High-strength corrosion-resistant copper alloy wire and method of making same

Abstract

The application discloses a preparation method of high-strength corrosion-resistant copper alloy wire, which comprises the following steps: (1) preparing a composite powder; (2) preparing a pretreated powder; (3) sensitizing treatment, activation, and surface chemical copper plating of the activated powder to obtain a copper-plated powder; (4) weighing copper powder, nickel powder, silicon powder and the copper-plated powder, heating and melting, adding the copper-plated powder into the melt, casting and forming, heating and stress elimination, cooling, and drawing into copper alloy wire by using a wire drawing machine; the copper alloy wire is kept at 220 DEG C for 30 min, then heated to 300 DEG C and kept for aging for 3 h, after the keeping, the copper alloy wire is cooled to below 200 DEG C in the furnace, then taken out and cooled to room temperature, and the high-strength corrosion-resistant copper alloy wire is obtained. The copper alloy casting prepared by using the method has high tensile strength, the copper alloy wire has high self-corrosion potential, and good strength and corrosion resistance are exhibited.

Description

Technical Field

[0001] This invention relates to the field of copper alloy conductor materials technology, and in particular to a high-strength corrosion-resistant copper alloy wire and its preparation method. Background Technology

[0002] High-strength copper alloy wire is a material that significantly improves mechanical properties while maintaining good conductivity, and is widely used in electronics, power, aerospace, automotive and other industries. In some demanding applications, copper alloy wires are required to have high strength and high corrosion resistance. Improper alloying or processing may lead to insufficient strength and make the wires prone to oxidation and rust (such as verdigris) in humid, salt spray or acidic environments, affecting their normal use. Summary of the Invention

[0003] Therefore, the present invention provides a method for preparing a high-strength corrosion-resistant copper alloy wire, comprising the following steps:

[0004] (1) Prepare a composite aqueous solution of erbium nitrate and zirconium nitrate in a reactor; then add boron trioxide powder, hexadecyltrimethylammonium bromide and urea to the solution under stirring. After the addition is completed, continue stirring until uniform. Then seal the reactor, heat to 150-180℃ and keep warm for more than 2 hours, then cool to room temperature, open the reactor, pour out the material in the reactor, evaporate the liquid phase, and then calcine at 950-1100℃ under a protective gas atmosphere to obtain composite powder.

[0005] (2) Dissolve cysteine ​​in deionized water to form a cysteine ​​solution; add the composite powder to the cysteine ​​solution to form a suspension; add 3-glycidyloxypropyltrimethoxysilane to the suspension while stirring; adjust the pH of the suspension to 9-11; heat to 90±5℃ and stir for more than 5 hours; after the heat preservation is completed, cool, separate the solid and liquid, wash the solid phase, and dry to obtain the pretreated powder.

[0006] (3) Prepare an aqueous solution of stannous chloride as a sensitizing solution and an aqueous solution of silver nitrate as an activating solution; immerse the pretreated powder in the sensitizing solution for sensitization treatment, then immerse it in the activating solution for activation, and perform surface chemical copper plating on the activated powder to obtain copper-plated powder.

[0007] (4) Mix copper powder, nickel powder and silicon powder to form a mixed powder. Heat the mixed powder to melt in a protective gas atmosphere, stir the melt, and then add the copper plating powder into the melt. After adding the material, stir and mix it evenly, and immediately cast it into a mold to form a copper alloy casting. Cool the copper alloy casting in the mold, and then heat the casting to 900-920℃ and hold it for 1-2 hours to relieve stress. Then cool it to 150-200℃ and draw it into a copper alloy wire using a wire drawing machine. Hold the copper alloy wire at 200-250℃ for 30-40 minutes, and then raise the temperature to 280-350℃ and hold it for 3-4 hours. After the holding period, cool it with the furnace to below 200℃, and then take it out and air cool it to room temperature to obtain the high-strength corrosion-resistant copper alloy wire.

[0008] Further, in step (1), the concentration of erbium nitrate in the composite aqueous solution of erbium nitrate and zirconium nitrate is 0.8-1.2 g / L, the concentration of zirconium nitrate is 20-30 g / L, and the solvent is water; the ratio of boron trioxide powder, hexadecyltrimethylammonium bromide, and urea added to the solution is: composite aqueous solution of erbium nitrate and zirconium nitrate: boron trioxide powder: hexadecyltrimethylammonium bromide: urea = 100 mL: 3-6 g: 0.5-0.8 g: 3-4 g; the calcination time is 1-2 h.

[0009] Further, in step (2), the concentration of cysteine ​​in the cysteine ​​solution is 2-4 g / 100 mL, and the solvent is water; the ratio of the composite powder, 3-glycidoxypropyltrimethoxysilane and cysteine ​​solution is composite powder: cysteine ​​solution: 3-glycidoxypropyltrimethoxysilane = 1 g: 50-200 mL: 1-2 g.

[0010] Further, in step (3), the stannous chloride aqueous solution contains 4% to 5% stannous chloride by mass and water as the solvent; the silver nitrate aqueous solution contains 9% to 10% silver nitrate by mass and water as the solvent.

[0011] Furthermore, in step (3), the formulation of the plating solution in the surface chemical copper plating is as follows: copper sulfate 8-10 g / L, potassium sodium tartrate 35-40 g / L, formaldehyde 14-16 mL / L, potassium hydroxide 7-9 g / L; the temperature of chemical plating is 60±3℃, and the plating time is more than 10 min.

[0012] Further, in step (4), the copper powder, nickel powder, silicon powder and copper plating powder used are in the following weight parts: 100 parts copper powder, 1.8 to 2.2 parts nickel powder, 0.5 to 0.6 parts silicon powder and 1 to 2 parts copper plating powder.

[0013] Furthermore, in step (4), the melting temperature is 1380–1420°C; and the casting temperature is 1200–1250°C.

[0014] The beneficial effects of this invention are as follows: the copper alloy castings prepared by the method described in this invention have high tensile strength, and the prepared copper alloy wires have high self-corrosion potential, exhibiting good strength and corrosion resistance. The main reason may be that by adding the copper-plating powder prepared in this invention, the compatibility between the powder particles and the copper alloy melt is improved through copper plating, reducing two-phase interface defects caused by insufficient compatibility between the powder particles and the copper alloy matrix during casting cooling, thereby improving the overall strength and corrosion resistance of the material. Furthermore, by adding boron-zirconium-erbium composite oxide powder, it can act as non-uniform nucleation sites, significantly refining the grain size of the as-cast copper alloy. The added zirconium and erbium elements can form granular phases with copper, located at the two-phase interface and grain boundaries, playing a second-phase strengthening role. Cysteine ​​solution and 3-glycidyloxypropyltrimethoxysilane are beneficial for improving the particle surface condition, promoting the electroless copper plating process, increasing the adhesion between the copper plating layer and the particle surface, and reducing interface defects. Attached Figure Description

[0015] Figure 1 The diagram shows a comparison of the tensile strength and self-corrosion potential of the copper alloy materials prepared by the methods described in the various embodiments and comparative examples. Detailed Implementation

[0016] The present invention will be further described below with reference to the embodiments.

[0017] Example 1

[0018] A method for preparing a high-strength, corrosion-resistant copper alloy wire includes the following steps:

[0019] (1) Prepare a composite aqueous solution of erbium nitrate and zirconium nitrate in a reaction vessel; the concentration of erbium nitrate in the composite aqueous solution of erbium nitrate and zirconium nitrate is 0.8 g / L, the concentration of zirconium nitrate is 20 g / L, and the solvent is water; then add boron trioxide powder, hexadecyltrimethylammonium bromide and urea to the solution under stirring, the ratio of boron trioxide powder, hexadecyltrimethylammonium bromide and urea added to the solution is composite aqueous solution of erbium nitrate and zirconium nitrate: boron trioxide powder: hexadecyltrimethylammonium bromide: urea = 100 mL: 3 g: 0.5 g: 3 g; after the addition is completed, continue stirring for 10 min to homogenize, then seal the reaction vessel, heat to 150℃ and keep warm for 2 h, then cool to room temperature, open the reaction vessel, pour out the material in the reaction vessel, evaporate the liquid phase in a 100℃ drying oven, and then calcine at 1000℃ for 30 min under an argon atmosphere to obtain composite powder;

[0020] (2) Cysteine ​​is dissolved in deionized water to form a cysteine ​​solution; the concentration of cysteine ​​in the cysteine ​​solution is 2g / 100mL, and the solvent is water; the composite powder is added to the cysteine ​​solution to form a suspension, and 3-glycidyloxypropyltrimethoxysilane is added to the suspension under stirring, with the ratio of the composite powder, 3-glycidyloxypropyltrimethoxysilane and cysteine ​​solution being composite powder: cysteine ​​solution: 3-glycidyloxypropyltrimethoxysilane = 1g: 100mL: 1g; the pH of the suspension is adjusted to 10 with a 10% sodium hydroxide aqueous solution, heated to 90℃ and stirred for 5h, cooled after the heating is completed, the solid and liquid are separated, the solid phase is washed 3 times with deionized water, and dried at 80℃ for 1h to obtain the pretreated powder;

[0021] (3) Prepare an aqueous solution of stannous chloride as a sensitizing solution and an aqueous solution of silver nitrate as an activating solution; the stannous chloride aqueous solution contains 4% stannous chloride by mass and water as the solvent; the silver nitrate aqueous solution contains 9% silver nitrate by mass and water as the solvent; sensitize the pretreated powder by immersing it in the sensitizing solution for 5 min, then activate it by immersing it in the activating solution for 10 min, and then perform surface chemical copper plating on the activated powder to obtain copper-plated powder; the formulation of the plating solution in the surface chemical copper plating is: 8 g / L copper sulfate, 35 g / L sodium potassium tartrate, 14 mL / L formaldehyde, and 7 g / L potassium hydroxide; the chemical plating temperature is 60℃ and the plating time is 10 min;

[0022] (4) Weigh out copper powder, nickel powder, silicon powder, and copper plating powder. The weight proportions of copper powder, nickel powder, silicon powder, and copper plating powder are as follows: 100 parts copper powder, 1.8 parts nickel powder, 0.5 parts silicon powder, and 1 part copper plating powder. Mix the copper powder, nickel powder, and silicon powder to form a mixed powder. Heat the mixed powder to 1400°C in an argon atmosphere to melt it. Stir the melt, then add the copper plating powder to the melt. Stir and mix for 5 minutes after adding the powder. Then cool it to 1200°C while stirring, and immediately pour it into a mold. The copper alloy casting is cooled in a mold, then removed and heated to 900℃ for 1 hour to relieve stress. Some samples are cooled to room temperature and processed into mechanical test specimens, while others are cooled to 180℃ and drawn into copper alloy wires using a wire drawing machine. The copper alloy wires are then held at 220℃ for 30 minutes, then heated to 300℃ and held for 3 hours. After the holding period, the wires are cooled to below 200℃ in the furnace and then air-cooled to room temperature to obtain the high-strength corrosion-resistant copper alloy wire.

[0023] Example 2

[0024] A method for preparing a high-strength, corrosion-resistant copper alloy wire includes the following steps:

[0025] (1) Prepare a composite aqueous solution of erbium nitrate and zirconium nitrate in a reaction vessel; the concentration of erbium nitrate in the composite aqueous solution of erbium nitrate and zirconium nitrate is 1 g / L, the concentration of zirconium nitrate is 25 g / L, and the solvent is water; then add boron trioxide powder, hexadecyltrimethylammonium bromide and urea to the solution under stirring, the ratio of boron trioxide powder, hexadecyltrimethylammonium bromide and urea added to the solution is composite aqueous solution of erbium nitrate and zirconium nitrate: boron trioxide powder: hexadecyltrimethylammonium bromide: urea = 100 mL: 4 g: 0.6 g: 3 g; after the addition is completed, continue stirring for 10 min to homogenize, then seal the reaction vessel, heat to 160℃ and keep warm for 2 h, then cool to room temperature, open the reaction vessel, pour out the material in the reaction vessel, evaporate the liquid phase in a 100℃ drying oven, and then calcine at 1000℃ for 30 min under an argon atmosphere to obtain composite powder;

[0026] (2) Cysteine ​​is dissolved in deionized water to form a cysteine ​​solution; the concentration of cysteine ​​in the cysteine ​​solution is 3g / 100mL, and the solvent is water; the composite powder is added to the cysteine ​​solution to form a suspension, and 3-glycidyloxypropyltrimethoxysilane is added to the suspension under stirring, with the ratio of the composite powder, 3-glycidyloxypropyltrimethoxysilane and cysteine ​​solution being composite powder: cysteine ​​solution: 3-glycidyloxypropyltrimethoxysilane = 1g: 100mL: 1g; the pH of the suspension is adjusted to 10 with a 10% sodium hydroxide aqueous solution, heated to 90℃ and stirred for 5h, cooled after the heating is completed, the solid and liquid are separated, the solid phase is washed 3 times with deionized water, and dried at 80℃ for 1h to obtain the pretreated powder;

[0027] (3) Prepare an aqueous solution of stannous chloride as a sensitizing solution and an aqueous solution of silver nitrate as an activating solution; the stannous chloride aqueous solution contains 4% stannous chloride by mass and water as the solvent; the silver nitrate aqueous solution contains 9% silver nitrate by mass and water as the solvent; sensitize the pretreated powder by immersing it in the sensitizing solution for 5 minutes, then activate it by immersing it in the activating solution for 10 minutes, and then perform surface chemical copper plating on the activated powder to obtain copper-plated powder; the formulation of the plating solution in the surface chemical copper plating is: 9 g / L copper sulfate, 35 g / L sodium potassium tartrate, 15 mL / L formaldehyde, and 8 g / L potassium hydroxide; the chemical plating temperature is 60℃ and the plating time is 10 minutes.

[0028] (4) Weigh out copper powder, nickel powder, silicon powder, and copper plating powder. The weight proportions of copper powder, nickel powder, silicon powder, and copper plating powder are: 100 parts copper powder, 2 parts nickel powder, 0.5 parts silicon powder, and 1 part copper plating powder. Mix the copper powder, nickel powder, and silicon powder to form a mixed powder. Heat the mixed powder to 1400°C in an argon atmosphere to melt it. Stir the melt, then add the copper plating powder to the melt. After adding the material, stir and mix for 5 minutes. Then, cool it to 1200°C while stirring, and immediately pour it into a mold to form a copper plating powder. The copper alloy casting is cooled in a mold, then removed and heated to 900℃ for 1 hour to relieve stress. Some samples are cooled to room temperature and processed into mechanical test specimens, while others are cooled to 180℃ and drawn into copper alloy wires using a wire drawing machine. The copper alloy wires are then held at 220℃ for 30 minutes, then heated to 300℃ and held for 3 hours. After the holding period, the wires are cooled to below 200℃ in the furnace and then air-cooled to room temperature to obtain the high-strength corrosion-resistant copper alloy wire.

[0029] Example 3

[0030] A method for preparing a high-strength, corrosion-resistant copper alloy wire includes the following steps:

[0031] (1) Prepare a composite aqueous solution of erbium nitrate and zirconium nitrate in a reaction vessel; the concentration of erbium nitrate in the composite aqueous solution of erbium nitrate and zirconium nitrate is 1 g / L, the concentration of zirconium nitrate is 25 g / L, and the solvent is water; then add boron trioxide powder, hexadecyltrimethylammonium bromide and urea to the solution under stirring, the ratio of boron trioxide powder, hexadecyltrimethylammonium bromide and urea added to the solution is composite aqueous solution of erbium nitrate and zirconium nitrate: boron trioxide powder: hexadecyltrimethylammonium bromide: urea = 100 mL: 5 g: 0.7 g: 4 g; after the addition is completed, continue stirring for 10 min to homogenize, then seal the reaction vessel, heat to 170℃ and keep warm for 2 h, then cool to room temperature, open the reaction vessel, pour out the material in the reaction vessel, evaporate the liquid phase in a 100℃ drying oven, and then heat to 1000℃ and calcine for 30 min under an argon atmosphere to obtain composite powder;

[0032] (2) Cysteine ​​is dissolved in deionized water to form a cysteine ​​solution; the concentration of cysteine ​​in the cysteine ​​solution is 3g / 100mL, and the solvent is water; the composite powder is added to the cysteine ​​solution to form a suspension, and 3-glycidyloxypropyltrimethoxysilane is added to the suspension under stirring, with the ratio of the composite powder, 3-glycidyloxypropyltrimethoxysilane and cysteine ​​solution being composite powder: cysteine ​​solution: 3-glycidyloxypropyltrimethoxysilane = 1g: 100mL: 2g; the pH of the suspension is adjusted to 10 with a 10% sodium hydroxide aqueous solution, heated to 90℃ and stirred for 5h, cooled after the heating is completed, the solid and liquid are separated, the solid phase is washed 3 times with deionized water and dried at 80℃ for 1h to obtain the pretreated powder;

[0033] (3) Prepare an aqueous solution of stannous chloride as a sensitizing solution and an aqueous solution of silver nitrate as an activating solution; the stannous chloride aqueous solution contains 5% stannous chloride by mass and water as the solvent; the silver nitrate aqueous solution contains 10% silver nitrate by mass and water as the solvent; sensitize the pretreated powder by immersing it in the sensitizing solution for 5 minutes, then activate it by immersing it in the activating solution for 10 minutes, and then perform surface chemical copper plating on the activated powder to obtain copper-plated powder; the formulation of the plating solution in the surface chemical copper plating is: 9 g / L copper sulfate, 40 g / L sodium potassium tartrate, 15 mL / L formaldehyde, and 8 g / L potassium hydroxide; the chemical plating temperature is 60℃ and the plating time is 10 minutes;

[0034] (4) Weigh out copper powder, nickel powder, silicon powder, and copper plating powder. The weight proportions of copper powder, nickel powder, silicon powder, and copper plating powder are: 100 parts copper powder, 2 parts nickel powder, 0.6 parts silicon powder, and 2 parts copper plating powder. Mix the copper powder, nickel powder, and silicon powder to form a mixed powder. Heat the mixed powder to 1400°C in an argon atmosphere to melt it. Stir the melt, then add the copper plating powder to the melt. After adding the material, stir and mix for 5 minutes. Then, cool it to 1200°C while stirring, and immediately pour it into a mold to form a copper plating powder. The copper alloy casting is cooled in a mold, then removed and heated to 900℃ for 1 hour to relieve stress. Some samples are cooled to room temperature and processed into mechanical test specimens, while others are cooled to 180℃ and drawn into copper alloy wires using a wire drawing machine. The copper alloy wires are then held at 220℃ for 30 minutes, then heated to 300℃ and held for 3 hours. After the holding period, the wires are cooled to below 200℃ in the furnace and then air-cooled to room temperature to obtain the high-strength corrosion-resistant copper alloy wire.

[0035] Example 4

[0036] A method for preparing a high-strength, corrosion-resistant copper alloy wire includes the following steps:

[0037] (1) Prepare a composite aqueous solution of erbium nitrate and zirconium nitrate in a reaction vessel; the concentration of erbium nitrate in the composite aqueous solution of erbium nitrate and zirconium nitrate is 1.2 g / L, the concentration of zirconium nitrate is 30 g / L, and the solvent is water; then add boron trioxide powder, hexadecyltrimethylammonium bromide and urea to the solution under stirring, the ratio of boron trioxide powder, hexadecyltrimethylammonium bromide and urea added to the solution is composite aqueous solution of erbium nitrate and zirconium nitrate: boron trioxide powder: hexadecyltrimethylammonium bromide: urea = 100 mL: 6 g: 0.8 g: 4 g; after the addition is completed, continue stirring for 10 min to homogenize, then seal the reaction vessel, heat to 180℃ and keep warm for 2 h, then cool to room temperature, open the reaction vessel, pour out the material in the reaction vessel, evaporate the liquid phase in a 100℃ drying oven, and then calcine at 1000℃ for 30 min under an argon atmosphere to obtain composite powder;

[0038] (2) Cysteine ​​is dissolved in deionized water to form a cysteine ​​solution; the concentration of cysteine ​​in the cysteine ​​solution is 4g / 100mL, and the solvent is water; the composite powder is added to the cysteine ​​solution to form a suspension, and 3-glycidyloxypropyltrimethoxysilane is added to the suspension under stirring, with the ratio of the composite powder, 3-glycidyloxypropyltrimethoxysilane and cysteine ​​solution being composite powder: cysteine ​​solution: 3-glycidyloxypropyltrimethoxysilane = 1g: 100mL: 2g; the pH of the suspension is adjusted to 10 with a 10% sodium hydroxide aqueous solution, heated to 90℃ and stirred for 5h, cooled after the heating is completed, the solid and liquid are separated, the solid phase is washed 3 times with deionized water and dried at 80℃ for 1h to obtain the pretreated powder;

[0039] (3) Prepare an aqueous solution of stannous chloride as a sensitizing solution and an aqueous solution of silver nitrate as an activating solution; the stannous chloride aqueous solution contains 5% stannous chloride by mass and water as the solvent; the silver nitrate aqueous solution contains 10% silver nitrate by mass and water as the solvent; sensitize the pretreated powder by immersing it in the sensitizing solution for 5 minutes, then activate it by immersing it in the activating solution for 10 minutes, and then perform surface chemical copper plating on the activated powder to obtain copper-plated powder; the formulation of the plating solution in the surface chemical copper plating is: 10 g / L copper sulfate, 40 g / L sodium potassium tartrate, 16 mL / L formaldehyde, and 9 g / L potassium hydroxide; the chemical plating temperature is 60℃ and the plating time is 10 minutes;

[0040] (4) Weigh out copper powder, nickel powder, silicon powder, and copper plating powder. The weight proportions of copper powder, nickel powder, silicon powder, and copper plating powder are as follows: 100 parts copper powder, 2.2 parts nickel powder, 0.6 parts silicon powder, and 2 parts copper plating powder. Mix the copper powder, nickel powder, and silicon powder to form a mixed powder. Heat the mixed powder to 1400°C in an argon atmosphere to melt it. Stir the melt, then add the copper plating powder to the melt. Stir and mix for 5 minutes after adding the powder. Then cool it to 1200°C while stirring, and immediately pour it into a mold. The copper alloy casting is cooled in a mold, then removed and heated to 900℃ for 1 hour to relieve stress. Some samples are cooled to room temperature and processed into mechanical test specimens, while others are cooled to 180℃ and drawn into copper alloy wires using a wire drawing machine. The copper alloy wires are then held at 220℃ for 30 minutes, then heated to 300℃ and held for 3 hours. After the holding period, the wires are cooled to below 200℃ in the furnace and then air-cooled to room temperature to obtain the high-strength corrosion-resistant copper alloy wire.

[0041] Comparative Example 1

[0042] A comparative method for preparing copper alloy wire includes the following steps:

[0043] (1) Prepare an aqueous solution of erbium nitrate in a reaction vessel; the concentration of erbium nitrate in the aqueous solution of erbium nitrate is 1 g / L, and the solvent is water; then add boron trioxide powder, hexadecyltrimethylammonium bromide and urea to the solution under stirring, and the ratio of the amount of boron trioxide powder, hexadecyltrimethylammonium bromide and urea added to the solution is aqueous solution of erbium nitrate: boron trioxide powder: hexadecyltrimethylammonium bromide: urea = 100 mL: 5 g: 0.7 g: 4 g; after the addition is completed, continue stirring for 10 min to make it uniform, then seal the reaction vessel, heat to 170℃ and keep it at that temperature for 2 h, then cool to room temperature, open the reaction vessel, pour out the material in the reaction vessel, evaporate the liquid phase in a 100℃ drying oven, and then calcine at 1000℃ for 30 min under an argon atmosphere to obtain composite powder;

[0044] (2) Cysteine ​​is dissolved in deionized water to form a cysteine ​​solution; the concentration of cysteine ​​in the cysteine ​​solution is 3g / 100mL, and the solvent is water; the composite powder is added to the cysteine ​​solution to form a suspension, and 3-glycidyloxypropyltrimethoxysilane is added to the suspension under stirring, with the ratio of the composite powder, 3-glycidyloxypropyltrimethoxysilane and cysteine ​​solution being composite powder: cysteine ​​solution: 3-glycidyloxypropyltrimethoxysilane = 1g: 100mL: 2g; the pH of the suspension is adjusted to 10 with a 10% sodium hydroxide aqueous solution, heated to 90℃ and stirred for 5h, cooled after the heating is completed, the solid and liquid are separated, the solid phase is washed 3 times with deionized water and dried at 80℃ for 1h to obtain the pretreated powder;

[0045] (3) Prepare an aqueous solution of stannous chloride as a sensitizing solution and an aqueous solution of silver nitrate as an activating solution; the stannous chloride aqueous solution contains 5% stannous chloride by mass and water as the solvent; the silver nitrate aqueous solution contains 10% silver nitrate by mass and water as the solvent; sensitize the pretreated powder by immersing it in the sensitizing solution for 5 minutes, then activate it by immersing it in the activating solution for 10 minutes, and then perform surface chemical copper plating on the activated powder to obtain copper-plated powder; the formulation of the plating solution in the surface chemical copper plating is: 9 g / L copper sulfate, 40 g / L sodium potassium tartrate, 15 mL / L formaldehyde, and 8 g / L potassium hydroxide; the chemical plating temperature is 60℃ and the plating time is 10 minutes;

[0046] (4) Weigh out copper powder, nickel powder, silicon powder, and copper plating powder. The weight proportions of copper powder, nickel powder, silicon powder, and copper plating powder are: 100 parts copper powder, 2 parts nickel powder, 0.6 parts silicon powder, and 2 parts copper plating powder. Mix the copper powder, nickel powder, and silicon powder to form a mixed powder. Heat the mixed powder to 1400°C in an argon atmosphere to melt it. Stir the melt, then add the copper plating powder to the melt. After adding the material, stir and mix for 5 minutes. Then, cool it to 1200°C while stirring, and immediately pour it into a mold to form a copper plating powder. The copper alloy casting is cooled in a mold, then removed and heated to 900℃ for 1 hour to relieve stress. Some samples are cooled to room temperature and processed into mechanical test specimens, while others are cooled to 180℃ and drawn into copper alloy wires using a wire drawing machine. The copper alloy wires are then held at 220℃ for 30 minutes, then heated to 300℃ and held for 3 hours. After the holding period, the wires are cooled to below 200℃ in the furnace and then air-cooled to room temperature to obtain the high-strength corrosion-resistant copper alloy wire.

[0047] Comparative Example 2

[0048] A comparative method for preparing copper alloy wire includes the following steps:

[0049] (1) Prepare an aqueous solution of zirconium nitrate in a reactor; the concentration of zirconium nitrate in the aqueous solution of zirconium nitrate is 25 g / L, and the solvent is water; then add boron trioxide powder, hexadecyltrimethylammonium bromide and urea to the solution under stirring, and the ratio of boron trioxide powder, hexadecyltrimethylammonium bromide and urea added to the solution is aqueous solution of zirconium nitrate: boron trioxide powder: hexadecyltrimethylammonium bromide: urea = 100 mL: 5 g: 0.7 g: 4 g; after the addition is completed, continue stirring for 10 min to make it uniform, then seal the reactor, heat to 170℃ and keep it at that temperature for 2 h, then cool to room temperature, open the reactor, pour out the material in the reactor, evaporate the liquid phase in a 100℃ drying oven, and then calcine at 1000℃ for 30 min under an argon atmosphere to obtain composite powder;

[0050] (2) Cysteine ​​is dissolved in deionized water to form a cysteine ​​solution; the concentration of cysteine ​​in the cysteine ​​solution is 3g / 100mL, and the solvent is water; the composite powder is added to the cysteine ​​solution to form a suspension, and 3-glycidyloxypropyltrimethoxysilane is added to the suspension under stirring, with the ratio of the composite powder, 3-glycidyloxypropyltrimethoxysilane and cysteine ​​solution being composite powder: cysteine ​​solution: 3-glycidyloxypropyltrimethoxysilane = 1g: 100mL: 2g; the pH of the suspension is adjusted to 10 with a 10% sodium hydroxide aqueous solution, heated to 90℃ and stirred for 5h, cooled after the heating is completed, the solid and liquid are separated, the solid phase is washed 3 times with deionized water and dried at 80℃ for 1h to obtain the pretreated powder;

[0051] (3) Prepare an aqueous solution of stannous chloride as a sensitizing solution and an aqueous solution of silver nitrate as an activating solution; the stannous chloride aqueous solution contains 5% stannous chloride by mass and water as the solvent; the silver nitrate aqueous solution contains 10% silver nitrate by mass and water as the solvent; sensitize the pretreated powder by immersing it in the sensitizing solution for 5 minutes, then activate it by immersing it in the activating solution for 10 minutes, and then perform surface chemical copper plating on the activated powder to obtain copper-plated powder; the formulation of the plating solution in the surface chemical copper plating is: 9 g / L copper sulfate, 40 g / L sodium potassium tartrate, 15 mL / L formaldehyde, and 8 g / L potassium hydroxide; the chemical plating temperature is 60℃ and the plating time is 10 minutes;

[0052] (4) Weigh out copper powder, nickel powder, silicon powder, and copper plating powder. The weight proportions of copper powder, nickel powder, silicon powder, and copper plating powder are: 100 parts copper powder, 2 parts nickel powder, 0.6 parts silicon powder, and 2 parts copper plating powder. Mix the copper powder, nickel powder, and silicon powder to form a mixed powder. Heat the mixed powder to 1400°C in an argon atmosphere to melt it. Stir the melt, then add the copper plating powder to the melt. After adding the material, stir and mix for 5 minutes. Then, cool it to 1200°C while stirring, and immediately pour it into a mold to form a copper plating powder. The copper alloy casting is cooled in a mold, then removed and heated to 900℃ for 1 hour to relieve stress. Some samples are cooled to room temperature and processed into mechanical test specimens, while others are cooled to 180℃ and drawn into copper alloy wires using a wire drawing machine. The copper alloy wires are then held at 220℃ for 30 minutes, then heated to 300℃ and held for 3 hours. After the holding period, the wires are cooled to below 200℃ in the furnace and then air-cooled to room temperature to obtain the high-strength corrosion-resistant copper alloy wire.

[0053] Comparative Example 3

[0054] A comparative method for preparing copper alloy wire includes the following steps:

[0055] (1) Prepare a composite aqueous solution of erbium nitrate and zirconium nitrate in a reaction vessel; the concentration of erbium nitrate in the composite aqueous solution of erbium nitrate and zirconium nitrate is 1 g / L, the concentration of zirconium nitrate is 25 g / L, and the solvent is water; then add boron trioxide powder, hexadecyltrimethylammonium bromide and urea to the solution under stirring, the ratio of boron trioxide powder, hexadecyltrimethylammonium bromide and urea added to the solution is composite aqueous solution of erbium nitrate and zirconium nitrate: boron trioxide powder: hexadecyltrimethylammonium bromide: urea = 100 mL: 5 g: 0.7 g: 4 g; after the addition is completed, continue stirring for 10 min to homogenize, then seal the reaction vessel, heat to 170℃ and keep warm for 2 h, then cool to room temperature, open the reaction vessel, pour out the material in the reaction vessel, evaporate the liquid phase in a 100℃ drying oven, and then heat to 1000℃ and calcine for 30 min under an argon atmosphere to obtain composite powder;

[0056] (2) Prepare an aqueous solution of stannous chloride as a sensitizing solution and an aqueous solution of silver nitrate as an activating solution; the stannous chloride aqueous solution contains 5% stannous chloride by mass and water as the solvent; the silver nitrate aqueous solution contains 10% silver nitrate by mass and water as the solvent; sensitize the composite powder by immersing it in the sensitizing solution for 5 minutes, then activate it by immersing it in the activating solution for 10 minutes, and then perform surface chemical copper plating on the activated powder to obtain copper-plated powder; the formulation of the plating solution in the surface chemical copper plating is: 9 g / L copper sulfate, 40 g / L sodium potassium tartrate, 15 mL / L formaldehyde, and 8 g / L potassium hydroxide; the chemical plating temperature is 60℃ and the plating time is 10 minutes.

[0057] (3) Weigh out copper powder, nickel powder, silicon powder, and copper plating powder. The weight proportions of copper powder, nickel powder, silicon powder, and copper plating powder are: 100 parts copper powder, 2 parts nickel powder, 0.6 parts silicon powder, and 2 parts copper plating powder. Mix the copper powder, nickel powder, and silicon powder to form a mixed powder. Heat the mixed powder to 1400°C in an argon atmosphere to melt it. Stir the melt, then add the copper plating powder to the melt. After adding the material, stir and mix for 5 minutes. Then, cool it to 1200°C while stirring, and immediately pour it into a mold to form a copper plating powder. The copper alloy casting is cooled in a mold, then removed and heated to 900℃ for 1 hour to relieve stress. Some samples are cooled to room temperature and processed into mechanical test specimens, while others are cooled to 180℃ and drawn into copper alloy wires using a wire drawing machine. The copper alloy wires are then held at 220℃ for 30 minutes, then heated to 300℃ and held for 3 hours. After the holding period, the wires are cooled to below 200℃ in the furnace and then air-cooled to room temperature to obtain the high-strength corrosion-resistant copper alloy wire.

[0058] Example 5

[0059] The tensile strength of the mechanical test specimens prepared by the methods described in the above embodiments and comparative examples was tested according to the requirements of standard GB / T228.1-2021; the self-corrosion potential of the copper alloy wires prepared by the methods described in the above embodiments and comparative examples in a 3.5wt% sodium chloride aqueous solution was tested, and the results are as follows. Figure 1 As shown.

[0060] Depend on Figure 1 It is known that the copper alloy castings prepared by the method described in this invention have high tensile strength, and the prepared copper alloy wires have high self-corrosion potential, exhibiting good strength and corrosion resistance. The main reason may be that, by adding the copper-plating powder prepared in this invention, the compatibility between the powder particles and the copper alloy melt is improved through copper plating, reducing interphase interface defects caused by insufficient compatibility between the powder particles and the copper alloy matrix during casting cooling, thereby improving the overall strength and corrosion resistance of the material. Furthermore, by adding boron-zirconium-erbium composite oxide powder, it can act as non-uniform nucleation sites, significantly refining the grain size of the as-cast copper alloy. The added zirconium and erbium elements can form granular phases with copper, located at the interphase interface and grain boundaries, playing a second-phase strengthening role. Cysteine ​​solution and 3-glycidyloxypropyltrimethoxysilane are beneficial for improving the particle surface state, promoting the chemical copper plating process, increasing the adhesion between the copper plating layer and the particle surface, and reducing interphase defects.

[0061] The technical solutions provided by the present invention have been described in detail above. For those skilled in the art, there will be changes in specific implementation methods and application scope based on the ideas of the embodiments of the present invention. Therefore, the content of this specification should not be construed as a limitation of the present invention.

Claims

1. A method for preparing a high-strength, corrosion-resistant copper alloy wire, characterized in that, Includes the following steps: (1) Prepare a composite aqueous solution of erbium nitrate and zirconium nitrate in a reactor; then add boron trioxide powder, hexadecyltrimethylammonium bromide and urea to the solution under stirring. After the addition is completed, continue stirring until uniform. Then seal the reactor, heat to 150-180℃ and keep warm for more than 2 hours, then cool to room temperature, open the reactor, pour out the material in the reactor, evaporate the liquid phase, and then calcine at 950-1100℃ under a protective gas atmosphere to obtain composite powder. (2) Dissolve cysteine ​​in deionized water to form a cysteine ​​solution; add the composite powder to the cysteine ​​solution to form a suspension; add 3-glycidyloxypropyltrimethoxysilane to the suspension while stirring; adjust the pH of the suspension to 9-11; heat to 90±5℃ and stir for more than 5 hours; after the heat preservation is completed, cool, separate the solid and liquid, wash the solid phase, and dry to obtain the pretreated powder. (3) Prepare an aqueous solution of stannous chloride as the sensitizing solution and an aqueous solution of silver nitrate as the activating solution; The pretreated powder is immersed in the sensitization solution for sensitization treatment, and then immersed in the activation solution for activation. The activated powder is then subjected to surface chemical copper plating to obtain copper-plated powder. (4) Mix copper powder, nickel powder and silicon powder to form a mixed powder. Heat the mixed powder to melt in a protective gas atmosphere, stir the melt, and then add the copper plating powder into the melt. After adding the material, stir and mix it evenly, and immediately cast it into a mold to form a copper alloy casting. Cool the copper alloy casting in the mold, and then heat the casting to 900-920℃ and hold it for 1-2 hours to relieve stress. Then cool it to 150-200℃ and draw it into a copper alloy wire using a wire drawing machine. Hold the copper alloy wire at 200-250℃ for 30-40 minutes, and then raise the temperature to 280-350℃ and hold it for 3-4 hours. After the holding period, cool it with the furnace to below 200℃, and then take it out and air cool it to room temperature to obtain the high-strength corrosion-resistant copper alloy wire.

2. The method for preparing a high-strength corrosion-resistant copper alloy wire according to claim 1, characterized in that, In step (1), the concentration of erbium nitrate in the composite aqueous solution of erbium nitrate and zirconium nitrate is 0.8-1.2 g / L, the concentration of zirconium nitrate is 20-30 g / L, and the solvent is water; boron trioxide powder, hexadecyltrimethylammonium bromide and urea are added to the solution in the following ratio: composite aqueous solution of erbium nitrate and zirconium nitrate: boron trioxide powder: hexadecyltrimethylammonium bromide: urea = 100 mL: 3-6 g: 0.5-0.8 g: 3-4 g; the calcination time is 1-2 h.

3. The method for preparing a high-strength, corrosion-resistant copper alloy wire according to claim 1, characterized in that, In step (2), the cysteine ​​concentration in the cysteine ​​solution is 2-4 g / 100 mL, and the solvent is water; the ratio of the composite powder, 3-glycidoxypropyltrimethoxysilane and cysteine ​​solution is composite powder: cysteine ​​solution: 3-glycidoxypropyltrimethoxysilane = 1 g: 50-200 mL: 1-2 g.

4. The method for preparing a high-strength, corrosion-resistant copper alloy wire according to claim 1, characterized in that, In step (3), the stannous chloride aqueous solution contains 4% to 5% stannous chloride by mass and water as the solvent; the silver nitrate aqueous solution contains 9% to 10% silver nitrate by mass and water as the solvent.

5. The method for preparing a high-strength, corrosion-resistant copper alloy wire according to claim 1, characterized in that, In step (3), the formulation of the plating solution for surface electroless copper plating is as follows: copper sulfate 8-10 g / L, potassium sodium tartrate 35-40 g / L, formaldehyde 14-16 mL / L, potassium hydroxide 7-9 g / L; the electroless plating temperature is 60±3℃, and the plating time is more than 10 min.

6. The method for preparing a high-strength, corrosion-resistant copper alloy wire according to claim 1, characterized in that, In step (4), the copper powder, nickel powder, silicon powder and copper plating powder used are in the following weight parts: 100 parts copper powder, 1.8 to 2.2 parts nickel powder, 0.5 to 0.6 parts silicon powder and 1 to 2 parts copper plating powder.

7. The method for preparing a high-strength, corrosion-resistant copper alloy wire according to claim 1, characterized in that, In step (4), the melting temperature is 1380-1420℃; the casting temperature is 1200-1250℃.

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