Preparation process of corrosion-resistant composite copper wire material

Abstract

The present invention relates to the field of chemical technology, and in particular to a preparation process for a corrosion-resistant composite copper wire material. The preparation process comprises the following steps: preparing aluminum oxide / silicon nitride whiskers; preparing aluminum oxide / silicon nitride whisker composite copper-based powder; preparing composite copper wire; and preparing a corrosion-resistant composite copper wire material. The present invention utilizes silicon nitride whiskers and aluminum oxide whiskers together with copper powder to prepare a composite material. The introduction of silicon nitride whiskers improves the Rockwell hardness and bending strength of the copper-based material. In addition, the growth of aluminum oxide whiskers can be promoted by silicon nitride whiskers, and aluminum oxide / silicon nitride whiskers have a denser structure than single whiskers, thereby improving the adhesion of aluminum oxide / silicon nitride whiskers to copper-based materials. As a result, the prepared corrosion-resistant copper wire material will not undergo material dissociation and aging due to electrical conductivity or voltage difference after long-term use, and its corrosion resistance will also be further improved.

Description

Technical Field

[0001] The present invention relates to the technical field of copper wire production, and in particular to a preparation process of a corrosion-resistant composite copper wire material. Background Art

[0002] With the development of the economy, the demand for copper wire is increasing, especially for copper wire used in the cable industry, which has particularly high quality requirements. In order to prevent the copper wire from being corroded, silver plating is generally used to protect the copper wire. Although the silver layer has strong corrosion resistance, the surface of the silver-plated copper wire is easily reacted with sulfides, halides, etc. in the air after long-term exposure to air, causing the surface to discolor. This not only destroys the appearance, but also increases the contact resistance and deteriorates the brazing performance.

[0003] There is also a method of using alumina particles and copper-based materials to compound to improve the corrosion resistance of copper wire. However, alumina particles are easy to aggregate and difficult to disperse, and the corrosion resistance of the prepared alumina composite copper wire material is limited. In addition, alumina also has good mechanical strength, but the alumina composite copper wire material cannot take advantage of this advantage of alumina. Summary of the Invention

[0004] In view of the shortcomings of the prior art, the present invention aims to provide a preparation process of a corrosion-resistant composite copper wire material.

[0005] A preparation process of a corrosion-resistant composite copper wire material comprises the following steps:

[0006] S1: Preparation of Aluminum Oxide / Silicon Nitride Whiskers

[0007] Dispersing aluminum oxide whiskers with a surfactant to obtain a suspension, placing the suspension in an ultrasonic mixer, stirring and filtering, removing the filtrate to obtain a filter residue, drying the filter residue to obtain aluminum oxide whiskers, using α-Si3N4 as a raw material, introducing Y2O3 as an additive and heat treating for 1-1.5 hours to obtain silicon nitride whiskers, and fully stirring and mixing the aluminum oxide whiskers and silicon nitride whiskers to obtain aluminum oxide / silicon nitride whiskers;

[0008] S2: Preparation of alumina / silicon nitride whisker composite copper-based powder

[0009] Copper powder and aluminum oxide are added to an aluminum nitrate solution to obtain a mixed solution, the mixed solution is fully stirred and transferred to a constant pressure water bath for heating to generate a mixed powder of aluminum nitrate crystals and copper powder, the mixed powder is transferred to a vacuum tube electric furnace for baking to generate a CuO-alumina mixed powder, the CuO-alumina mixed powder is mixed with aluminum oxide / silicon nitride whiskers, planetary ball milling is performed, and vacuum freeze drying is performed to obtain a composite powder, and the composite powder is placed in a vacuum tube furnace for reduction to obtain an aluminum oxide / silicon nitride whisker composite copper-based powder;

[0010] S3: Preparation of composite copper wire

[0011] Alumina / silicon nitride whisker composite copper-based powder is frozen and then statically sintered into a copper rod. The copper rod is passed through a drawing die and annealed in the middle, and then immersed in a drawing liquid and annealed during the drawing process to produce a composite copper wire.

[0012] S4: Preparation of corrosion-resistant composite copper wire materials

[0013] First, ZrB2 powder is mixed with a dispersant and a binder to prepare a slurry, which is then applied to the surface of a composite copper wire to obtain a pretreated copper wire. The pretreated copper wire is then subjected to a high-temperature heat treatment to obtain a treated copper wire. CaF2 powder, SiO2 powder and TiO2 powder are dried and then mixed with Al-NiO powder and Al-Fe2O3 powder to obtain a coating powder. The coating powder is then added to an outer wrapping device and placed in a centrifuge mold with the treated copper wire to initiate a SHS reaction. After the reaction stops, the centrifuge speed is gradually reduced to stop, and the wire is naturally cooled to room temperature to obtain a corrosion-resistant composite copper wire material.

[0014] Furthermore, step S1 of preparing aluminum oxide / silicon nitride whiskers comprises the following steps:

[0015] S1.1: Disperse the aluminum oxide whiskers with a surfactant at a concentration of 1.5-2 g / L at a solid-to-liquid ratio of (0.1-0.3):50 to obtain a suspension. Place the suspension in an ultrasonic mixer and ultrasonically stir for 25-30 minutes. After standing for 20-24 hours, filter and remove the filtrate to obtain a filter residue. Dry the filter residue in a vacuum drying oven for 4-6 hours to obtain aluminum oxide whiskers.

[0016] S1.2: Using α-Si3N4 as raw material, Y2O3 is introduced as an additive and heat treated at 1700-1750℃ for 1-1.5h. The ratio of α-Si3N4 to Y2O3 is 1:(0.5-1). High-purity nitrogen and hydrogen mixture is used as the protective gas to obtain silicon nitride whiskers.

[0017] S1.3: Fully stir and mix the aluminum oxide whiskers and silicon nitride whiskers to obtain aluminum oxide / silicon nitride whiskers.

[0018] Furthermore, step S2 of preparing alumina / silicon nitride whisker composite copper-based powder comprises the following steps:

[0019] S2.1: Add copper powder and aluminum oxide to a 5-8 wt% aluminum nitrate solution until the solution is saturated, with the volume ratio of copper powder to aluminum oxide being (98-99):(1-2) to obtain a mixed solution;

[0020] S2.2: The mixed solution is thoroughly stirred and transferred to a constant pressure water bath for heating at 70-85°C while being dried. During this process, the aluminum nitrate powder and the copper powder are evenly stirred and fused to form a mixed powder of aluminum nitrate crystals and copper powder.

[0021] S2.3: Transfer the mixed powder to a vacuum tube electric furnace, bake at 450-550°C under nitrogen protection for 1.5-2 hours, and cool naturally to produce a CuO-alumina mixed powder;

[0022] S2.4: Mix the CuO-alumina mixed powder and alumina / silicon nitride whiskers, and perform planetary ball milling. Add an appropriate amount of tert-butyl alcohol as a grinding medium, and ball mill for 1.5-2 h at a rotation speed of 350-400 r / min, with a ball-to-material ratio of 1:10. Vacuum freeze-dry to obtain a composite powder.

[0023] S2.5: Place the composite powder in a vacuum tube furnace and reduce it at 180-200° C. in a hydrogen atmosphere for 1.5-2 hours to obtain an aluminum oxide / silicon nitride whisker composite copper-based powder.

[0024] Furthermore, step S4 of preparing the corrosion-resistant composite copper wire material comprises the following steps:

[0025] S4.1: ZrB2 powder is mixed with a dispersant and a binder, wherein the volume ratio of ZrB2 powder, dispersant and binder is 1:(5-6):(2-3) to prepare a slurry, and the slurry is applied to the surface of the composite copper wire, followed by drying at 80-100°C to obtain a pretreated copper wire, and then the pretreated copper wire is subjected to a high-temperature heat treatment by sintering at 450-550°C in a high-temperature furnace for 1-2 hours, and then cooled to room temperature to obtain a treated copper wire in the high-temperature furnace;

[0026] S4.2: Drying the CaF2 powder, SiO2 powder, and TiO2 powder at 80-100°C, respectively, and then mixing with Al-NiO powder and Al-Fe2O3 powder to obtain a coating powder;

[0027] S4.3: The coating powder is then added to the outer wrapping device and placed in a centrifuge mold. The treated copper wire is placed in the center of the centrifuge mold. The centrifuge is then started and maintained at 1800-2200 r / min for 5 seconds. The ignition device is started to initiate the SHS reaction. After the reaction stops, the centrifuge speed is gradually reduced to stop, and the centrifuge is naturally cooled to room temperature to obtain a corrosion-resistant composite copper wire material.

[0028] Furthermore, the surfactant in step S1.1 is specifically sodium lauryl sulfate.

[0029] Furthermore, the volume ratio of nitrogen to hydrogen in the high-purity nitrogen-hydrogen mixed gas in step S1.2 is 8:2.

[0030] Furthermore, in step S1.3, the volume ratio of the aluminum oxide whiskers to the silicon nitride whiskers is 1:1.

[0031] Furthermore, in step 2.4, the mass ratio of the CuO-alumina mixed powder to the alumina / silicon nitride whiskers is (50-80):1.

[0032] Furthermore, the static pressure sintering in step S3 is specifically performed by pressing at 550-600 MPa twice.

[0033] Furthermore, the contents of the components of the coating powder in step S4.2 are, in percentage terms, 1.5-2% CaF2 powder, 0.5-1% SiO2 powder, 15-22% TiO2 powder, 15-18% Al-NiO powder, and 50-60% Al-Fe2O3 powder.

[0034] Compared with the prior art, the present invention has at least the following beneficial effects:

[0035] 1. The present invention utilizes silicon nitride whiskers and aluminum oxide whiskers together with copper powder to prepare a composite material. The introduction of silicon nitride whiskers improves the Rockwell hardness and bending strength of the copper-based material. In addition, the growth of aluminum oxide whiskers can be promoted by silicon nitride whiskers. Compared with single whiskers, aluminum oxide / silicon nitride whiskers have a denser structure, thereby improving the adhesion of aluminum oxide / silicon nitride whiskers to the copper-based material. As a result, the prepared corrosion-resistant copper wire material will not dissociate and age due to electrical conductivity or voltage difference after long-term use, and its corrosion resistance will be further improved.

[0036] 2. The present invention first treats the composite copper wire so that the ZrB2 powder is bonded to the composite copper wire through high-temperature heat treatment. The ZrB2 powder is organically bonded to the silicon nitride attached to the copper wire to form an intermediate layer. This intermediate layer has a dense structure and is therefore well bonded to the composite copper wire. Subsequently, the coating powder is centrifuged and ignited to induce an SHS reaction. The coating powder undergoes centrifugal self-propagation and is thus coated on the surface of the treated copper wire. Due to the action of centrifugal force, the ZrB2 coating and the CaF2 powder, SiO2 powder, TiO2 powder, Al-NiO powder and Al-Fe2O3 powder are formed layer by layer on the surface of the copper wire according to a certain weight density, so that the layers are neat and uniform and densely bonded, thereby slowing down the corrosion rate and improving the copper wire material's resistance to dry-wet alternating smoke corrosion.

[0037] 3. The present invention improves the mechanical strength of the copper-based material by introducing alumina into the copper-based material. Alumina has good thermal stability and mechanical strength and is an ideal reinforcement. In addition, the present invention uses alumina whiskers to reinforce the copper-based material, which improves the wear resistance of the composite copper wire material compared to alumina powder. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] The accompanying drawings, which are incorporated herein and constitute a part of the specification, illustrate embodiments of the present disclosure and, together with the description, further serve to explain the principles of the present disclosure and to enable one skilled in the relevant art to make and use the present disclosure.

[0039] Figure 1 This is a preparation process of the corrosion-resistant composite copper wire material used in an embodiment of the present invention. DETAILED DESCRIPTION Example 1

[0040] A preparation process of a corrosion-resistant composite copper wire material, such as Figure 1 As shown, the following steps are included:

[0041] S1: Preparation of Aluminum Oxide / Silicon Nitride Whiskers

[0042] S1.1: Disperse alumina whiskers with a surfactant (sodium lauryl sulfate) at a concentration of 2 g / L at a solid-to-liquid ratio of 0.1:50 to obtain a suspension. Place the suspension in an ultrasonic mixer and ultrasonically stir for 30 minutes. After standing for 24 hours, filter and remove the filtrate to obtain a filter residue. Dry the filter residue in a vacuum drying oven for 6 hours to obtain alumina whiskers.

[0043] S1.2: Using α-Si3N4 as raw material, Y2O3 is introduced as an additive and heat treated at 1700-1750℃ for 1.5h. The molar ratio of the two substances is 1:0.5. High-purity nitrogen and hydrogen mixed gas is used as the protective gas to obtain silicon nitride whiskers.

[0044] S1.3: Fully stir and mix the aluminum oxide whiskers and silicon nitride whiskers to obtain aluminum oxide / silicon nitride whiskers.

[0045] S2: Preparation of alumina / silicon nitride whisker composite copper-based powder

[0046] S2.1: Copper powder and aluminum oxide were added to an 8 wt % aluminum nitrate solution until the solution was saturated, with the volume ratio of copper powder to aluminum oxide being 98:2, to obtain a mixed solution;

[0047] S2.2: The mixed solution is thoroughly stirred and transferred to a constant pressure water bath for heating at 85°C while being dried. During this process, the aluminum nitrate powder and the copper powder are evenly stirred and fused to form a mixed powder of aluminum nitrate crystals and copper powder.

[0048] S2.3: Transfer the mixed powder to a vacuum tube electric furnace, bake at 550°C under nitrogen protection for 2 h, and cool naturally to produce a CuO-alumina mixed powder;

[0049] S2.4: Mix the CuO-alumina mixed powder and alumina / silicon nitride whiskers (mass ratio 80:1) and perform planetary ball milling. Add an appropriate amount of tert-butyl alcohol as a grinding medium. Mill for 2 h at a speed of 400 r / min and a ball-to-material ratio of 1:10. Vacuum freeze-dry to obtain a composite powder.

[0050] S2.5: Place the composite powder in a vacuum tube furnace and reduce it at 200° C. in a hydrogen atmosphere for 2 h to obtain an aluminum oxide / silicon nitride whisker composite copper-based powder.

[0051] S3: Preparation of composite copper wire

[0052] The aluminum oxide / silicon nitride whisker composite copper-based powder was frozen, then pressed twice at 600 MPa, and statically sintered into a copper rod. The copper rod was passed through a drawing die and annealed in the middle, and then immersed in a drawing liquid and annealed during the drawing process to produce a composite copper wire.

[0053] S4: Preparation of corrosion-resistant composite copper wire materials

[0054] S4.1: ZrB2 powder is mixed with a dispersant and a binder in a volume ratio of 1:6:2 to prepare a slurry, which is applied to the surface of the composite copper wire and then dried at 80°C to obtain a pretreated copper wire. The pretreated copper wire is then subjected to a high-temperature heat treatment by sintering it in a high-temperature furnace at 450°C for 1 hour and cooling it to room temperature to obtain a treated copper wire in a high-temperature furnace.

[0055] S4.2: Drying CaF2 powder, SiO2 powder, and TiO2 powder at 100°C, respectively, and then mixing with Al-NiO powder and Al-Fe2O3 powder to obtain a coating powder, wherein the percentages of the components are as follows: 1.5% CaF2, 0.5% SiO2, 20% TiO2, 18% Al-NiO, and 60% Al-Fe2O3 powder;

[0056] S4.3: The coating powder is then added to the outer wrapping device and placed in a centrifuge mold. The treated copper wire is placed in the center of the centrifuge mold and maintained at 2200 r / min for 5 seconds. The ignition device is started to initiate the SHS reaction. After the reaction stops, the centrifuge speed is gradually reduced to stop, and the centrifuge is naturally cooled to room temperature to obtain a corrosion-resistant composite copper wire material. Example 2

[0057] A preparation process of a corrosion-resistant composite copper wire material, such as Figure 1 As shown, the following steps are included:

[0058] S1: Preparation of Aluminum Oxide / Silicon Nitride Whiskers

[0059] S1.1: Disperse alumina whiskers with a surfactant (sodium lauryl sulfate) at a concentration of 2 g / L at a solid-to-liquid ratio of 0.1:50 to obtain a suspension. Place the suspension in an ultrasonic mixer and ultrasonically stir for 30 minutes. After standing for 24 hours, filter and remove the filtrate to obtain a filter residue. Dry the filter residue in a vacuum drying oven for 6 hours to obtain alumina whiskers.

[0060] S1.2: Using α-Si3N4 as raw material, Y2O3 is introduced as an additive and heat treated at 1700-1750℃ for 1.5h, with the molar ratio of the two being 1:1, and using a high-purity nitrogen-hydrogen mixture as the protective gas to obtain silicon nitride whiskers;

[0061] S1.3: Fully stir and mix the aluminum oxide whiskers and silicon nitride whiskers to obtain aluminum oxide / silicon nitride whiskers.

[0062] S2: Preparation of alumina / silicon nitride whisker composite copper-based powder

[0063] S2.1: Copper powder and aluminum oxide were added to an 8 wt % aluminum nitrate solution until the solution was saturated, with the volume ratio of copper powder to aluminum oxide being 99:1, to obtain a mixed solution;

[0064] S2.2: The mixed solution is thoroughly stirred and transferred to a constant pressure water bath for heating at 85°C while being dried. During this process, the aluminum nitrate powder and the copper powder are evenly stirred and fused to form a mixed powder of aluminum nitrate crystals and copper powder.

[0065] S2.3: Transfer the mixed powder to a vacuum tube electric furnace, bake at 550°C under nitrogen protection for 2 h, and cool naturally to produce a CuO-alumina mixed powder;

[0066] S2.4: Mix the CuO-alumina mixed powder and alumina / silicon nitride whiskers (mass ratio 80:1) and perform planetary ball milling. Add an appropriate amount of tert-butyl alcohol as a grinding medium. Mill for 2 h at a speed of 400 r / min and a ball-to-material ratio of 1:10. Vacuum freeze-dry to obtain a composite powder.

[0067] S2.5: Place the composite powder in a vacuum tube furnace and reduce it at 200° C. in a hydrogen atmosphere for 2 h to obtain an aluminum oxide / silicon nitride whisker composite copper-based powder.

[0068] S3: Preparation of composite copper wire

[0069] The aluminum oxide / silicon nitride whisker composite copper-based powder was frozen, then pressed twice at 600 MPa, and statically sintered into a copper rod. The copper rod was passed through a drawing die and annealed in the middle, and then immersed in a drawing liquid and annealed during the drawing process to produce a composite copper wire.

[0070] S4: Preparation of corrosion-resistant composite copper wire materials

[0071] S4.1: ZrB2 powder is mixed with a dispersant and a binder in a volume ratio of 1:5:3 to prepare a slurry, which is applied to the surface of the composite copper wire and then dried at 80°C to obtain a pretreated copper wire. The pretreated copper wire is then subjected to a high-temperature heat treatment by sintering it at 450°C in a high-temperature furnace for 1 hour and cooling it to room temperature to obtain a treated copper wire in a high-temperature furnace.

[0072] S4.2: Drying CaF2 powder, SiO2 powder, and TiO2 powder at 100°C, respectively, and then mixing with Al-NiO powder and Al-Fe2O3 powder to obtain a coating powder, wherein the percentages of the components are as follows: 2% CaF2, 1% SiO2, 22% TiO2, 18% Al-NiO, and 57% Al-Fe2O3 powder;

[0073] S4.3: The coating powder is then added to the outer wrapping device and placed in a centrifuge mold. The treated copper wire is placed in the center of the centrifuge mold and maintained at 2200 r / min for 5 seconds. The ignition device is started to initiate the SHS reaction. After the reaction stops, the centrifuge speed is gradually reduced to stop, and the centrifuge is naturally cooled to room temperature to obtain a corrosion-resistant composite copper wire material. Example 3

[0074] A preparation process of a corrosion-resistant composite copper wire material, such as Figure 1 As shown, the following steps are included:

[0075] S1: Preparation of Aluminum Oxide / Silicon Nitride Whiskers

[0076] S1.1: Disperse alumina whiskers with a surfactant (sodium lauryl sulfate) at a concentration of 1.5 g / L at a solid-to-liquid ratio of 0.1:50 to obtain a suspension. Place the suspension in an ultrasonic mixer and ultrasonically stir for 25 minutes. After standing for 24 hours, filter and remove the filtrate to obtain a filter residue. Dry the filter residue in a vacuum drying oven for 5 hours to obtain alumina whiskers.

[0077] S1.2: Using α-Si3N4 as raw material, Y2O3 was introduced as an additive and heat treated at 1700℃ for 1.5h. The molar ratio of the two substances was 1:0.5. High-purity nitrogen and hydrogen mixed gas was used as the protective gas to obtain silicon nitride whiskers.

[0078] S1.3: Add copper powder and aluminum oxide to a 5 wt % aluminum nitrate solution until the solution is saturated to obtain aluminum oxide / silicon nitride whiskers.

[0079] S2: Preparation of alumina / silicon nitride whisker composite copper-based powder

[0080] S2.1: Add copper powder and aluminum oxide to an aluminum nitrate solution in a volume ratio of 98:2 to obtain a mixed solution;

[0081] S2.2: The mixed solution is thoroughly stirred and transferred to a constant pressure water bath for heating at 85°C while being dried. During this process, the aluminum nitrate powder and the copper powder are evenly stirred and fused to form a mixed powder of aluminum nitrate crystals and copper powder.

[0082] S2.3: Transfer the mixed powder to a vacuum tube electric furnace, bake at 500°C under nitrogen protection for 2 h, and cool naturally to produce a CuO-alumina mixed powder;

[0083] S2.4: Mix the CuO-alumina mixed powder and alumina / silicon nitride whiskers (mass ratio 80:1) and perform planetary ball milling. Add an appropriate amount of tert-butyl alcohol as a grinding medium. Mill for 2 h at a speed of 400 r / min and a ball-to-material ratio of 1:10. Vacuum freeze-dry to obtain a composite powder.

[0084] S2.5: Place the composite powder in a vacuum tube furnace and reduce it at 200° C. in a hydrogen atmosphere for 2 h to obtain an aluminum oxide / silicon nitride whisker composite copper-based powder.

[0085] S3: Preparation of composite copper wire

[0086] The aluminum oxide / silicon nitride whisker composite copper-based powder was frozen, then pressed twice at 550 MPa, and statically sintered into a copper rod. The copper rod was passed through a drawing die and annealed in the middle, and then immersed in a drawing liquid and annealed during the drawing process to produce a composite copper wire.

[0087] S4: Preparation of corrosion-resistant composite copper wire materials

[0088] S4.1: ZrB2 powder is mixed with a dispersant and a binder in a volume ratio of 1:6:2 to prepare a slurry, which is applied to the surface of the composite copper wire and then dried at 100°C to obtain a pretreated copper wire. The pretreated copper wire is then subjected to a high-temperature heat treatment by sintering at 550°C for 1 hour in a high-temperature furnace and cooling to room temperature to obtain a treated copper wire in a high-temperature furnace.

[0089] S4.2: Drying CaF2 powder, SiO2 powder, and TiO2 powder at 80°C, respectively, and then mixing with Al-NiO powder and Al-Fe2O3 powder to obtain a coating powder, wherein the percentages of the components are as follows: 1.5% CaF2, 0.5% SiO2, 20% TiO2, 18% Al-NiO, and 60% Al-Fe2O3 powder;

[0090] S4.3: The coating powder is then added to the outer wrapping device and placed in a centrifuge mold. The treated copper wire is placed in the center of the centrifuge mold and maintained at 2200 r / min for 5 seconds. The ignition device is started to initiate the SHS reaction. After the reaction stops, the centrifuge speed is gradually reduced to stop, and the centrifuge is naturally cooled to room temperature to obtain a corrosion-resistant composite copper wire material.

[0091] Comparative Example 1:

[0092] Compared with Example 1, Comparative Example 1 is a method of cladding coating powder using laser cladding technology, specifically: "S4.1: mixing ZrB2 powder with a dispersant and a binder, wherein the volume ratio of ZrB2 powder, dispersant, and binder is 1:6:2 to prepare a slurry, applying the slurry to the surface of the composite copper wire, and then drying at 80°C to obtain a pretreated copper wire, and then subjecting the pretreated copper wire to a high-temperature heat treatment, sintering it at 450°C in a high-temperature furnace for 1 hour, cooling it to room temperature, and obtaining a treated copper wire in the high-temperature furnace;

[0093] S4.2: Drying CaF2 powder, SiO2 powder, and TiO2 powder at 100°C, respectively, and then mixing with Al-NiO powder and Al-Fe2O3 powder to obtain a coating powder, wherein the percentages of the components are as follows: 1.5% CaF2, 0.5% SiO2, 20% TiO2, 18% Al-NiO, and 60% Al-Fe2O3 powder;

[0094] S4.3: Add the coating powder to a laser cladding machine at a powder feed rate of 20 g / min, a linear speed of 500 mm / min, and nitrogen as the shielding gas. Then, place the treated copper wire in the laser cladding machine for laser cladding treatment to obtain a corrosion-resistant composite copper wire material. The obtained corrosion-resistant composite copper wire material is recorded as Comparative Example 1.

[0095] Comparative Example 2:

[0096] Compared with Example 1, Comparative Example 2 is a step in which only aluminum oxide whiskers are prepared in step S1, specifically: "Aluminum oxide whiskers are dispersed with a surfactant (sodium lauryl sulfate) at a concentration of 2 g / L, and a solid-liquid ratio of 0.1:50 to obtain a suspension, and the suspension is placed in an ultrasonic stirrer, ultrasonically stirred for 30 minutes, and filtered after standing for 24 hours. The filtrate is removed to obtain a filter residue, and the filter residue is placed in a vacuum blast drying oven and dried for 6 hours to obtain aluminum oxide whiskers." Aluminum oxide whiskers are used instead of aluminum oxide / silicon nitride whiskers for subsequent steps, and the obtained corrosion-resistant composite copper wire material is recorded as Comparative Example 2.

[0097] Comparative Example 3:

[0098] Compared with Example 1, Comparative Example 3 is a step in which only silicon nitride whiskers are prepared in step S1, specifically: "Using α-Si3N4 as raw material, introducing Y2O3 as an additive and heat treating at 1750°C for 1.5h, the ratio of the amounts of the two substances is 1:0.5, and using high-purity nitrogen and hydrogen mixed gas as a protective gas to obtain silicon nitride whiskers" and using silicon nitride whiskers instead of aluminum oxide / silicon nitride whiskers to carry out subsequent steps. The corrosion-resistant composite copper wire material obtained is recorded as Comparative Example 3.

[0099] Comparative Example 4:

[0100] Compared with Example 1, Comparative Example 4 does not perform step S4.1 in step S4, and replaces the treated copper wire with the composite copper wire, specifically: "S4.2: Drying the CaF2 powder, SiO2 powder, and TiO2 powder at 80°C, and then mixing them with Al-NiO powder and Al-Fe2O3 powder to obtain a coating powder; wherein the content of each component, in percentage, is as follows: 1.5% CaF2, 0.5% SiO2, 20% TiO2, 18% Al-NiO, and 60% Al-Fe2O3 powder;

[0101] S4.3: The coating powder is then added to the outer wrapping device and placed in a centrifuge mold. The treated copper wire is placed in the center of the centrifuge mold and maintained at 2200 r / min for 5 seconds. The ignition device is started to initiate the SHS reaction. After the reaction stops, the centrifuge speed is gradually reduced to stop, and the centrifuge is naturally cooled to room temperature to obtain a corrosion-resistant composite copper wire material.

[0102] Corrosion resistance test

[0103] The corrosion resistance of Examples 1-3 and Comparative Examples 1-3 was tested according to the neutral salt spray test (NSS) specified in GB / T10125 “Artificial atmosphere corrosion test salt spray test”, and the corrosion time and corrosion rating of the copper wire surface were recorded, as shown in Table 1.

[0104] Table 1: Corrosion time and corrosion area

[0105] Time to corrosion onset (h) Corrosion area (%) Time to 10% corrosion (h) Time to 50% corrosion (h) Example 1 26-28 0.50% 58-74 92-99 Example 2 26-28 0.50% 59-74 91-100 Example 3 26-28 0.50% 58-73 92-101 Comparative Example 1 23-25 0.60% 54-57 85-92 Comparative Example 2 19-22 0.70% 51-55 79-84 Comparative Example 3 19-21 0.60% 50-54 74-80 Comparative Example 4 24-27 0.50% 52-58 67-71

[0106] It can be seen that the time for the embodiment to begin to corrode is 26-28 hours, while the time for the comparative example 1 is at most 25 hours. In addition, the initial corrosion area of ​​the embodiment is also 0.1% smaller than that of the comparative example 1. Subsequently, the embodiment corrodes to 10% between 58-74 hours, while the comparative example 1 has already corroded to 10% around 54-57 hours, and the time for corrosion to reach 50% is even shorter. This is because, although the coating powder used in the comparative example 1 has not changed, the coating powder is applied by the laser cladding method, and the bonding between the coating and the copper wire material is not tight enough. Therefore, the overall corrosion resistance is not as good as that of the embodiment using the centrifugal self-propagating method.

[0107] Comparative Examples 2 and 3 show that both aluminum oxide and silicon nitride whiskers provide a certain degree of corrosion resistance for the copper wire material. When used alone, the time for both to begin corrosion is about 19-22 hours, and the time to corrosion to 10% is about 50-55 hours. The time to corrosion to 50% is different. When aluminum oxide whiskers are used alone, it is 79-84 hours, and when silicon nitride is used alone, it is 74-80 hours. When used together in the examples, there is a synergistic effect, and the time to corrosion to 50% increases to 91-101 hours, which has a good corrosion resistance effect.

[0108] After removing ZrB2 from Comparative Example 4, the corrosion resistance was not greatly affected in a short period of time. The time to corrosion to 10% decreased slightly to 52-58h, while the time to corrosion to 50% was greatly reduced to only 67-71h. This is because after removing the ZrB2 coating, the adhesion between the coating powder and the copper wire material is insufficient and it is easy to fall off. Therefore, after a period of time, the coating powder falls off, thereby significantly reducing the corrosion resistance.

[0109] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the present invention. Anyone skilled in the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by one of ordinary skill in the art without departing from the spirit and technical principles disclosed herein are intended to be covered by the claims of the present invention.

Claims

1. A process for preparing a corrosion-resistant composite copper wire material, characterized in that: The following steps are involved: S1: Preparation of Aluminum Oxide / Silicon Nitride Whiskers Dispersing aluminum oxide whiskers with a surfactant to obtain a suspension, placing the suspension in an ultrasonic mixer, stirring and filtering, removing the filtrate to obtain a filter residue, drying the filter residue to obtain aluminum oxide whiskers, using α-Si3N4 as a raw material, introducing Y2O3 as an additive and heat treating for 1-1.5 hours to obtain silicon nitride whiskers, and fully stirring and mixing the aluminum oxide whiskers and silicon nitride whiskers to obtain aluminum oxide / silicon nitride whiskers; S2: Preparation of alumina / silicon nitride whisker composite copper-based powder Copper powder and aluminum oxide are added to an aluminum nitrate solution to obtain a mixed solution, the mixed solution is fully stirred and transferred to a constant pressure water bath for heating to generate a mixed powder of aluminum nitrate crystals and copper powder, the mixed powder is transferred to a vacuum tube electric furnace for baking to generate a CuO-alumina mixed powder, the CuO-alumina mixed powder is mixed with aluminum oxide / silicon nitride whiskers, planetary ball milling is performed, and vacuum freeze drying is performed to obtain a composite powder, and the composite powder is placed in a vacuum tube furnace for reduction to obtain an aluminum oxide / silicon nitride whisker composite copper-based powder; S3: Preparation of composite copper wire Alumina / silicon nitride whisker composite copper-based powder is frozen and then statically sintered into a copper rod. The copper rod is passed through a drawing die and annealed in the middle, and then immersed in a drawing liquid and annealed during the drawing process to produce a composite copper wire. S4: Preparation of corrosion-resistant composite copper wire materials First, ZrB2 powder is mixed with a dispersant and a binder to prepare a slurry, which is then applied to the surface of a composite copper wire to obtain a pretreated copper wire. The pretreated copper wire is then subjected to a high-temperature heat treatment to obtain a treated copper wire. CaF2 powder, SiO2 powder and TiO2 powder are dried and then mixed with Al-NiO powder and Al-Fe2O3 powder to obtain a coating powder. The coating powder is then added to an outer wrapping device and placed in a centrifuge mold with the treated copper wire to initiate a SHS reaction. After the reaction stops, the centrifuge speed is gradually reduced to stop, and the wire is naturally cooled to room temperature to obtain a corrosion-resistant composite copper wire material.

2. The preparation process of a corrosion-resistant composite copper wire material according to claim 1, characterized in that: Step S1: preparing aluminum oxide / silicon nitride whiskers, comprising the following steps: S1.1: Disperse the aluminum oxide whiskers with a surfactant at a concentration of 1.5-2 g / L at a solid-to-liquid ratio of (0.1-0.3):50 to obtain a suspension. Place the suspension in an ultrasonic mixer and ultrasonically stir for 25-30 minutes. After standing for 20-24 hours, filter and remove the filtrate to obtain a filter residue. Dry the filter residue in a vacuum drying oven for 4-6 hours to obtain aluminum oxide whiskers. S1.2: Using α-Si3N4 as raw material, Y2O3 is introduced as an additive and heat treated at 1700-1750℃ for 1-1.5h. The ratio of α-Si3N4 to Y2O3 is 1:(0.5-1). High-purity nitrogen and hydrogen mixture is used as the protective gas to obtain silicon nitride whiskers. S1.3: Fully stir and mix the aluminum oxide whiskers and silicon nitride whiskers to obtain aluminum oxide / silicon nitride whiskers.

3. The preparation process of a corrosion-resistant composite copper wire material according to claim 2, characterized in that: Step S2 is to prepare alumina / silicon nitride whisker composite copper-based powder, comprising the following steps: S2.1: Add copper powder and aluminum oxide to a 5-8 wt% aluminum nitrate solution until the solution is saturated, with the volume ratio of copper powder to aluminum oxide being (98-99):(1-2) to obtain a mixed solution; S2.2: The mixed solution is thoroughly stirred and transferred to a constant pressure water bath for heating at 70-85°C while being dried. During this process, the aluminum nitrate powder and the copper powder are evenly stirred and fused to form a mixed powder of aluminum nitrate crystals and copper powder. S2.3: Transfer the mixed powder to a vacuum tube electric furnace, bake at 450-550°C under nitrogen protection for 1.5-2 hours, and cool naturally to produce a CuO-alumina mixed powder; S2.4: Mix the CuO-alumina mixed powder and alumina / silicon nitride whiskers, and perform planetary ball milling. Add an appropriate amount of tert-butyl alcohol as a grinding medium, and ball mill for 1.5-2 h at a rotation speed of 350-400 r / min, with a ball-to-material ratio of 1:

10. Vacuum freeze-dry to obtain a composite powder. S2.5: Place the composite powder in a vacuum tube furnace and reduce it at 180-200° C. in a hydrogen atmosphere for 1.5-2 hours to obtain an aluminum oxide / silicon nitride whisker composite copper-based powder.

4. The process for preparing a corrosion-resistant composite copper wire material according to claim 3, wherein step S4 of preparing the corrosion-resistant composite copper wire material comprises the following steps: S4.1: ZrB2 powder is mixed with a dispersant and a binder, wherein the volume ratio of ZrB2 powder, dispersant and binder is 1:(5-6):(2-3) to prepare a slurry, and the slurry is applied to the surface of the composite copper wire, followed by drying at 80-100°C to obtain a pretreated copper wire, and then the pretreated copper wire is subjected to a high-temperature heat treatment by sintering at 450-550°C in a high-temperature furnace for 1-2 hours, and then cooled to room temperature to obtain a treated copper wire in the high-temperature furnace; S4.2: Drying the CaF2 powder, SiO2 powder, and TiO2 powder at 80-100°C, respectively, and then mixing with Al-NiO powder and Al-Fe2O3 powder to obtain a coating powder; S4.3: The coating powder is then added to the outer wrapping device and placed in a centrifuge mold. The treated copper wire is placed in the center of the centrifuge mold. The centrifuge is then started and maintained at 1800-2200 r / min for 5 seconds. The ignition device is started to initiate the SHS reaction. After the reaction stops, the centrifuge speed is gradually reduced to stop, and the centrifuge is naturally cooled to room temperature to obtain a corrosion-resistant composite copper wire material.

5. The process for preparing a corrosion-resistant composite copper wire material according to claim 4, characterized in that: The surfactant in step S1.1 is specifically sodium lauryl sulfate.

6. The process for preparing a corrosion-resistant composite copper wire material according to claim 5, characterized in that: The volume ratio of nitrogen to hydrogen in the high-purity nitrogen-hydrogen mixed gas in step S1.2 is 8:

2.

7. The process for preparing a corrosion-resistant composite copper wire material according to claim 6, characterized in that: The volume ratio of the aluminum oxide whiskers to the silicon nitride whiskers in step S1.3 is 1:

1.

8. The process for preparing a corrosion-resistant composite copper wire material according to claim 7, characterized in that: The mass ratio of CuO-alumina mixed powder and alumina / silicon nitride whiskers in step 2.4 is (50-80):

1.

9. The process for preparing a corrosion-resistant composite copper wire material according to claim 8, characterized in that: The static pressure sintering in step S3 is specifically performed by pressing at 550-600 MPa twice.

10. The process for preparing a corrosion-resistant composite copper wire material according to claim 9, characterized in that: The coating powder in step S4.2 has the following components in percentage: 1.5-2% CaF2 powder, 0.5-1% SiO2 powder, 15-22% TiO2 powder, 15-18% Al-NiO powder and 50-60% Al-Fe2O3 powder.

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