cu powder, 3.0-5.0 parts Ag powder, 1.1-4.5 parts silver-loaded carbon nanotubes, 0.5-1.2 parts Cr powder, 0.2-0.5 parts ZrO2 powder, 0.05-0.15 parts rare earth elements, 0.3-0.8 parts nano TiB2 particles, 1-6 parts ball milling reinforcing agent, and 220-250 parts ethanol solution. Set aside for later use.

[0023] Step 2: Add Cu powder, Ag powder, Cr powder, ZrO2 powder, ball milling enhancer, and anhydrous ethanol into a ball mill. Ball mill for 5-6 hours at a ball-to-material ratio of 2:1 and a ball milling speed of 80-100 r / min. Then, vacuum filter the mixture and place the filter cake in a vacuum drying oven. Dry the cake at a temperature of 70-75℃ for 3-4 hours to obtain the ball milled powder.

[0024] Step 3: Place the ball-milled powder in a vacuum induction furnace, introduce argon gas for protection, and heat and melt at a temperature of 1250-1300℃ for 30-40 minutes to obtain a molten alloy liquid.

[0025] Step 4: Add silver-loaded carbon nanotubes, rare earth elements and nano TiB2 particles to the molten alloy, and hold it at an ultrasonic frequency of 40-50kHz for 15-25 minutes to obtain a particle dispersion reinforced alloy liquid.

[0026] Step 5: Cool the particle dispersion reinforced alloy liquid to 800℃ at a cooling rate of 5-10℃ / min, then perform ultra-fast solidification with liquid metal coolant under a cooling interface pressure of 0.2-0.5MPa, followed by multi-stage aging treatment to obtain a high-strength alloy conductor.

[0027] As a further aspect of the present invention: the liquid metal coolant is a Ga-In-Sn alloy, and the composition of the Ga-In-Sn alloy is Ga... 62 In 25 Sn 13 The cooling rate during the ultra-fast solidification process is ≥1000℃ / s.

[0028] As a further aspect of the present invention, the specific process of the multi-stage aging treatment is as follows: heat preservation at a temperature of 450°C for 2 hours, followed by heat preservation at a temperature of 300°C for 6 hours, and then heat preservation at a temperature of 150°C for 24 hours.

[0029] As a further aspect of the present invention: the rare earth elements are a mixture of yttrium oxide and lanthanum oxide in a mass ratio of 2:1; the volume fraction of the ethanol solution is 90%.

[0030] The beneficial effects of this invention are:

[0031] This invention discloses a high-strength alloy conductor and its preparation method. The method involves ball milling Cu powder, Ag powder, Cr powder, ZrO2 powder, a ball milling reinforcing agent, and anhydrous ethanol, followed by vacuum filtration and drying of the filter cake to obtain ball-milled powder. This powder is then subjected to heat-insulating smelting to obtain a molten alloy. Silver-loaded carbon nanotubes, rare earth elements, and nano-TiB2 particles are added to the molten alloy and subjected to heat-insulating ultrasonic treatment to obtain a particle-dispersion reinforced alloy. The particle-dispersion reinforced alloy is then cooled and solidified, followed by multi-stage aging treatment to obtain a high-strength alloy conductor. The preparation method uses Cu powder as the main raw material and adds Ag powder to impart excellent conductivity to the conductor. Adding silver-loaded carbon nanotubes and nano-TiB2 particles can significantly improve the mechanical properties of the conductor and further enhance its conductivity. The use of a ball milling enhancer during the ball milling process can refine the alloy grains, improve the density and uniformity of the alloy, and further improve the mechanical and conductivity properties of the conductor. This high-strength alloy conductor has excellent comprehensive performance and can be widely used in high-requirement conductive components in high-speed trains, aerospace, new energy vehicles and other fields.

[0032] In the preparation of high-strength alloy conductors, silver-loaded carbon nanotubes were first prepared. The carbon nanotubes were treated with concentrated nitric acid and concentrated sulfuric acid to effectively remove impurities and introduce oxygen-containing groups, achieving an etching effect to obtain acidified carbon nanotubes. Then, stannous chloride was used to sensitize the acidified carbon nanotubes to obtain sensitized carbon nanotubes. Finally, silver was plated onto the surface of the sensitized carbon nanotubes using a silver-ammonia reaction to obtain silver-loaded carbon nanotubes. The carbon nanotubes in these silver-loaded carbon nanotubes possess excellent mechanical properties. Adding them to the conductor can effectively bear external loads and prevent crack propagation, thereby improving the conductor's strength and toughness. Simultaneously, carbon nanotubes have excellent electrical conductivity, promoting rapid electron transport and thus improving the overall conductivity of the conductor. Silver plating on the surface enhances the interfacial bonding between the carbon nanotubes and the substrate, forming a tighter bond and reducing defects and porosity at the interface, thereby improving the conductor's mechanical properties. Furthermore, the surface silver can form conductive bridges between carbon nanotubes and between the carbon nanotubes and the substrate, further reducing the conductor's resistance and improving conductivity.

[0033] In the process of preparing high-strength alloy conductors, a ball milling reinforcing agent was also prepared. This agent was obtained by reacting 3-chloropropyltriethoxysilane with triethanolamine. The chlorine atom on 3-chloropropyltriethoxysilane reacts with the hydroxyl group on triethanolamine. The siloxane on this ball milling reinforcing agent hydrolyzes to form silanols, which can be grafted onto the surface of each component particle. Simultaneously, a large number of hydroxyl groups are introduced, which can adsorb onto the surface of other component particles, giving each particle the same charge. This generates electrostatic repulsion, preventing the particles from approaching each other and agglomerating, and producing a steric hindrance effect. This prevents powder particle agglomeration, promotes more thorough refinement of each component particle during ball milling, ensures uniform mixing and good density of each component particle, improves the density and microstructure uniformity of the alloy, and enhances its mechanical properties. Detailed Implementation

[0034] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0035] Example 1:

[0036] This embodiment describes a method for preparing a high-strength alloy conductor, comprising the following steps:

[0037] Step S1: Add 30 mL of 67% concentrated nitric acid and 30 mL of 98% concentrated sulfuric acid to a three-necked flask equipped with a stirrer and thermometer. Stir the reaction at 25°C and 200 r / min for 3 min. Then add 2 g of high-purity multi-walled carbon nanotubes TNMO and continue stirring for 10 min. Then raise the temperature to 95°C and continue stirring for 3 h. After the reaction is complete, cool the reaction product to room temperature, centrifuge, wash the precipitate three times with distilled water, and then place it in a vacuum drying oven and dry it at 70°C for 1 h to obtain acidified carbon nanotubes.

[0038] Step S2: Add 0.8g of stannous chloride and 100mL of 1mol / L hydrochloric acid solution to a three-necked flask equipped with a stirrer and thermometer. Stir the reaction at 25℃ and 200r / min for 10min. Then add 2g of acidified carbon nanotubes and continue stirring for 2h. After the reaction is complete, centrifuge the reaction product, wash the precipitate three times with distilled water, and then place it in a vacuum drying oven and dry it at 70℃ for 1h to obtain sensitized carbon nanotubes.

[0039] Step S3: Add 2g silver nitrate, 5mL concentrated ammonia (25% by mass), 0.2g sodium hydroxide, 0.1g polyvinylpyrrolidone (PVP K30), and 80mL deionized water to a three-necked flask equipped with a stirrer and thermometer. Stir the mixture at 25℃ and 200r / min for 20min. Then add 3g sensitized carbon nanotubes and continue stirring for another 20min. Next, add 80mL of a glucose solution prepared by mixing glucose, sodium tartrate, deionized water, and anhydrous ethanol in a ratio of 7g:0.5g:90mL:10mL and continue stirring for 2h. After the reaction is complete, centrifuge the reaction product, wash the precipitate three times with distilled water, and then place it in a vacuum drying oven at 50℃ for 2h to obtain silver-loaded carbon nanotubes.

[0040] Step S4: 10 mmol of 3-chloropropyltriethoxysilane, 10 mmol of triethanolamine, 11 mmol of potassium carbonate, 0.05 g of potassium iodide and 60 mL of anhydrous acetone were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 0 °C and 200 r / min for 20 min. Then the temperature was raised to 80 °C and the mixture was stirred for 10 h. After the reaction was completed, the reaction product was cooled to room temperature and then filtered under vacuum. The solvent was removed by rotary evaporation of the filtrate to obtain the ball milling enhancer.

[0041] Step S5: Weigh out 92.5 parts by weight of Cu powder, 3.0 parts by weight of Ag powder, 1.1 parts by weight of silver-loaded carbon nanotubes, 0.5 parts by weight of Cr powder, 0.2 parts by weight of ZrO2 powder, 0.05 parts by weight of rare earth elements, 0.3 parts by weight of nano-TiB2 particles, 1 part by weight of ball milling reinforcing agent, and 220 parts by weight of ethanol solution, and set aside for later use; the rare earth elements are a mixture of yttrium oxide and lanthanum oxide in a mass ratio of 2:1; the volume fraction of the ethanol solution is 90%.

[0042] Step S6: Add Cu powder, Ag powder, Cr powder, ZrO2 powder, ball milling enhancer and anhydrous ethanol into a ball mill, and ball mill for 5 hours at a ball-to-material ratio of 2:1 and a ball milling speed of 80 r / min. Then vacuum filter, place the filter cake in a vacuum drying oven and dry it at a temperature of 70℃ for 3 hours to obtain ball milled powder.

[0043] Step S7: Place the ball-milled powder in a vacuum induction furnace, introduce argon gas for protection, and heat and melt at 1250℃ for 30 minutes to obtain a molten alloy liquid.

[0044] Step S8: Add silver-loaded carbon nanotubes, rare earth elements and nano TiB2 particles to the molten alloy, and hold at a temperature of 40kHz for 15 minutes to obtain a particle dispersion reinforced alloy liquid.

[0045] Step S9: Cool the particle dispersion reinforced alloy liquid to 800℃ at a cooling rate of 5℃ / min, and then pass it through Ga under a cooling interface pressure of 0.2MPa. 62 In 25 Sn 13 Liquid metal coolant is subjected to ultra-rapid solidification at a cooling rate ≥1000℃ / s, followed by holding at 450℃ for 2 hours, then at 300℃ for 6 hours, and finally at 150℃ for 24 hours to complete multi-stage aging treatment, resulting in a high-strength alloy conductor.

[0046] Example 2:

[0047] This embodiment describes a method for preparing a high-strength alloy conductor, comprising the following steps:

[0048] Step S1: Add 32 mL of 67% concentrated nitric acid and 32 mL of 98% concentrated sulfuric acid to a three-necked flask equipped with a stirrer and thermometer. Stir the reaction at 28°C and 250 r / min for 4 min. Then add 2 g of high-purity multi-walled carbon nanotubes TNMO and continue stirring for 15 min. Then raise the temperature to 98°C and continue stirring for 4 h. After the reaction is complete, cool the reaction product to room temperature, centrifuge, wash the precipitate four times with distilled water, and then place it in a vacuum drying oven and dry at 72°C for 1.5 h to obtain acidified carbon nanotubes.

[0049] Step S2: Add 1.2g of stannous chloride and 110mL of 1.1mol / L hydrochloric acid solution to a three-necked flask equipped with a stirrer and thermometer. Stir the reaction at 28℃ and 250r / min for 15min. Then add 2g of acidified carbon nanotubes and continue stirring for 3h. After the reaction is complete, centrifuge the reaction product, wash the precipitate four times with distilled water, and then place it in a vacuum drying oven and dry it at 72℃ for 1.5h to obtain sensitized carbon nanotubes.

[0050] Step S3: Add 2.5g silver nitrate, 6mL concentrated ammonia (26% by mass), 0.3g sodium hydroxide, 0.2g polyvinylpyrrolidone (PVP K30), and 85mL deionized water to a three-necked flask equipped with a stirrer and thermometer. Stir the mixture at 28℃ and 250r / min for 25min. Then add 3g sensitized carbon nanotubes and continue stirring for another 25min. Next, add 85mL of a glucose solution prepared by mixing glucose, sodium tartrate, deionized water, and anhydrous ethanol in a ratio of 8g:0.55g:95mL:11mL and continue stirring for 3h. After the reaction is complete, centrifuge the reaction product, wash the precipitate four times with distilled water, and then place it in a vacuum drying oven at 52℃ for 2.5h to obtain silver-loaded carbon nanotubes.

[0051] Step S4: 10 mmol of 3-chloropropyltriethoxysilane, 10 mmol of triethanolamine, 12 mmol of potassium carbonate, 0.06 g of potassium iodide and 65 mL of anhydrous acetone were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 3 °C and 250 r / min for 25 min. Then the temperature was raised to 82 °C and the mixture was stirred for 11 h. After the reaction was completed, the reaction product was cooled to room temperature and then filtered under vacuum. The solvent was removed by rotary evaporation of the filtrate to obtain the ball milling reinforcing agent.

[0052] Step S5: Weigh out 94.1 parts by weight of Cu powder, 4.0 parts by weight of Ag powder, 2.8 parts by weight of silver-loaded carbon nanotubes, 0.8 parts by weight of Cr powder, 0.35 parts by weight of ZrO2 powder, 0.1 parts by weight of rare earth elements, 0.55 parts by weight of nano-TiB2 particles, 3.5 parts by weight of ball milling reinforcing agent, and 235 parts by weight of ethanol solution, and set aside for later use; the rare earth elements are a mixture of yttrium oxide and lanthanum oxide in a mass ratio of 2:1; the volume fraction of the ethanol solution is 90%;

[0053] Step S6: Add Cu powder, Ag powder, Cr powder, ZrO2 powder, ball milling enhancer and anhydrous ethanol into a ball mill, and ball mill for 5.5 hours at a ball-to-material ratio of 2:1 and a ball milling speed of 90 r / min. Then vacuum filter, place the filter cake in a vacuum drying oven and dry it at a temperature of 72℃ for 3.5 hours to obtain ball milled powder.

[0054] Step S7: Place the ball-milled powder in a vacuum induction furnace, introduce argon gas for protection, and heat and melt at 1275℃ for 35 minutes to obtain a molten alloy liquid.

[0055] Step S8: Add silver-loaded carbon nanotubes, rare earth elements and nano TiB2 particles to the molten alloy, and hold it at an ultrasonic frequency of 45kHz for 20 minutes to obtain a particle dispersion reinforced alloy liquid.

[0056] Step S9: Cool the particle dispersion reinforced alloy liquid to 800℃ at a cooling rate of 8℃ / min, and then pass it through Ga under a cooling interface pressure of 0.35MPa. 62 In 25 Sn 13 Liquid metal coolant is subjected to ultra-rapid solidification at a cooling rate ≥1000℃ / s, followed by holding at 450℃ for 2 hours, then at 300℃ for 6 hours, and finally at 150℃ for 24 hours to complete multi-stage aging treatment, resulting in a high-strength alloy conductor.

[0057] Example 3:

[0058] This embodiment describes a method for preparing a high-strength alloy conductor, comprising the following steps:

[0059] Step S1: Add 35 mL of 67% concentrated nitric acid and 35 mL of 98% concentrated sulfuric acid to a three-necked flask equipped with a stirrer and thermometer. Stir the reaction at 30°C and 300 r / min for 5 min. Then add 2 g of high-purity multi-walled carbon nanotubes (TNM0) and continue stirring for 20 min. Then raise the temperature to 100°C and continue stirring for 5 h. After the reaction is complete, cool the reaction product to room temperature, centrifuge, wash the precipitate 5 times with distilled water, and then place it in a vacuum drying oven and dry it at 75°C for 2 h to obtain acidified carbon nanotubes.

[0060] Step S2: 1.6g of stannous chloride and 120mL of 1.2mol / L hydrochloric acid solution were added to a three-necked flask equipped with a stirrer and thermometer. The mixture was stirred at 30℃ and 300r / min for 20min. Then, 2g of acidified carbon nanotubes were added and the mixture was stirred for another 4h. After the reaction was completed, the reaction product was centrifuged and the precipitate was washed 5 times with distilled water. Then, it was placed in a vacuum drying oven and dried at 75℃ for 2h to obtain sensitized carbon nanotubes.

[0061] Step S3: Add 3g silver nitrate, 7mL concentrated ammonia (27% by mass), 0.4g sodium hydroxide, 0.3g polyvinylpyrrolidone (PVP K30), and 90mL deionized water to a three-necked flask equipped with a stirrer and thermometer. Stir the mixture at 30℃ and 300r / min for 30min. Then add 3g sensitized carbon nanotubes and continue stirring for another 30min. Next, add 90mL of a glucose solution prepared by mixing glucose, sodium tartrate, deionized water, and anhydrous ethanol in a ratio of 9g:0.6g:100mL:12mL and continue stirring for 4h. After the reaction is complete, centrifuge the reaction product, wash the precipitate five times with distilled water, and then place it in a vacuum drying oven at 55℃ for 3h to obtain silver-loaded carbon nanotubes.

[0062] Step S4: 10 mmol of 3-chloropropyltriethoxysilane, 10 mmol of triethanolamine, 13 mmol of potassium carbonate, 0.07 g of potassium iodide and 70 mL of anhydrous acetone were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 5 °C and 300 r / min for 30 min. Then the temperature was raised to 85 °C and the mixture was stirred for 12 h. After the reaction was completed, the reaction product was cooled to room temperature and then filtered under vacuum. The solvent was removed by rotary evaporation of the filtrate to obtain the ball milling reinforcing agent.

[0063] Step S5: Weigh out 95.8 parts by weight of Cu powder, 5.0 parts by weight of Ag powder, 4.5 parts by weight of silver-loaded carbon nanotubes, 1.2 parts by weight of Cr powder, 0.5 parts by weight of ZrO2 powder, 0.15 parts by weight of rare earth elements, 0.8 parts by weight of nano-TiB2 particles, 6 parts by weight of ball milling reinforcing agent, and 250 parts by weight of ethanol solution, and set aside for later use; the rare earth elements are a mixture of yttrium oxide and lanthanum oxide in a mass ratio of 2:1; the volume fraction of the ethanol solution is 90%.

[0064] Step S6: Add Cu powder, Ag powder, Cr powder, ZrO2 powder, ball milling enhancer and anhydrous ethanol into a ball mill, and ball mill for 6 hours at a ball-to-material ratio of 2:1 and a ball milling speed of 100 r / min. Then vacuum filter, place the filter cake in a vacuum drying oven and dry it at a temperature of 75℃ for 4 hours to obtain ball milled powder.

[0065] Step S7: Place the ball-milled powder in a vacuum induction furnace, introduce argon gas for protection, and heat and melt at 1300℃ for 40 minutes to obtain a molten alloy liquid.

[0066] Step S8: Add silver-loaded carbon nanotubes, rare earth elements and nano TiB2 particles to the molten alloy liquid, and hold it at an ultrasonic frequency of 50kHz for 25 minutes to obtain a particle dispersion reinforced alloy liquid.

[0067] Step S9: Cool the particle dispersion reinforced alloy liquid to 800℃ at a cooling rate of 10℃ / min, and then pass it through Ga under a cooling interface pressure of 0.5MPa. 62 In 25 Sn 13 Liquid metal coolant is subjected to ultra-rapid solidification at a cooling rate ≥1000℃ / s, followed by holding at 450℃ for 2 hours, then at 300℃ for 6 hours, and finally at 150℃ for 24 hours to complete multi-stage aging treatment, resulting in a high-strength alloy conductor.

[0068] Comparative Example 1:

[0069] This comparative example illustrates a method for preparing a high-strength alloy conductor, comprising the following steps:

[0070] Step S1: Weigh out 95.8 parts Cu powder, 5.0 parts Ag powder, 1.2 parts Cr powder, 0.5 parts ZrO2 powder, 0.15 parts rare earth elements, and 250 parts ethanol solution according to their weight proportions, and set aside for later use; the rare earth elements are a mixture of yttrium oxide and lanthanum oxide in a mass ratio of 2:1; the volume fraction of the ethanol solution is 90%.

[0071] Step S2: Add Cu powder, Ag powder, Cr powder, ZrO2 powder and anhydrous ethanol into a ball mill and ball mill for 6 hours at a ball-to-material ratio of 2:1 and a ball milling speed of 100 r / min. Then vacuum filter and place the filter cake in a vacuum drying oven and dry it at a temperature of 75℃ for 4 hours to obtain ball milled powder.

[0072] Step S3: Place the ball-milled powder in a vacuum induction furnace, introduce argon gas for protection, and heat and melt at 1300℃ for 40 minutes to obtain a molten alloy liquid.

[0073] Step S4: Add rare earth elements to the molten alloy and hold it at a temperature of 50 kHz for 25 min to obtain a particle dispersion reinforced alloy liquid.

[0074] Step S5: Cool the particle dispersion reinforced alloy liquid to 800℃ at a cooling rate of 10℃ / min, and then pass it through Ga under a cooling interface pressure of 0.5MPa. 62 In 25 Sn 13 Liquid metal coolant is subjected to ultra-rapid solidification at a cooling rate ≥1000℃ / s, followed by holding at 450℃ for 2 hours, then at 300℃ for 6 hours, and finally at 150℃ for 24 hours to complete multi-stage aging treatment, resulting in a high-strength alloy conductor.

[0075] Comparative Example 2:

[0076] This comparative example illustrates a method for preparing a high-strength alloy conductor, comprising the following steps:

[0077] Step S1: Weigh out 95.8 parts by weight of Cu powder, 5.0 parts by weight of Ag powder, 1.2 parts by weight of Cr powder, 0.5 parts by weight of ZrO2 powder, 0.15 parts by weight of rare earth elements, 0.8 parts by weight of nano-TiB2 particles, and 250 parts by weight of ethanol solution, and set aside for later use; the rare earth elements are a mixture of yttrium oxide and lanthanum oxide in a mass ratio of 2:1; the volume fraction of the ethanol solution is 90%.

[0078] Step S2: Add Cu powder, Ag powder, Cr powder, ZrO2 powder and anhydrous ethanol into a ball mill and ball mill for 6 hours at a ball-to-material ratio of 2:1 and a ball milling speed of 100 r / min. Then vacuum filter and place the filter cake in a vacuum drying oven and dry it at a temperature of 75℃ for 4 hours to obtain ball milled powder.

[0079] Step S3: Place the ball-milled powder in a vacuum induction furnace, introduce argon gas for protection, and heat and melt at 1300℃ for 40 minutes to obtain a molten alloy liquid.

[0080] Step S4: Add rare earth elements and nano TiB2 particles to the molten alloy, and hold it at an ultrasonic frequency of 50kHz for 25 minutes to obtain a particle dispersion reinforced alloy liquid.

[0081] Step S5: Cool the particle dispersion reinforced alloy liquid to 800℃ at a cooling rate of 10℃ / min, and then pass it through Ga under a cooling interface pressure of 0.5MPa. 62 In 25 Sn 13 Liquid metal coolant is subjected to ultra-rapid solidification at a cooling rate ≥1000℃ / s, followed by holding at 450℃ for 2 hours, then at 300℃ for 6 hours, and finally at 150℃ for 24 hours to complete multi-stage aging treatment, resulting in a high-strength alloy conductor.

[0082] Comparative Example 3:

[0083] This comparative example illustrates a method for preparing a high-strength alloy conductor, comprising the following steps:

[0084] Step S1: Add 35 mL of 67% concentrated nitric acid and 35 mL of 98% concentrated sulfuric acid to a three-necked flask equipped with a stirrer and thermometer. Stir the reaction at 30°C and 300 r / min for 5 min. Then add 2 g of high-purity multi-walled carbon nanotubes (TNM0) and continue stirring for 20 min. Then raise the temperature to 100°C and continue stirring for 5 h. After the reaction is complete, cool the reaction product to room temperature, centrifuge, wash the precipitate 5 times with distilled water, and then place it in a vacuum drying oven and dry it at 75°C for 2 h to obtain acidified carbon nanotubes.

[0085] Step S2: 1.6g of stannous chloride and 120mL of 1.2mol / L hydrochloric acid solution were added to a three-necked flask equipped with a stirrer and thermometer. The mixture was stirred at 30℃ and 300r / min for 20min. Then, 2g of acidified carbon nanotubes were added and the mixture was stirred for another 4h. After the reaction was completed, the reaction product was centrifuged and the precipitate was washed 5 times with distilled water. Then, it was placed in a vacuum drying oven and dried at 75℃ for 2h to obtain sensitized carbon nanotubes.

[0086] Step S3: Add 3g silver nitrate, 7mL concentrated ammonia (27% by mass), 0.4g sodium hydroxide, 0.3g polyvinylpyrrolidone (PVP K30), and 90mL deionized water to a three-necked flask equipped with a stirrer and thermometer. Stir the mixture at 30℃ and 300r / min for 30min. Then add 3g sensitized carbon nanotubes and continue stirring for another 30min. Next, add 90mL of a glucose solution prepared by mixing glucose, sodium tartrate, deionized water, and anhydrous ethanol in a ratio of 9g:0.6g:100mL:12mL and continue stirring for 4h. After the reaction is complete, centrifuge the reaction product, wash the precipitate five times with distilled water, and then place it in a vacuum drying oven at 55℃ for 3h to obtain silver-loaded carbon nanotubes.

[0087] Step S4: Weigh out 95.8 parts by weight of Cu powder, 5.0 parts by weight of Ag powder, 4.5 parts by weight of silver-loaded carbon nanotubes, 1.2 parts by weight of Cr powder, 0.5 parts by weight of ZrO2 powder, 0.15 parts by weight of rare earth elements, 0.8 parts by weight of nano-TiB2 particles, and 250 parts by weight of ethanol solution, and set aside for later use; the rare earth elements are a mixture of yttrium oxide and lanthanum oxide in a mass ratio of 2:1; the volume fraction of the ethanol solution is 90%.

[0088] Step S5: Add Cu powder, Ag powder, Cr powder, ZrO2 powder and anhydrous ethanol into a ball mill and ball mill for 6 hours at a ball-to-material ratio of 2:1 and a ball milling speed of 100 r / min. Then vacuum filter and place the filter cake in a vacuum drying oven and dry it at a temperature of 75℃ for 4 hours to obtain ball milled powder.

[0089] Step S6: Place the ball-milled powder in a vacuum induction furnace, introduce argon gas for protection, and heat and melt at 1300℃ for 40 minutes to obtain a molten alloy liquid.

[0090] Step S7: Add silver-loaded carbon nanotubes, rare earth elements and nano TiB2 particles to the molten alloy, and hold it at an ultrasonic frequency of 50kHz for 25 minutes to obtain a particle dispersion reinforced alloy liquid.

[0091] Step S8: Cool the particle dispersion reinforced alloy liquid to 800℃ at a cooling rate of 10℃ / min, and then pass it through Ga under a cooling interface pressure of 0.5MPa. 62 In 25 Sn 13Liquid metal coolant is subjected to ultra-rapid solidification at a cooling rate ≥1000℃ / s, followed by holding at 450℃ for 2 hours, then at 300℃ for 6 hours, and finally at 150℃ for 24 hours to complete multi-stage aging treatment, resulting in a high-strength alloy conductor.

[0092] Comparative Example 4:

[0093] This comparative example illustrates a method for preparing a high-strength alloy conductor, comprising the following steps:

[0094] Step S1: 10 mmol of 3-chloropropyltriethoxysilane, 10 mmol of triethanolamine, 13 mmol of potassium carbonate, 0.07 g of potassium iodide and 70 mL of anhydrous acetone were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 5 °C and 300 r / min for 30 min. Then the temperature was raised to 85 °C and the mixture was stirred for 12 h. After the reaction was completed, the reaction product was cooled to room temperature and then filtered under vacuum. The solvent was removed by rotary evaporation of the filtrate to obtain the ball milling enhancer.

[0095] Step S2: Weigh out 95.8 parts by weight of Cu powder, 5.0 parts by weight of Ag powder, 1.2 parts by weight of Cr powder, 0.5 parts by weight of ZrO2 powder, 0.15 parts by weight of rare earth elements, 0.8 parts by weight of nano-TiB2 particles, 6 parts by weight of ball milling enhancer, and 250 parts by weight of ethanol solution, and set aside for later use; the rare earth elements are a mixture of yttrium oxide and lanthanum oxide in a mass ratio of 2:1; the volume fraction of the ethanol solution is 90%.

[0096] Step S3: Add Cu powder, Ag powder, Cr powder, ZrO2 powder, ball milling enhancer and anhydrous ethanol into a ball mill, and ball mill for 6 hours at a ball-to-material ratio of 2:1 and a ball milling speed of 100 r / min. Then vacuum filter, place the filter cake in a vacuum drying oven and dry it at a temperature of 75℃ for 4 hours to obtain ball milled powder.

[0097] Step S4: Place the ball-milled powder in a vacuum induction furnace, introduce argon gas for protection, and heat and melt at 1300℃ for 40 minutes to obtain a molten alloy liquid.

[0098] Step S5: Add rare earth elements and nano TiB2 particles to the molten alloy, and hold it at a temperature of 50kHz for 25 minutes to obtain a particle dispersion reinforced alloy liquid.

[0099] Step S6: Cool the particle dispersion reinforced alloy liquid to 800℃ at a cooling rate of 10℃ / min, and then pass it through Ga under a cooling interface pressure of 0.5MPa. 62 In25 Sn 13 Liquid metal coolant is subjected to ultra-rapid solidification at a cooling rate ≥1000℃ / s, followed by holding at 450℃ for 2 hours, then at 300℃ for 6 hours, and finally at 150℃ for 24 hours to complete multi-stage aging treatment, resulting in a high-strength alloy conductor.

[0100] Comparative Example 5:

[0101] This comparative example illustrates a method for preparing a high-strength alloy conductor, comprising the following steps:

[0102] Step S1: Add 35 mL of 67% concentrated nitric acid and 35 mL of 98% concentrated sulfuric acid to a three-necked flask equipped with a stirrer and thermometer. Stir the reaction at 30°C and 300 r / min for 5 min. Then add 2 g of high-purity multi-walled carbon nanotubes (TNM0) and continue stirring for 20 min. Then raise the temperature to 100°C and continue stirring for 5 h. After the reaction is complete, cool the reaction product to room temperature, centrifuge, wash the precipitate 5 times with distilled water, and then place it in a vacuum drying oven and dry it at 75°C for 2 h to obtain acidified carbon nanotubes.

[0103] Step S2: 1.6g of stannous chloride and 120mL of 1.2mol / L hydrochloric acid solution were added to a three-necked flask equipped with a stirrer and thermometer. The mixture was stirred at 30℃ and 300r / min for 20min. Then, 2g of acidified carbon nanotubes were added and the mixture was stirred for another 4h. After the reaction was completed, the reaction product was centrifuged and the precipitate was washed 5 times with distilled water. Then, it was placed in a vacuum drying oven and dried at 75℃ for 2h to obtain sensitized carbon nanotubes.

[0104] Step S3: Add 3g silver nitrate, 7mL concentrated ammonia (27% by mass), 0.4g sodium hydroxide, 0.3g polyvinylpyrrolidone (PVP K30), and 90mL deionized water to a three-necked flask equipped with a stirrer and thermometer. Stir the mixture at 30℃ and 300r / min for 30min. Then add 3g sensitized carbon nanotubes and continue stirring for another 30min. Next, add 90mL of a glucose solution prepared by mixing glucose, sodium tartrate, deionized water, and anhydrous ethanol in a ratio of 9g:0.6g:100mL:12mL and continue stirring for 4h. After the reaction is complete, centrifuge the reaction product, wash the precipitate five times with distilled water, and then place it in a vacuum drying oven at 55℃ for 3h to obtain silver-loaded carbon nanotubes.

[0105] Step S4: 10 mmol of 3-chloropropyltriethoxysilane, 10 mmol of triethanolamine, 13 mmol of potassium carbonate, 0.07 g of potassium iodide and 70 mL of anhydrous acetone were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 5 °C and 300 r / min for 30 min. Then the temperature was raised to 85 °C and the mixture was stirred for 12 h. After the reaction was completed, the reaction product was cooled to room temperature and then filtered under vacuum. The solvent was removed by rotary evaporation of the filtrate to obtain the ball milling reinforcing agent.

[0106] Step S5: Weigh out 95.8 parts by weight of Cu powder, 5.0 parts by weight of Ag powder, 4.5 parts by weight of silver-loaded carbon nanotubes, 1.2 parts by weight of Cr powder, 0.5 parts by weight of ZrO2 powder, 0.15 parts by weight of rare earth elements, 6 parts by weight of ball milling enhancer, and 250 parts by weight of ethanol solution, and set aside for later use; the rare earth elements are a mixture of yttrium oxide and lanthanum oxide in a mass ratio of 2:1; the volume fraction of the ethanol solution is 90%.

[0107] Step S6: Add Cu powder, Ag powder, Cr powder, ZrO2 powder, ball milling enhancer and anhydrous ethanol into a ball mill, and ball mill for 6 hours at a ball-to-material ratio of 2:1 and a ball milling speed of 100 r / min. Then vacuum filter, place the filter cake in a vacuum drying oven and dry it at a temperature of 75℃ for 4 hours to obtain ball milled powder.

[0108] Step S7: Place the ball-milled powder in a vacuum induction furnace, introduce argon gas for protection, and heat and melt at 1300℃ for 40 minutes to obtain a molten alloy liquid.

[0109] Step S8: Add silver-loaded carbon nanotubes and rare earth elements to the molten alloy liquid, and hold it at an ultrasonic frequency of 50kHz for 25 minutes to obtain a particle dispersion reinforced alloy liquid.

[0110] Step S9: Cool the particle dispersion reinforced alloy liquid to 800℃ at a cooling rate of 10℃ / min, and then pass it through Ga under a cooling interface pressure of 0.5MPa. 62 In 25 Sn 13 Liquid metal coolant is subjected to ultra-rapid solidification at a cooling rate ≥1000℃ / s, followed by holding at 450℃ for 2 hours, then at 300℃ for 6 hours, and finally at 150℃ for 24 hours to complete multi-stage aging treatment, resulting in a high-strength alloy conductor.

[0111] The high-strength alloy conductors of Examples 1-3 and Comparative Examples 1-5 were tested for tensile strength and elongation according to GB / T 228.1-2021, and their conductivity was tested at 20°C using a four-point probe resistivity tester.

[0112] The test results are shown in the table below:

[0113]

[0114] Referring to the data in the table above, and based on the comparison between Examples 1-3 and Comparative Examples 1-5, it can be seen that adding nano-TiB2 particles, silver-loaded carbon nanotubes, and using a ball milling reinforcing agent can effectively improve the overall performance of the conductor, ultimately resulting in a high-strength alloy conductor with excellent mechanical and electrical properties.

[0115] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0116] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in this application, they should all fall within the protection scope of the present invention.

Claims

1. A high-strength alloy conductor, characterized in that, Includes the following components by weight: 92.5-95.8 parts Cu powder, 3.0-5.0 parts Ag powder, 1.1-4.5 parts silver-loaded carbon nanotubes, 0.5-1.2 parts Cr powder, 0.2-0.5 parts ZrO2 powder, 0.05-0.15 parts rare earth elements, 0.3-0.8 parts nano TiB2 particles, 1-6 parts ball milling reinforcing agent, and 220-250 parts ethanol solution; The silver-loaded carbon nanotubes are prepared by the following steps: Step a1: Stir concentrated nitric acid and concentrated sulfuric acid to react, then add carbon nanotubes and continue stirring to react. After the reaction is complete, cool the reaction product, then centrifuge, wash and dry the precipitate to obtain acidified carbon nanotubes. Step a2: Stir the stannous chloride and hydrochloric acid solution together, then add the acidified carbon nanotubes and continue stirring. After the reaction is complete, centrifuge the reaction product, wash and dry the precipitate to obtain the sensitized carbon nanotubes. Step a3: Silver nitrate, concentrated ammonia, sodium hydroxide, polyvinylpyrrolidone and deionized water are stirred and reacted. Then, sensitized carbon nanotubes and glucose solution are added and the reaction is continued to be stirred. After the reaction is completed, the reaction product is centrifuged, and the precipitate is washed and dried to obtain silver-loaded carbon nanotubes. The ball milling enhancer is prepared by the following steps: 3-Chloropropyltriethoxysilane, triethanolamine, potassium carbonate, potassium iodide, and anhydrous acetone were stirred and reacted. After the reaction was completed, the reaction product was cooled and then filtered under vacuum. The filtrate was evaporated by rotary evaporation to obtain a ball milling enhancer. The ratio of 3-chloropropyltriethoxysilane, triethanolamine, potassium carbonate, potassium iodide, and anhydrous acetone was 10 mmol: 10 mmol: 11-13 mmol: 0.05-0.07 g: 60-70 mL.

2. The high-strength alloy conductor according to claim 1, characterized in that, In step a1, the ratio of concentrated nitric acid, concentrated sulfuric acid, and carbon nanotubes is 30-35 mL: 30-35 mL: 2 g; the mass fraction of the concentrated nitric acid is 67%; the mass fraction of the concentrated sulfuric acid is 98%; and the carbon nanotubes are high-purity multi-walled carbon nanotubes (TNM0).

3. The high-strength alloy conductor according to claim 1, characterized in that, In step a2, the ratio of stannous chloride, hydrochloric acid solution, and acidified carbon nanotubes is 0.8-1.6g:100-120mL:2g; the molar concentration of the hydrochloric acid solution is 1-1.2mol / L.

4. The high-strength alloy conductor according to claim 1, characterized in that, In step a3, the ratio of silver nitrate, concentrated ammonia, sodium hydroxide, polyvinylpyrrolidone, deionized water, sensitized carbon nanotubes, and glucose solution is 2-3g: 5-7mL: 0.2-0.4g: 0.1-0.3g: 80-90mL: 3g: 80-90mL; the mass fraction of the concentrated ammonia is 25-27%; the polyvinylpyrrolidone is PVP K30; and the glucose solution is a mixture of glucose, sodium tartrate, deionized water, and anhydrous ethanol in a ratio of 7-9g: 0.5-0.6g: 90-100mL: 10-12mL.

5. A method for preparing a high-strength alloy conductor as described in any one of claims 1-4, characterized in that, Includes the following steps: Step 1: Weigh out the following components by weight: 92.5-95.8 parts Cu powder, 3.0-5.0 parts Ag powder, 1.1-4.5 parts silver-loaded carbon nanotubes, 0.5-1.2 parts Cr powder, 0.2-0.5 parts ZrO2 powder, 0.05-0.15 parts rare earth elements, 0.3-0.8 parts nano TiB2 particles, 1-6 parts ball milling reinforcing agent, and 220-250 parts ethanol solution. Set aside for later use. Step 2: Add Cu powder, Ag powder, Cr powder, ZrO2 powder, ball milling enhancer, and ethanol solution to a ball mill. Ball mill for 5-6 hours at a ball-to-material ratio of 2:1 and a ball milling speed of 80-100 r / min. Then, vacuum filter the mixture and place the filter cake in a vacuum drying oven. Dry the cake at 70-75℃ for 3-4 hours to obtain the ball milled powder. Step 3: Place the ball-milled powder in a vacuum induction furnace, introduce argon gas for protection, and heat and melt at a temperature of 1250-1300℃ for 30-40 minutes to obtain a molten alloy liquid. Step 4: Add silver-loaded carbon nanotubes, rare earth elements and nano TiB2 particles to the molten alloy, and hold it at an ultrasonic frequency of 40-50kHz for 15-25 minutes to obtain a particle dispersion reinforced alloy liquid. Step 5: Cool the particle dispersion reinforced alloy liquid to 800℃ at a cooling rate of 5-10℃ / min, then perform ultra-fast solidification with liquid metal coolant under a cooling interface pressure of 0.2-0.5MPa, followed by multi-stage aging treatment to obtain a high-strength alloy conductor.

6. The method for preparing a high-strength alloy conductor according to claim 5, characterized in that, The liquid metal coolant is a Ga-In-Sn alloy, and the composition of the Ga-In-Sn alloy is Ga... 62 In 25 Sn 13 The cooling rate during the ultra-fast solidification process is ≥1000℃ / s.

7. The method for preparing a high-strength alloy conductor according to claim 5, characterized in that, The specific process of the multi-stage aging treatment is as follows: keep warm at 450℃ for 2 hours, then keep warm at 300℃ for 6 hours, and then keep warm at 150℃ for 24 hours.

8. The method for preparing a high-strength alloy conductor according to claim 5, characterized in that, The rare earth elements are a mixture of yttrium oxide and lanthanum oxide in a mass ratio of 2:1; the volume fraction of the ethanol solution is 90%.

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