Multi-element copper-tin alloy wire with nanocrystals and preparation method of multi-element copper-tin alloy wire

Abstract

The invention discloses a multi-element copper-tin alloy wire with nanocrystals and a preparation method of the multi-element copper-tin alloy wire, and belongs to the technical field of non-ferrous metal processing. The alloy wire comprises the following components in percentage by weight: 0.03%-0.85% of Sn, 0.06%-0.3% of Ag, 0.05%-0.9% of Cr, 0.05%-0.2% of a component A, 0.005%-0.01% of a component B and the balance of Cu, the component A is any one of Ti, Mg, Zr, Fe, Si and Zn; the component B is any one of La, Ce, Y, Sc, Gd and Sm; the preparation method comprises the steps of burdening, feeding, smelting, casting, homogenizing annealing, continuous hot extrusion, solution treatment, drawing and online annealing treatment. The tensile strength of the alloy wire is 400-600 MPa, the yield strength is 280-350 MPa, the elongation is 15%-30%, the electric conductivity is 75%-90% IACS, the softening temperature is 450-580 DEG C, the pitting corrosion density after a salt spray environment corrosion experiment is 8-15 cm <-2 >, and the alloy wire can meet the requirements in the important fields of precise cables, electrified railway contact wires, resistance welding electrodes and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of nonferrous metal processing, and in particular relates to a multinary copper-tin alloy wire with nanocrystals and a preparation method thereof. Background Art

[0002] Cu-Sn alloys possess excellent electrical and thermal conductivity, as well as good weldability and wear resistance. They have been applied in fields such as integrated circuits, electric locomotive wires, and heat exchanger components. They are promising structural functional materials for the high-strength and high-conductivity applications of the electronic circuit industry. However, the relatively weak mechanical properties and corrosion resistance of Cu-Sn alloys have limited their wider application. Improving the strength and corrosion resistance of Cu-Sn alloys has become a key issue that needs to be addressed. Summary of the Invention

[0003] In order to solve the problems existing in the prior art, the present invention provides a multinary copper-tin alloy wire with nanocrystals and a preparation method thereof.

[0004] As a technical solution of the present invention, the present invention provides a multinary copper-tin alloy wire with nanocrystals, wherein the multinary copper-tin alloy wire is mainly composed of the following raw materials in the following mass percentages:

[0005] Sn 0.25%-0.75%, Ag 0.05%-0.15%, Cr 0.08%-0.20%, component A 0.05%-0.2% and component B 0.005%-0.01%, and the rest is Cu;

[0006] Wherein, component A is any one of the six elements of Ti, Mg, Zr, Fe, Si and Zn;

[0007] Wherein, component B is any one of six elements: La, Ce, Y, Sc, Gd and Sm.

[0008] Furthermore, the diameter of the multi-element copper-tin alloy wire is 0.08-0.30 mm.

[0009] Furthermore, in the multi-component copper-tin alloy wire, the alloy <100> Texture accounts for 22% to 35%, alloy <110> Texture accounts for 10% to 22%, alloy <111> Texture accounts for 30% to 40%, alloy <112> Texture accounts for 20 to 36.

[0010] Furthermore, the tensile strength of the multi-element copper-tin alloy wire is 400-600 MPa, the yield strength is 280-350 MPa, the elongation is 15%-30%, the conductivity is 75%-90 IACS, the softening temperature is 450-580 ° C, and the pitting density after the salt spray environment corrosion test is 8-15 cm-2 .

[0011] As another technical solution of the present application, the present application provides a preparation method of the aforementioned multi-element copper-tin alloy wire with nanocrystals, comprising the following steps:

[0012] Step S1, batching and casting, using a non-vacuum power frequency induction furnace to melt the prepared raw materials and then continuously casting to obtain a copper alloy rod, wherein the melting temperature is 1290-1340℃, and the casting temperature is controlled at 1190-1250℃;

[0013] Step S2, homogenization annealing treatment, placing the copper alloy rod obtained in step S1 in a box furnace for heating, annealing at 850-890℃ for 4-8h;

[0014] Step S3, continuous hot extrusion, continuously hot extruding the copper alloy rod treated in step S2, the heating temperature of the extrusion wheel is 500-700℃, the extrusion speed is 10-15r / min, the extrusion pass is 10-15 passes, the extrusion ratio is 20-35, and an alcohol and water mixed solution is used for cooling to obtain a copper alloy wire;

[0015] Step S4, solid solution treatment, placing the copper alloy wire obtained in step S3 in a box annealing furnace for solid solution treatment, the solid solution treatment temperature is 750-850℃, and after holding for 3-5h, water cooling is used for cooling;

[0016] Step S5, drawing treatment, drawing the copper alloy wire treated in step S4 at a processing rate of 90%-98% to obtain a copper alloy wire;

[0017] Step S6, online annealing treatment, placing the copper alloy wire obtained in step S5 in an online annealing furnace for online continuous annealing treatment to obtain a final copper alloy wire; during the online continuous annealing treatment, the annealing temperature is controlled at 420-450℃, the annealing speed is 5-10cm / s, the cooling method is room temperature cooling, and argon is used as the protective gas.

[0018] Further, the diameter of the final copper alloy wire in step S6 is 0.08-0.30mm.

[0019] Further, the tensile strength of the final copper alloy wire in step S6 is 400-600 MPa, the yield strength is 280-350 MPa, the elongation is 15%-30%, the electrical conductivity is 75%-90% IACS, the softening temperature is 450-580℃, and the pitting corrosion density after the salt spray environmental corrosion experiment is 8-15cm -2 .

[0020] Furthermore, the final copper alloy wire in step S6, alloy <100> Texture accounts for 22% to 35%, alloy <110> Texture accounts for 10% to 22%, alloy <111> Texture accounts for 30% to 40%, alloy <112> Texture accounts for 20% to 36%.

[0021] Furthermore, the specific process of step S1 is as follows: before smelting, electrolytic copper, pure tin, pure silver and pure chromium are added to a vacuum induction furnace; after the above materials are melted, high-purity argon gas is introduced for protection; any one of pure titanium, pure magnesium, pure zirconium, pure silicon and pure iron, and any one of copper lanthanum, copper cerium, copper yttrium, copper scandium, copper gadolinium and copper samarium intermediate alloy are added; the molten pool temperature is raised to 1290-1340°C; after all materials are completely melted, they are uniformly stirred; the casting temperature is controlled at 1190-1250°C; and after keeping warm for 20 minutes, upward continuous casting is performed.

[0022] Furthermore, during the upward continuous casting, the pitch is 2 to 5 mm, the stop time is 0.2 to 0.9 s, the pulling time is 0.1 to 0.3 s, the stop-pull ratio is 2 to 5, the upward speed is 250 to 500 mm / min, and a copper alloy rod with a diameter of 25 mm is cast.

[0023] Compared with the prior art, the nanocrystalline multi-element copper-tin alloy wire and preparation method provided by the present invention have the following beneficial effects:

[0024] 1. The present invention simultaneously adds Ag and Cr to the alloy to produce a synergistic strengthening effect of solid solution, aging, and grain refinement. The Ag element, due to its larger atomic radius, can pin the diffusion of the Cr element, inhibiting the precipitation of the second phase, thereby obtaining nano-scale fine grains. At the same time, it limits the over-aging of the Cu-Sn alloy, improves the mechanical and nanostructure high-temperature stability of the alloy, and expands the operating temperature range of the Cu-Sn alloy.

[0025] 2. The present invention also adds rare earth elements such as La, Ce, Y, Sc, Gd and Sm to the Cu-Sn alloy to obtain nano-grained structure and further enhance grain refinement. The main principle is that during the smelting process, rare earth elements react with some impurity elements or copper elements to form high-melting-point compounds suspended in the melt, becoming additional nucleation centers and promoting grain refinement. The radius of rare earth atoms themselves is 40% to 60% larger than that of copper atoms. Therefore, during the solidification process, they are easily adsorbed on the surface of new copper and copper alloy grains, hindering the continued growth of grains and thus obtaining microcrystalline nanocrystals. After the nanocrystals are formed, they can not only improve the strength of the Cu-Sn alloy through the Hall-Petch effect, but also accelerate the outward diffusion of elements such as Cr during the corrosion process, promote the formation of a passivation film, and improve the corrosion resistance of the alloy.

[0026] 3. The addition of rare earth elements can also purify the melt during the smelting process, effectively removing impurity elements such as S, O, Pb, and Bi;

[0027] 4. The present invention adds Ag and Cr, as well as rare earth elements such as La, Ce, Y, Sc, Gd and Sm, to the Cu-Sn alloy, and then performs annealing, hot extrusion, solid solution, drawing, online annealing and other process treatments to refine the grains and maintain the uniformity and stability of the organizational structure;

[0028] In summary, the present invention significantly improves the microstructure and produces nanocrystalline grains by adding trace elements and rare earth elements to a Cu-Sn alloy. Simultaneously, the processing technology is optimized to generate multiple synergistic strengthening mechanisms, resulting in a nanocrystalline, multi-element, high-strength, high-conductivity, and corrosion-resistant Cu-Sn alloy. The related alloy design principles and processing and heat treatment optimization procedures can provide valuable insights for the preparation, production, and performance improvement of copper alloys, while further expanding the application scope and fields of Cu-Sn alloys.

[0029] Figures in the specification

[0030] Figure 1 The composition table of the copper alloy wires of Examples 1-12;

[0031] Figure 2 These are microstructure photos of different parts of the nanocrystalline multi-component copper-tin alloy wire in Example 9. DETAILED DESCRIPTION

[0032] The following will clearly and completely describe the technical solutions of the present invention in conjunction with the embodiments of the present invention. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts are within the scope of protection of the present invention.

[0033] As a technical solution of the present invention, the present invention provides a multinary copper-tin alloy wire with nanocrystals, wherein the multinary copper-tin alloy wire is mainly composed of the following raw materials in the following mass percentages:

[0034] Sn 0.25%-0.75%, Ag 0.05%-0.15%, Cr 0.08%-0.20%, component A 0.05%-0.2% and component B 0.005%-0.01%, and the rest is Cu;

[0035] Wherein, component A is any one of the six elements of Ti, Mg, Zr, Fe, Si and Zn;

[0036] Wherein, component B is any one of six elements: La, Ce, Y, Sc, Gd and Sm.

[0037] In the present invention, the diameter of the multi-element copper-tin alloy wire is 0.08-0.30 mm.

[0038] In the present invention, the multi-component copper-tin alloy wire material includes: <100> Texture accounts for 22% to 35%, alloy <110> Texture accounts for 10% to 22%, alloy <111> Texture accounts for 30% to 40%, alloy <112> Texture accounts for 20 to 36.

[0039] In the present invention, the tensile strength of the multi-element copper-tin alloy wire is 400-600 MPa, the yield strength is 280-350 MPa, the elongation is 15%-30%, the conductivity is 75%-90 IACS, the softening temperature is 450-580 ° C, and the pitting density after the salt spray environment corrosion test is 8-15 cm -2 .

[0040] As another technical solution of the present invention, the present invention provides a method for preparing the aforementioned multinary copper-tin alloy wire having nanocrystals, comprising the following steps:

[0041] Step S1, mixing and melting the raw materials, using a vacuum frequency induction furnace to melt and then continuously cast to obtain a copper alloy rod, wherein the melting temperature is 1290-1340° C., and the casting temperature is controlled at 1190-1250° C.;

[0042] Step S2, homogenization annealing treatment, placing the copper alloy rod obtained in step S1 in a box furnace for heating, and annealing at 850-890° C. for 4-8 hours;

[0043] Step S3, continuous hot extrusion, continuously hot extruding the copper alloy rod treated in step S2, with the extrusion wheel heating temperature being 500-700° C., the extrusion speed being 10-15 r / min, the extrusion passes being 10-15 passes, the extrusion ratio being 20-35, and cooling with a mixed solution of alcohol and water to obtain a copper alloy wire;

[0044] Step S4, solution treatment, placing the copper alloy wire obtained in step S3 in a box-type annealing furnace for solution treatment at a temperature of 750-850° C., keeping the temperature for 3-5 hours, and then cooling by water cooling;

[0045] Step S5: drawing the copper alloy wire processed in step S4 at a processing rate of 90% to 98% to obtain a copper alloy wire;

[0046] Step S6, online annealing treatment, placing the copper alloy wire obtained in step S5 in an online annealing furnace for online continuous annealing treatment to obtain the final copper alloy wire; during the online continuous annealing treatment, the annealing temperature is controlled at 420-450° C., the annealing speed is 5-10 cm / s, the cooling method is room temperature cooling, and argon is used as the protective gas.

[0047] In the present invention, the diameter of the final copper alloy wire in step S6 is 0.08-0.30 mm.

[0048] In the present invention, the final copper alloy wire in step S6 has a tensile strength of 400-600 MPa, a yield strength of 280-350 MPa, an elongation of 15%-30%, a conductivity of 75%-90 IACS, a softening temperature of 450-580 ° C, and a pitting density of 8-15 cm after the salt spray environment corrosion test. -2 .

[0049] In the present invention, the final copper alloy wire in step S6, alloy <100> Texture accounts for 22% to 35%, alloy <110> Texture accounts for 10% to 22%, alloy <111> Texture accounts for 30% to 40%, alloy <112> Texture accounts for 20% to 36%.

[0050] In the present invention, the specific process of step S1 is as follows: before smelting, electrolytic copper, pure tin, pure silver and pure chromium are added to a vacuum induction furnace. After the above materials are melted, high-purity argon gas is introduced for protection, and any one of pure titanium, pure magnesium, pure zirconium, pure silicon and pure iron, as well as any one of copper lanthanum, copper cerium, copper yttrium, copper scandium, copper gadolinium and copper samarium intermediate alloys are added. The molten pool temperature is raised to 1290-1340°C. After all materials are completely melted, they are uniformly stirred, the casting temperature is controlled at 1190-1250°C, and after being kept warm for 20 minutes, upward continuous casting is performed.

[0051] In the present invention, during the upward continuous casting, the pitch is 2-5 mm, the stop time is 0.2-0.9 s, the pulling time is 0.1-0.3 s, the stop-pull ratio is 2-5, the upward speed is 250-500 mm / min, and a copper alloy rod with a diameter of 25 mm is cast.

[0052] Example 1

[0053] The alloy of the present invention is smelted using the following raw materials: electrolytic copper, pure tin, pure silver, pure chromium, sponge titanium, and copper-lanthanum master alloy. The composition of the alloy is shown in Example 1 in Table 1.

[0054] Step S1, melting and casting: electrolytic copper, pure chromium, pure silver, and pure chromium are added to a non-vacuum power frequency induction furnace. After all materials are melted, high-purity argon gas is introduced for protection. Sponge titanium and copper-lanthanum master alloy are then added, and the temperature is raised to 1300°C. After the melt is completely melted, it is uniformly stirred. The casting temperature is maintained at 1250°C. After holding for 20 minutes, upward continuous casting is performed with a pitch of 3 mm, a dwell time of 0.5 s, a pull time of 0.2 s, a dwell-pull ratio of 2.5, and an upward speed of 400 mm / min to cast a copper rod with a diameter of 25 mm;

[0055] Step S2, homogenization annealing treatment: the copper alloy rod obtained in step S1 is placed in a box furnace for heating and homogenization annealing at 850° C. for 5 h.

[0056] Step S3, continuous hot extrusion: The copper alloy rod treated in step S2 is subjected to multiple continuous hot extrusion passes on a Conform continuous hot extruder, with an extrusion wheel temperature of 500°C, an extrusion speed of 12 r / min, 10 extrusion passes, and an extrusion ratio of 20, and is cooled with a mixed solution of alcohol and water to obtain a copper alloy wire;

[0057] Step S4, solution treatment: the copper alloy wire obtained in step S3 is placed in a box-type annealing furnace for solution treatment at a temperature of 750° C., and after a holding time of 3 h, the wire is cooled by water cooling.

[0058] Step S5, drawing treatment: drawing the copper alloy wire processed in step S4 at a processing rate of 92% to obtain a copper alloy wire;

[0059] Step S6, online annealing treatment: placing the copper alloy wire obtained in step S5 in an online annealing furnace for online continuous annealing treatment to obtain the final copper alloy wire; during the online continuous annealing treatment, the annealing temperature is controlled at 430° C., the annealing speed is 5 cm / s, the cooling method is room temperature cooling, and argon is used as the protective gas.

[0060] After the above ingredients are melt-cast, homogenized annealing, continuous hot extrusion, solution treatment, drawing treatment, and online annealing treatment, its properties are shown in Example 1 in Table 2.

[0061] Example 2

[0062] The alloy of the present invention is smelted using the following raw materials: electrolytic copper, pure tin, pure silver, pure chromium, sponge titanium, and a copper-lanthanum master alloy. The composition of the alloy is shown in Example 2 of Table 1.

[0063] Step S1, melting and casting: electrolytic copper, pure chromium, pure silver, and pure chromium are added to a non-vacuum power frequency induction furnace. After all materials are melted, high-purity argon gas is introduced for protection. Sponge titanium and copper-lanthanum master alloy are then added, and the temperature is raised to 1340°C. After the melt is completely melted, it is uniformly stirred. The casting temperature is maintained at 1250°C. After holding for 20 minutes, upward continuous casting is performed with a pitch of 4 mm, a dwell time of 0.4 s, a pull time of 0.2 s, a dwell-pull ratio of 2.0, and an upward pull speed of 450 mm / min to cast a copper rod with a diameter of 25 mm;

[0064] Step S2, homogenization annealing treatment: the copper alloy rod obtained in step S1 is placed in a box furnace for heating and homogenization annealing at 850° C. for 8 h;

[0065] Step S3, continuous hot extrusion: The copper alloy rod treated in step S2 is subjected to multiple continuous hot extrusion passes on a Conform continuous hot extruder, with an extrusion wheel temperature of 700°C, an extrusion speed of 10 r / min, 15 extrusion passes, and an extrusion ratio of 35, and is cooled with a mixed solution of alcohol and water to obtain a copper alloy wire;

[0066] Step S4, solution treatment: placing the copper alloy wire obtained in step S3 in a box-type annealing furnace for solution treatment at a temperature of 850° C., holding for 5 hours, and then cooling by water cooling;

[0067] Step S5, drawing treatment: drawing the copper alloy wire material processed in step S4 at a processing rate of 98% to obtain a copper alloy wire material;

[0068] Step S6, online annealing treatment: placing the copper alloy wire obtained in step S5 in an online annealing furnace for online continuous annealing treatment to obtain the final copper alloy wire; during the online continuous annealing treatment, the annealing temperature is 450°C, the annealing speed is 5 cm / s, the cooling method is room temperature cooling, and argon is used as the protective gas.

[0069] After the above-mentioned ingredients are melt-cast, homogenized annealing, continuous hot extrusion, solution treatment, drawing, and online annealing, its properties are shown in Example 2 in Table 2.

[0070] Example 3

[0071] The alloy of the present invention is smelted using the following raw materials: electrolytic copper, pure tin, pure silver, pure chromium, sponge titanium, and a copper-cerium master alloy. The composition of the alloy is shown in Example 3 of Table 1.

[0072] Step S1, batching and casting: electrolytic copper, pure chromium, pure silver, pure chromium, and titanium sponge and copper-cerium intermediate alloy are added in a non-vacuum power frequency induction furnace, high-purity argon is introduced for protection after the materials are all melted, the temperature is raised to 1320 DEG C, the melt is uniformly stirred after completely melting, the casting temperature is maintained at 1200 DEG C, and after 20 min of heat preservation, continuous casting is carried out by upward drawing, the pitch is 3 mm, the stopping time is 0.8 s, the drawing time is 0.2 s, the stopping-drawing ratio is 4.0, the upward drawing speed is 480 mm / min, and a copper rod with a diameter of 25 mm is cast;

[0073] Step S2, homogenization annealing treatment: the copper alloy rod obtained in step S1 is placed in a box furnace for heating, and homogenization annealing is carried out at 880 DEG C for 6 h;

[0074] Step S3, continuous hot extrusion: the copper alloy rod treated in step S2 is subjected to multi-pass continuous hot extrusion on a Conform continuous hot extrusion machine, the extrusion wheel temperature is 600 DEG C, the extrusion speed is 12 r / min, the extrusion pass is 10 passes, the extrusion ratio is 32, and an alcohol and water mixed solution is used for cooling to obtain a copper alloy wire;

[0075] Step S5, solution treatment: the copper alloy wire obtained in step S3 is placed in a box annealing furnace for solution treatment, the solution treatment temperature is 800 DEG C, the heat preservation time is 4 h, and then water cooling is adopted for cooling;

[0076] Step S5, drawing treatment: the copper alloy wire after step S4 treatment is drawn at a processing rate of 95% to obtain a copper alloy wire;

[0077] Step S6, online annealing treatment: the copper alloy wire obtained in step S5 is placed in an online annealing furnace for online continuous annealing treatment to obtain a final copper alloy wire; during the online continuous annealing treatment, the annealing temperature is 450 DEG C, the annealing speed is 8 cm / s, the cooling method is room temperature cooling, and argon is used as the protective gas.

[0078] After the above batching and casting, homogenization annealing, continuous hot extrusion, solution treatment, drawing, and online annealing treatment, the performance is shown in example 3 in table 2.

[0079] Example 4

[0080] The alloy of the application is melted by using the following raw materials: electrolytic copper, pure tin, pure silver, pure chromium, titanium sponge, and copper-yttrium intermediate alloy. The composition of the alloy is shown in example 4 in table 1.

[0081] Step S1, melting and casting: electrolytic copper, pure chromium, pure silver, and pure chromium are added to a non-vacuum power frequency induction furnace. After all materials are melted, high-purity argon gas is introduced for protection. Sponge titanium and copper-yttrium master alloy are then added, and the temperature is raised to 1320°C. After the melt is completely melted, it is uniformly stirred. The casting temperature is maintained at 1220°C. After holding for 20 minutes, upward continuous casting is performed with a pitch of 2 mm, a dwell time of 0.7 s, a pull time of 0.3 s, a dwell-pull ratio of 2.3, and an upward speed of 400 mm / min. A copper rod with a diameter of 25 mm is cast;

[0082] Step S2, homogenization annealing treatment: the copper alloy rod obtained in step S1 is placed in a box furnace for heating and homogenization annealing at 880° C. for 4 h;

[0083] Step S3, continuous hot extrusion: The copper alloy rod treated in step S2 is subjected to multiple continuous hot extrusion passes on a Conform continuous hot extruder, with an extrusion wheel temperature of 700°C, an extrusion speed of 14 r / min, 12 extrusion passes, and an extrusion ratio of 30, and is cooled with a mixed solution of alcohol and water to obtain a copper alloy wire;

[0084] Step S4, solution treatment: placing the copper alloy wire obtained in step S3 in a box-type annealing furnace for solution treatment at a temperature of 820° C., holding for 4 hours, and then cooling by water cooling;

[0085] Step S5, drawing treatment: drawing the copper alloy wire material processed in step S4 at a processing rate of 94% to obtain a copper alloy wire material;

[0086] Step S6, online annealing treatment: placing the copper alloy wire obtained in step S5 in an online annealing furnace for online continuous annealing treatment to obtain the final copper alloy wire; during the online continuous annealing treatment, the annealing temperature is 420°C, the annealing speed is 9 cm / s, the cooling method is room temperature cooling, and argon is used as the shielding gas.

[0087] After the above-mentioned ingredients are melt-cast, homogenized annealing, continuous hot extrusion, solution treatment, drawing, and online annealing, its properties are shown in Example 4 in Table 2.

[0088] Example 5

[0089] The alloy of the present invention is smelted using the following raw materials: electrolytic copper, pure tin, pure silver, pure chromium, sponge titanium, and a copper-scandium master alloy. The composition of the alloy is shown in Example 5 of Table 1.

[0090] Step S1, melting and casting: electrolytic copper, pure chromium, pure silver, and pure chromium are added to a non-vacuum power frequency induction furnace. After all materials are melted, high-purity argon gas is introduced for protection. Sponge titanium and copper-scandium master alloy are then added, and the temperature is raised to 1300°C. After the melt is completely melted, it is uniformly stirred. The casting temperature is maintained at 1200°C. After holding for 20 minutes, upward continuous casting is performed with a pitch of 3 mm, a dwell time of 0.8 s, a pull time of 0.3 s, a dwell-pull ratio of 2.6, and an upward pull speed of 350 mm / min to cast a copper rod with a diameter of 25 mm;

[0091] Step S2, homogenization annealing treatment: the copper alloy rod obtained in step S1 is placed in a box furnace for heating and homogenization annealing at 850° C. for 6 h;

[0092] Step S3, continuous hot extrusion: The copper alloy rod treated in step S2 is subjected to multiple continuous hot extrusion passes on a Conform continuous hot extruder, with an extrusion wheel temperature of 600°C, an extrusion speed of 12 r / min, 14 extrusion passes, and an extrusion ratio of 33, and is cooled with a mixed solution of alcohol and water to obtain a copper alloy wire;

[0093] Step S4, solution treatment: placing the copper alloy wire obtained in step S3 in a box-type annealing furnace for solution treatment at a temperature of 800° C., holding for 4 hours, and then cooling by water cooling;

[0094] Step S5, drawing treatment: drawing the copper alloy wire processed in step S4 at a processing rate of 94% to obtain a copper alloy wire;

[0095] Step S6, online annealing treatment: placing the copper alloy wire obtained in step S5 in an online annealing furnace for online continuous annealing treatment to obtain the final copper alloy wire; during the online continuous annealing treatment, the annealing temperature is 450°C, the annealing speed is 8 cm / s, the cooling method is room temperature cooling, and argon is used as the protective gas.

[0096] After the above-mentioned ingredients are melt-cast, homogenized annealing, continuous hot extrusion, solution treatment, drawing, and online annealing, its properties are shown in Example 5 in Table 2.

[0097] Example 6

[0098] The alloy of the present invention is smelted using the following raw materials: electrolytic copper, pure tin, pure silver, pure chromium, sponge titanium, and a copper-gadolinium master alloy. The composition of the alloy is shown in Example 6 in Table 1.

[0099] Step S1, melting and casting: electrolytic copper, pure chromium, pure silver, and pure chromium are added to a non-vacuum power frequency induction furnace. After all materials are melted, high-purity argon gas is introduced for protection. Sponge titanium and copper-gadolinium master alloy are then added. The temperature is raised to 1310°C. After the melt is completely melted, it is uniformly stirred. The casting temperature is maintained at 1200°C. After holding for 20 minutes, upward continuous casting is performed with a pitch of 5 mm, a dwell time of 0.8 s, a pull time of 0.2 s, a dwell-pull ratio of 4.0, and an upward pull speed of 270 mm / min. A copper rod with a diameter of 25 mm is cast.

[0100] Step S2, homogenization annealing treatment: the copper alloy rod obtained in step S1 is placed in a box furnace for heating and homogenization annealing at 800° C. for 6 h;

[0101] Step S3, continuous hot extrusion: The copper alloy rod treated in step S2 is subjected to multiple continuous hot extrusion passes on a Conform continuous hot extruder, with an extrusion wheel temperature of 550° C., an extrusion speed of 11 r / min, 12 extrusion passes, and an extrusion ratio of 30, and is cooled with a mixed solution of alcohol and water to obtain a copper alloy wire;

[0102] Step S4, solution treatment: placing the copper alloy wire obtained in step S3 in a box-type annealing furnace for solution treatment at a temperature of 820° C., keeping the temperature for 5 hours, and then cooling by water cooling;

[0103] Step S5, drawing treatment: drawing the copper alloy wire processed in step S4 at a processing rate of 92% to obtain a copper alloy wire;

[0104] Step S6, online annealing treatment: placing the copper alloy wire obtained in step S5 in an online annealing furnace for online continuous annealing treatment to obtain the final copper alloy wire; during the online continuous annealing treatment, the annealing temperature is 430°C, the annealing speed is 9 cm / s, the cooling method is room temperature cooling, and argon is used as the protective gas.

[0105] After the above-mentioned ingredients are melt-cast, homogenized annealing, continuous hot extrusion, solution treatment, drawing, and online annealing, its properties are shown in Example 6 in Table 2.

[0106] Example 7

[0107] The alloy of the present invention is smelted using the following raw materials: electrolytic copper, pure tin, pure silver, pure chromium, sponge titanium, and copper-samarium master alloy. The composition of the alloy is shown in Example 7 of Table 1.

[0108] Step S1, melting and casting: electrolytic copper, pure chromium, pure silver, and pure chromium are added to a non-vacuum power frequency induction furnace. After all materials are melted, high-purity argon gas is introduced for protection. Sponge titanium and copper-samarium master alloy are then added. The temperature is raised to 1290°C. After the melt is completely melted, it is uniformly stirred. The casting temperature is maintained at 1220°C. After holding for 20 minutes, upward continuous casting is performed with a pitch of 3 mm, a dwell time of 0.9 s, a pull time of 0.3 s, a dwell-pull ratio of 3.0, and an upward pull speed of 400 mm / min. A copper rod with a diameter of 25 mm is cast.

[0109] Step S2, homogenization annealing treatment: the copper alloy rod obtained in step S1 is placed in a box furnace for heating and homogenization annealing at 820° C. for 4 h;

[0110] Step S3, continuous hot extrusion: The copper alloy rod treated in step S2 is subjected to multiple continuous hot extrusion passes on a Conform continuous hot extruder, with an extrusion wheel temperature of 650°C, an extrusion speed of 10 r / min, 15 extrusion passes, and an extrusion ratio of 24, and is cooled with a mixed solution of alcohol and water to obtain a copper alloy wire;

[0111] Step S4, solution treatment: the copper alloy wire obtained in step S3 is placed in a box-type annealing furnace for solution treatment at a temperature of 800° C., kept at this temperature for 4 h, and then cooled by water cooling.

[0112] Step S5, drawing treatment: drawing the copper alloy wire material processed in step S4 at a processing rate of 95% to obtain a copper alloy wire material;

[0113] Step S6, online annealing treatment: placing the copper alloy wire obtained in step S5 in an online annealing furnace for online continuous annealing treatment to obtain the final copper alloy wire; during the online continuous annealing treatment, the annealing temperature is 440°C, the annealing speed is 8 cm / s, the cooling method is room temperature cooling, and argon is used as the protective gas.

[0114] After the above-mentioned ingredients are melt-cast, homogenized annealing, continuous hot extrusion, solution treatment, drawing, and online annealing, its properties are shown in Example 7 in Table 2.

[0115] Example 8

[0116] The alloy of the present invention is smelted using the following raw materials: electrolytic copper, pure tin, pure silver, pure chromium, pure magnesium, and a copper-cerium master alloy. The composition of the alloy is shown in Example 8 in Table 1.

[0117] Step S1, melting and casting: electrolytic copper, pure chromium, pure silver, and pure chromium are added to a non-vacuum power frequency induction furnace. After all materials are melted, high-purity argon gas is introduced for protection. Pure magnesium and copper-cerium master alloy are then added, and the temperature is raised to 1310°C. After the melt is completely melted, it is uniformly stirred. The casting temperature is maintained at 1240°C. After holding for 20 minutes, upward continuous casting is performed with a pitch of 2 mm, a dwell time of 0.6 s, a pull time of 0.2 s, a dwell-pull ratio of 3.0, and an upward pull speed of 490 mm / min. A copper rod with a diameter of 25 mm is cast.

[0118] Step S2, homogenization annealing treatment: the copper alloy rod obtained in step S1 is placed in a box furnace for heating and homogenization annealing at 820° C. for 6 h;

[0119] Step S3, continuous hot extrusion: The copper alloy rod treated in step S2 is subjected to multiple continuous hot extrusion passes on a Conform continuous hot extruder, with an extrusion wheel temperature of 680°C, an extrusion speed of 12 r / min, 12 extrusion passes, and an extrusion ratio of 28, and is cooled with a mixed solution of alcohol and water to obtain a copper alloy wire;

[0120] Step S4, solution treatment: placing the copper alloy wire obtained in step S3 in a box-type annealing furnace for solution treatment at a temperature of 820° C., keeping the temperature for 5 hours, and then cooling by water cooling;

[0121] Step S5, drawing treatment: drawing the copper alloy wire processed in step S4 at a processing rate of 96% to obtain a copper alloy wire;

[0122] Step S6, online annealing treatment: placing the copper alloy wire obtained in step S5 in an online annealing furnace for online continuous annealing treatment to obtain the final copper alloy wire; during the online continuous annealing treatment, the annealing temperature is 430° C., the annealing speed is 9 cm / s, the cooling method is room temperature cooling, and argon is used as the shielding gas;

[0123] After the above-mentioned ingredients are melt-cast, homogenized annealing, continuous hot extrusion, solution treatment, drawing, and online annealing, its properties are shown in Example 8 in Table 2.

[0124] Example 9

[0125] The alloy of the present invention is smelted using the following raw materials: electrolytic copper, pure tin, pure silver, pure chromium, sponge zirconium, and copper-yttrium master alloy. The composition of the alloy is shown in Example 9 in Table 1.

[0126] Step S1, batching and casting: electrolytic copper, pure chromium, pure silver, pure chromium are added in a non-vacuum power frequency induction furnace, after each material is melted, high-purity argon is introduced for protection, then sponge zirconium and copper-yttrium intermediate alloy are added, the temperature is raised to 1310 DEG C, after the melt is completely melted, uniform stirring is carried out, the casting temperature is kept at 1250 DEG C, after 20 min of insulation, up-drawing continuous casting is carried out, the pitch is 3 mm, the stopping time is 0.7 s, the drawing time is 0.2 s, the stopping-drawing ratio is 3.5, the up-drawing speed is 450 mm / min, and a copper rod with a diameter of 25 mm is cast;

[0127] Step S2, homogenization annealing treatment: the copper alloy rod obtained in step S1 is placed in a box furnace for heating, and homogenization annealing is carried out at 850 DEG C for 5 h;

[0128] Step S3, continuous hot extrusion: the copper alloy rod treated in step S2 is subjected to multi-pass continuous hot extrusion on a Conform continuous hot extrusion machine, the extrusion wheel temperature is 590 DEG C, the extrusion speed is 13 r / min, the extrusion pass is 15 passes, the extrusion ratio is 33, and an alcohol and water mixed solution is used for cooling to obtain a copper alloy wire;

[0129] Step S4, solid solution treatment: the copper alloy wire obtained in step S3 is placed in a box annealing furnace for solid solution treatment, the solid solution treatment temperature is 830 DEG C, after 5 h of insulation, water cooling is used for cooling;

[0130] Step S5, drawing treatment: the copper alloy wire after step S4 treatment is drawn at a processing rate of 95% to obtain a copper alloy wire;

[0131] Step S6, online annealing treatment: the copper alloy wire obtained in step S5 is placed in an online annealing furnace for online continuous annealing treatment to obtain a final copper alloy wire; during the online continuous annealing treatment, the annealing temperature is 440 DEG C, the annealing speed is 10 cm / s, the cooling method is room temperature cooling, and argon is used as the protective gas.

[0132] After the above batching and casting, homogenization annealing, continuous hot extrusion, solid solution treatment, drawing and online annealing treatment, the performance is shown in example 9 in table 2.

[0133] Example 10

[0134] The alloy of the application is smelted by using the following raw materials: electrolytic copper, pure tin, pure silver, pure chromium, pure iron, copper-scandium intermediate alloy. The composition of the alloy is shown in example 10 of table 1.

[0135] Step S1, melting and casting: electrolytic copper, pure chromium, pure silver, and pure chromium are added to a non-vacuum power frequency induction furnace. After all materials are melted, high-purity argon gas is introduced for protection. Pure iron and copper-scandium master alloy are then added, and the temperature is raised to 1330°C. After the melt is completely melted, it is uniformly stirred. The casting temperature is maintained at 1220°C. After holding for 20 minutes, upward continuous casting is performed with a pitch of 3 mm, a dwell time of 0.9 s, a pull time of 0.2 s, a dwell-pull ratio of 4.5, and an upward pull speed of 400 mm / min to cast a copper rod with a diameter of 25 mm;

[0136] Step S2, homogenization annealing treatment: the copper alloy rod obtained in step S1 is placed in a box furnace for heating and homogenization annealing at 880° C. for 6 h;

[0137] Step S3, continuous hot extrusion: The copper alloy rod treated in step S2 is subjected to multiple continuous hot extrusion passes on a Conform continuous hot extruder, with an extrusion wheel temperature of 600° C., an extrusion speed of 12 r / min, 14 extrusion passes, and an extrusion ratio of 30, and is cooled with a mixed solution of alcohol and water to obtain a copper alloy wire;

[0138] Step S4, solution treatment: placing the copper alloy wire obtained in step S3 in a box-type annealing furnace for solution treatment at a temperature of 760° C., keeping the temperature for 5 hours, and then cooling by water cooling;

[0139] Step S5, drawing treatment: drawing the copper alloy wire material processed in step S4 at a processing rate of 95% to obtain a copper alloy wire material;

[0140] Step S6, online annealing treatment: placing the copper alloy wire obtained in step S5 in an online annealing furnace for online continuous annealing treatment to obtain the final copper alloy wire; during the online continuous annealing treatment, the annealing temperature is 430°C, the annealing speed is 8 cm / s, the cooling method is room temperature cooling, and argon is used as the protective gas.

[0141] After the above-mentioned ingredients are melt-cast, homogenized annealing, continuous hot extrusion, solution treatment, drawing, and online annealing, its properties are shown in Example 10 in Table 2.

[0142] Example 11

[0143] The alloy of the present invention is smelted using the following raw materials: electrolytic copper, pure tin, pure silver, pure chromium, pure silicon, and a copper-gadolinium master alloy. The composition of the alloy is shown in Example 11 in Table 1.

[0144] Step S1, melting and casting: electrolytic copper, pure chromium, pure silver, and pure chromium are added to a non-vacuum power frequency induction furnace. After all materials are melted, high-purity argon gas is introduced for protection. Pure silicon and a copper-gadolinium master alloy are then added. The temperature is raised to 1300°C. After the melt is completely melted, it is uniformly stirred. The casting temperature is maintained at 1240°C. After holding for 20 minutes, upward continuous casting is performed with a pitch of 2 mm, a dwell time of 0.9 s, a pull time of 0.4 s, a dwell-pull ratio of 2.3, and an upward pull speed of 360 mm / min. A copper rod with a diameter of 25 mm is cast.

[0145] Step S2, homogenization annealing treatment: the copper alloy rod obtained in step S1 is placed in a box furnace for heating and homogenization annealing at 880° C. for 6 h;

[0146] Step S3, continuous hot extrusion: The copper alloy rod treated in step S2 is subjected to multiple continuous hot extrusion passes on a Conform continuous hot extruder, with an extrusion wheel temperature of 690° C., an extrusion speed of 10 r / min, 10 extrusion passes, and an extrusion ratio of 35, and is cooled with a mixed solution of alcohol and water to obtain a copper alloy wire;

[0147] Step S4, solution treatment: Place the copper alloy wire obtained in step S3 in a box-type annealing furnace for solution treatment at a temperature of 840°C, keep the temperature for 4 hours, and then cool it by water cooling.

[0148] Step S5, drawing treatment: drawing the copper alloy wire processed in step S4 at a processing rate of 92% to obtain a copper alloy wire;

[0149] Step S6, online annealing treatment: placing the copper alloy wire obtained in step S5 in an online annealing furnace for online continuous annealing treatment to obtain the final copper alloy wire; during the online continuous annealing treatment, the annealing temperature is 430°C, the annealing speed is 8 cm / s, the cooling method is room temperature cooling, and argon is used as the protective gas.

[0150] After the above-mentioned ingredients are melt-cast, homogenized annealing, continuous hot extrusion, solution treatment, drawing, and online annealing, its properties are shown in Example 11 in Table 2.

[0151] Example 12

[0152] The alloy of the present invention is smelted using the following raw materials: electrolytic copper, pure tin, pure silver, pure chromium, pure zinc, and a copper-samarium master alloy. The composition of the alloy is shown in Example 12 of Table 1.

[0153] Step S1, melting and casting: electrolytic copper, pure chromium, pure silver, and pure chromium are added to a non-vacuum power frequency induction furnace. After all materials are melted, high-purity argon gas is introduced for protection. Pure zinc and copper-samarium master alloy are then added. The temperature is raised to 1330°C. After the melt is completely melted, it is uniformly stirred. The casting temperature is maintained at 1220°C. After holding for 20 minutes, upward continuous casting is performed with a pitch of 3 mm, a dwell time of 0.6 s, a pull time of 0.2 s, a dwell-pull ratio of 3.0, and an upward pull speed of 480 mm / min. A copper rod with a diameter of 25 mm is cast.

[0154] Step S2, homogenization annealing treatment: the copper alloy rod obtained in step S1 is placed in a box furnace for heating, and homogenization annealing is performed at 860° C. for 7 h;

[0155] Step S3, continuous hot extrusion: The copper alloy rod treated in step S2 is subjected to multiple continuous hot extrusion passes on a Conform continuous hot extruder, with an extrusion wheel temperature of 570°C, an extrusion speed of 11 r / min, 12 extrusion passes, and an extrusion ratio of 30, and is cooled with a mixed solution of alcohol and water to obtain a copper alloy wire;

[0156] Step S4, solution treatment: placing the copper alloy wire obtained in step S3 in a box-type annealing furnace for solution treatment at a temperature of 800° C., keeping the temperature for 3 h, and then cooling by water cooling;

[0157] Step S5, drawing treatment: drawing the copper alloy wire material processed in step S4 at a processing rate of 96% to obtain a copper alloy wire material;

[0158] Step S6, online annealing treatment: placing the copper alloy wire obtained in step S5 in an online annealing furnace for online continuous annealing treatment to obtain the final copper alloy wire; during the online continuous annealing treatment, the annealing temperature is 440°C, the annealing speed is 8 cm / s, the cooling method is room temperature cooling, and argon is used as the protective gas.

[0159] After the above-mentioned ingredients are melt-cast, homogenized annealing, continuous hot extrusion, solution treatment, drawing, and online annealing, its properties are shown in Example 12 in Table 2.

[0160] Table 1 Alloy composition formula of Examples 1-12 (wt.%)

[0161]

[0162] Table 2 Physical properties of copper alloy wires of Examples 1-12

[0163]

[0164] The foregoing merely illustrates the principles of the application and application of its leading features. This application is not limited to the exact details shown above and described herein, and obvious modifications and variations are possible in light of the above teachings or can be acquired from practice of the application. Accordingly, all changes and modifications that come within the meaning and range of equivalents of the claims are to be embraced within the scope thereof as herein set forth.

[0165] Furthermore, it should be understood that although the description herein is made on the basis of the embodiments, not every embodiment contains only one independent technical solution, and the description herein is only for the sake of clarity, and those skilled in the art should understand the description as a whole, and the technical solutions in each embodiment can also be properly combined to form other embodiments that those skilled in the art can understand.

Claims

1. A multi-component copper-tin alloy wire with nanocrystals, characterized in that: The multi-element copper-tin alloy wire is mainly composed of the following raw materials in percentage by mass: Sn 0.25%-0.75%, Ag 0.05%-0.15%, Cr 0.08%-0.20%, component A 0.05%-0.2% and component B 0.005%-0.01%, and the rest is Cu; Wherein, component A is any one of the six elements of Ti, Mg, Zr, Fe, Si and Zn; Wherein, component B is any one of the six elements La, Ce, Y, Sc, Gd and Sm.

2. The nanocrystalline multi-component copper-tin alloy wire according to claim 1, wherein: The diameter of the multi-component copper-tin alloy wire is 0.08-0.30 mm.

3. The nanocrystalline multi-component copper-tin alloy wire according to claim 1 or 2, characterized in that: In the multi-element copper-tin alloy wire, the alloy <100> Texture accounts for 22% to 35%, alloy <110> Texture accounts for 10% to 22%, alloy <111> Texture accounts for 30% to 40%, alloy <112> Texture accounts for 20 to 36.

4. The nanocrystalline multinary copper-tin alloy wire according to claim 1 or 2, characterized in that: The multi-element copper-tin alloy wire has a tensile strength of 400-600 MPa, a yield strength of 280-350 MPa, an elongation of 15%-30%, a conductivity of 75%-90 IACS, a softening temperature of 450-580°C, and a pitting density of 8-15 cm after a salt spray environment corrosion test. -2 .

5. A method for preparing the nanocrystalline multinary copper-tin alloy wire according to claim 1, characterized in that: The following steps are involved: Step S1, preparing materials for melting and casting, using a non-vacuum power frequency induction furnace to melt the prepared raw materials and then continuously casting them to obtain copper alloy rods, wherein the melting temperature is 1290-1340° C., wherein the casting temperature is controlled at 1190-1250° C.; Step S2, homogenization annealing treatment, placing the copper alloy rod obtained in step S1 in a box furnace for heating, and annealing at 850-890° C. for 4-8 hours; Step S3, continuous hot extrusion, continuously hot extruding the copper alloy rod treated in step S2, with the extrusion wheel heating temperature being 500-700° C., the extrusion speed being 10-15 r / min, the extrusion passes being 10-15 passes, the extrusion ratio being 20-35, and cooling with a mixed solution of alcohol and water to obtain a copper alloy wire; Step S4, solution treatment, placing the copper alloy wire obtained in step S3 in a box-type annealing furnace for solution treatment at a temperature of 750-850° C., keeping the temperature for 3-5 hours, and then cooling by water cooling; Step S5: drawing the copper alloy wire processed in step S4 at a processing rate of 90% to 98% to obtain a copper alloy wire; Step S6, online annealing treatment, placing the copper alloy wire obtained in step S5 in an online annealing furnace for online continuous annealing treatment to obtain the final copper alloy wire; during the online continuous annealing treatment, the annealing temperature is controlled at 420-450° C., the annealing speed is 5-10 cm / s, the cooling method is room temperature cooling, and argon is used as the protective gas.

6. The method for preparing a nanocrystalline multinary copper-tin alloy wire according to claim 5, wherein: The final diameter of the copper alloy wire in step S6 is 0.08-0.30 mm.

7. The method for preparing a nanocrystalline multinary copper-tin alloy wire according to claim 5, wherein: The final copper alloy wire in step S6 has a tensile strength of 400-600 MPa, a yield strength of 280-350 MPa, an elongation of 15%-30%, a conductivity of 75%-90 IACS, a softening temperature of 450-580°C, and a pitting density of 8-15 cm after the salt spray environment corrosion test. -2 .

8. The method for preparing nanocrystalline multinary copper-tin alloy wire according to claim 5, characterized in that: The final copper alloy wire in step S6, alloy <100> Texture accounts for 22% to 35%, alloy <110> Texture accounts for 10% to 22%, alloy <111> Texture accounts for 30% to 40%, alloy <112> Texture accounts for 20% to 36%.

9. The method for preparing a multinary copper-tin alloy wire having nanocrystals according to claim 5, characterized in that: The specific process of step S1 is as follows: before smelting, electrolytic copper, pure tin, pure silver and pure chromium are added to a vacuum induction furnace. After the above materials are melted, high-purity argon gas is introduced for protection. Any one of pure titanium, pure magnesium, pure zirconium, pure silicon and pure iron, as well as any one of copper lanthanum, copper cerium, copper yttrium, copper scandium, copper gadolinium and copper samarium master alloy are added. The molten pool temperature is raised to 1290-1340°C. After all materials are completely melted, they are uniformly stirred, the casting temperature is controlled at 1190-1250°C, and the upward continuous casting is performed after the heat is maintained for 20 minutes.

10. The method for preparing a nanocrystalline multinary copper-tin alloy wire according to claim 9, wherein: During the upward continuous casting, the pitch is 2-5 mm, the stopping time is 0.2-0.9 s, the pulling time is 0.1-0.3 s, the stopping-pulling ratio is 2-5, the upward pulling speed is 250-500 mm / min, and a copper alloy rod with a diameter of 25 mm is cast.

Images