CN109355525B - Multi-scale multi-element high-strength high-conductivity copper chromium zirconium alloy material and preparation method thereof - Google Patents
Multi-scale multi-element high-strength high-conductivity copper chromium zirconium alloy material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a multi-scale multi-element high-strength high-conductivity copper chromium zirconium alloy material and a preparation method thereof, belonging to the field of nonferrous metal processing. The alloy material comprises, by weight, 0.05-0.75% of Cr, 0.05-0.2% of Zr and the balance of Cu, and is obtained by batching, feeding, smelting and casting, homogenizing annealing treatment, hot extrusion, solution treatment, cold drawing, aging treatment, secondary cold drawing and online annealing treatment. The alloy material has the tensile strength of 300-700 MPa, the yield strength of 150-600 MPa, the elongation of 10-30%, the electric conductivity of 70-95% IACS, the softening temperature of 500-600 ℃, and the repeated bending frequency of 1 multiplied by 105～1×108Secondly, the requirements of important fields such as precise cables, electrified railway contact wires, resistance welding electrodes and the like are completely met.
Description
Technical Field
The invention belongs to the field of nonferrous metal processing, and particularly relates to a multi-scale multi-element high-strength high-conductivity copper chromium zirconium alloy material and a preparation method thereof.
Background
The Cu-Cr-Zr alloy has higher strength, good electric and thermal conductivity, good weldability, oxidation resistance, wear resistance and other excellent comprehensive properties, is widely applied to the fields of lead frames of large-scale integrated circuits, overhead conductors of large-scale electric locomotives, liners of crystallizer of continuous casting machines in heat exchange environments, resistance welding electrodes and the like, and becomes a structural functional material in the high-strength and high-conductivity field of the electronic circuit industry.
The strengthening means of the high-strength and high-conductivity Cu-Cr-Zr series copper alloy mainly comprises solid solution strengthening, aging strengthening, fine grain strengthening, deformation strengthening and the like. In the Cu-Cr-Zr alloy, the elements for strengthening the copper alloy in the form of solid solution atoms mainly include Sn, Ag, Ce, Ni, Al, Zn, and the like. Ag and Sn are selected alloy elements in the alloy, and the addition of Ag mainly acts for hindering the diffusion process of Cr atoms, effectively inhibiting the precipitation and aggregation growth of a Cr phase and delaying the overaging of the Cu-Cr-Zr alloy, so that the high-temperature stability of the alloy is improved, and the strength of the alloy is increased; the addition of Sn has the effect that Sn is easy to segregate on grain boundaries and dislocation lines, thereby not only inhibiting the precipitation of Cr in the aging process after hot rolling and making the Cr precipitate fine, but also pinning dislocations, hindering the movement of dislocations and delaying recovery and recrystallization. The invention develops a multi-scale multi-element high-strength high-conductivity Cu-Cr-Zr alloy material by mainly adding various trace elements into Cu-Cr alloy and improving a processing heat treatment system, and meets the use requirements of different fields on copper alloy materials.
Disclosure of Invention
The invention aims to provide a multi-scale multi-element high-strength high-conductivity copper chromium zirconium alloy material and a preparation method thereof, and is characterized in that the weight percentage of the alloy material is 0.05-0.75% of Cr, 0.05-0.2% of Zr and the balance of Cu;
the alloy material has bean-shaped Cr phase with 2-10 nm grain size and 1 x 10 density21～5×1022m-3；
The alloy material has Moire fringe-shaped Cr phase with body-centered cubic structure with grain diameter of 5-10 nm on transverse and longitudinal sections, and the precipitation density is 5 x 1022～2×1023m-3；
The alloy material has a disc-shaped Cu structure with a face-centered cubic structure with the grain diameter of 50-100 nm on the transverse and longitudinal sections5Zr phase with a precipitation density of 1X 1017～5×1018m-3；
The alloy material has grains on the transverse and longitudinal sectionsThe CuCrZr phase with the diameter of 20nm to 50nm and the precipitation density of 1 multiplied by 1017～5×1017m-3；
The alloy material comprises 15-25% of alloy <100> texture, 15-25% of alloy <110> texture, 25-45% of alloy <111> texture and 13-30% of alloy <112> texture.
The alloy at least comprises one or two of Ti, Ag, Mg and Sn, wherein the content of Ti, Ag, Mg and Sn is 0.05-0.2%, and the total content of alloy elements is 0.1-0.4%.
The total content of alloy elements in the alloy is preferably 0.15-0.3%.
The alloy material has a tensile strength of 300-700 MPa, a yield strength of 150-600 MPa, an elongation of 10-30%, an electrical conductivity of 70-95% IACS, a softening temperature of 500-600 ℃, and a number of repeated bending times of 1 × 105～1×108Next, the process is carried out.
The preparation method of the multi-scale multielement high-strength high-conductivity copper chromium zirconium series alloy material is characterized by comprising the following steps of: a. proportioning, feeding, smelting and casting according to mass percentage; b. carrying out homogenization annealing treatment; c. hot extrusion; d. solution treatment; e. cold drawing; f. aging treatment; g. cold drawing; h. and (4) carrying out online annealing treatment.
And c, smelting and casting in the step a by using a vacuum medium-frequency induction furnace, wherein the smelting temperature is 1230-1280 ℃, and the casting temperature is 1150-1200 ℃.
The smelting and casting process in the step a comprises the following steps: adding electrolytic copper, copper-chromium intermediate alloy and copper-zirconium intermediate alloy into a vacuum induction furnace before smelting, adding one or two of pure titanium, pure silver, pure tin and pure magnesium after the materials are all molten, raising the temperature to 1230-1280 ℃, uniformly stirring after the melt is completely molten, controlling the casting temperature at 1150-1200 ℃, and casting after heat preservation for 20 min.
And c, the homogenizing annealing treatment in the step b is to heat the alloy ingot in a stepping box type furnace at 900-950 ℃ for 6-12 hours.
Wherein the extrusion finishing temperature of the hot extrusion in the step c is 800-850 ℃, and the extrusion ratio is 15-30.
And d, performing solid solution treatment at 900-1000 ℃, keeping the temperature for 2-6 h, and performing water cooling in the cooling mode.
Wherein the processing rate of the cold drawing in the step e is 60-80%.
And f, the aging treatment temperature in the step f is 400-500 ℃, the heat preservation time is 6-10 hours, and the cooling mode is air cooling.
And g, wherein the processing rate of the cold drawing in the step g is 30-50%.
And h, performing on-line annealing treatment at the temperature of 450-550 ℃, at the annealing speed of 10-20 cm/s, wherein the cooling mode is air cooling, and the protective gas is pure hydrogen.
The invention has the beneficial effects that:
the method comprises the steps of designing and optimizing components of the copper alloy and regulating and controlling microstructure through thermodynamic software, high-temperature solution treatment and corresponding aging matching treatment technology to obtain the high-strength high-conductivity copper-chromium-zirconium alloy material with multi-scale multi-element precipitated phase dispersed distribution, wherein the tensile strength of the alloy material is 300-700 MPa, the yield strength is 150-600 MPa, the elongation is 10-30%, the conductivity is 70-95% IACS, the softening temperature is 500-600 ℃, and the repeated bending frequency is 1 multiplied by 105～1×108Secondly, the requirements of important fields such as precise cables, electrified railway contact wires, resistance welding electrodes and the like are completely met.
Drawings
FIG. 1 is a TEM image of a Cu-Cr-Zr-Ag alloy;
FIGS. 2 and 3 are HRTEM images of Cu-Cr-Zr-Ag alloys.
Detailed Description
The invention provides a multi-scale multi-element high-strength high-conductivity copper chromium zirconium alloy material and a preparation method thereof, and the invention is further explained by combining with the embodiment.
Example 1:
in the embodiment, the alloy is smelted by adopting the following raw materials: electrolytic copper, copper chromium master alloy, copper zirconium master alloy and pure silver, the alloy composition is shown in table 1 below as example 1.
a. Smelting: adding electrolytic copper, copper-chromium intermediate alloy, copper-zirconium intermediate alloy and pure silver into a vacuum induction furnace, heating to 1230 ℃ after the materials are all melted, uniformly stirring after the melt is completely melted, controlling the casting temperature at 1150 ℃, and casting after heat preservation for 20 min.
b. Homogenization and hot extrusion: heating the alloy cast ingot in a stepping box type furnace at 900 ℃ for 12h, then carrying out hot extrusion on the cast ingot, controlling the temperature to be 800 ℃ after extrusion, and carrying out water cooling on the cast ingot at an extrusion ratio of 15.
c. Solution treatment: and carrying out solid solution treatment on the extruded alloy, wherein the solid solution treatment temperature is 900 ℃, the heat preservation time is 6h, and the cooling mode is water cooling.
d. Cold drawing: and (3) performing cold drawing on the bar subjected to the solution treatment, wherein the processing rate is 60%.
e. Aging treatment: and (3) placing the cold-drawn wire into a bell-type annealing furnace for aging treatment, wherein the aging temperature is 400 ℃, the heat preservation time is 10 hours, and cooling in an air cooling mode.
f. Cold drawing: and (3) performing cold drawing on the alloy subjected to the aging treatment, wherein the processing rate is 30%.
g. And (3) online annealing treatment: and carrying out on-line annealing treatment on the alloy wire rod after drawing, wherein the annealing temperature is 450 ℃, the annealing speed is 20cm/s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
The microstructure and properties of the alloy treated by the above steps are shown in table 2 and table 3, which are given in example 1 below.
Example 2:
in the embodiment, the alloy is smelted by adopting the following raw materials: electrolytic copper, copper chromium master alloy, copper zirconium master alloy, pure silver and pure titanium, the alloy composition is shown in table 1 below as example 2.
a. Smelting: adding electrolytic copper, copper-chromium intermediate alloy, copper-zirconium intermediate alloy, pure silver and pure titanium into a vacuum induction furnace, heating to 1280 ℃ after the materials are all melted, uniformly stirring after the melt is completely melted, controlling the casting temperature at 1200 ℃, and carrying out casting after heat preservation for 20 min.
b. Homogenization and hot extrusion: heating the alloy cast ingot in a stepping box type furnace at 950 ℃ for 6h, then carrying out hot extrusion on the cast ingot, controlling the temperature to be 850 ℃ after extrusion, carrying out extrusion ratio to be 30, and then carrying out water cooling.
c. Solution treatment: and (3) carrying out solid solution treatment on the extruded copper rod, wherein the solid solution treatment temperature is 1000 ℃, the heat preservation time is 2 hours, and the cooling mode is water cooling.
d. Cold drawing: and (5) performing cold drawing on the bar subjected to the solution treatment, wherein the processing rate is 80%.
e. Aging treatment: and placing the cold-drawn wire in a bell-type annealing furnace for aging treatment, wherein the aging temperature is 500 ℃, the heat preservation time is 6h, and the cooling mode is air cooling.
f. Cold drawing: and (3) performing cold drawing on the alloy subjected to the aging treatment, wherein the processing rate is 50%.
g. And (3) online annealing treatment: and carrying out on-line annealing treatment on the alloy wire rod after drawing, wherein the annealing temperature is 550 ℃, the annealing speed is 10cm/s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
The microstructure and properties of the alloy treated by the above procedure are shown in table 2 and table 3, which are given in example 2 below.
Example 3:
in the embodiment, the alloy is smelted by adopting the following raw materials: electrolytic copper, copper chromium master alloy, copper zirconium master alloy, pure magnesium and pure titanium, the alloy composition is shown in table 1, example 3.
a. Smelting: adding electrolytic copper, copper-chromium intermediate alloy, copper-zirconium intermediate alloy, pure magnesium and pure titanium into a vacuum induction furnace, heating to 1260 ℃ after the materials are all melted, uniformly stirring after the melt is completely melted, controlling the casting temperature to 1170 ℃, and carrying out casting after heat preservation for 20 min.
b. Homogenization and hot extrusion: heating the alloy cast ingot in a stepping box type furnace at 920 ℃ for 8h, then carrying out hot extrusion on the cast ingot, controlling the temperature after extrusion at 820 ℃ and the extrusion ratio at 25, and then carrying out water cooling.
c. Solution treatment: and (3) carrying out solid solution treatment on the extruded copper rod, wherein the solid solution treatment temperature is 950 ℃, the heat preservation time is 4h, and the cooling mode is water cooling.
d. Cold drawing: and (4) performing cold drawing on the bar subjected to the solution treatment, wherein the processing rate is 70%.
e. Aging treatment: and (3) placing the cold-drawn wire in a bell-type annealing furnace for aging treatment, wherein the aging temperature is 475 ℃, the heat preservation time is 4h, and the cooling mode is air cooling.
f. Cold drawing: and (3) performing cold drawing on the alloy subjected to the aging treatment, wherein the processing rate is 40%.
g. And (3) online annealing treatment: and carrying out on-line annealing treatment on the alloy wire rod after drawing, wherein the annealing temperature is 500 ℃, the annealing speed is 15cm/s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
The microstructure and properties of the alloy treated by the above procedure are shown in table 2 and table 3, which is example 3 below.
Example 4:
in the embodiment, the alloy is smelted by adopting the following raw materials: electrolytic copper, copper chromium master alloy, copper zirconium master alloy, pure magnesium and pure tin, the composition of the alloys is given in table 1, example 4.
a. Smelting: adding electrolytic copper, copper-chromium intermediate alloy, copper-zirconium intermediate alloy, pure magnesium and pure tin into a vacuum induction furnace, heating to 1250 ℃ after the materials are all melted, uniformly stirring after the melt is completely melted, controlling the casting temperature at 1200 ℃, and casting after heat preservation for 20 min.
b. Homogenization and hot extrusion: heating the alloy cast ingot in a stepping box type furnace at the temperature of 910 ℃ for 10h, then carrying out hot extrusion on the cast ingot, controlling the temperature after extrusion to be 850 ℃, carrying out extrusion ratio to be 20, and then carrying out water cooling.
c. Solution treatment: and (3) carrying out solid solution treatment on the extruded copper rod, wherein the solid solution treatment temperature is 900 ℃, the heat preservation time is 4h, and the cooling mode is water cooling.
d. Cold drawing: and (3) performing cold drawing on the bar subjected to the solution treatment, wherein the processing rate is 60%.
e. Aging treatment: and placing the cold-drawn wire in a bell-type annealing furnace for aging treatment, wherein the aging temperature is 500 ℃, the heat preservation time is 8h, and the cooling mode is air cooling.
f. Cold drawing: and (3) performing cold drawing on the alloy subjected to the aging treatment, wherein the processing rate is 40%.
g. And (3) online annealing treatment: and carrying out on-line annealing treatment on the alloy wire rod after drawing, wherein the annealing temperature is 500 ℃, the annealing speed is 20cm/s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
The microstructure and properties of the alloy treated by the above steps are shown in table 2 and table 3 for example 4.
Example 5:
the alloy in the embodiment is smelted by adopting the following raw materials: electrolytic copper, copper chromium master alloy, copper zirconium master alloy, pure magnesium and pure tin, the alloy composition is shown in table 1, example 5.
a. Smelting: adding electrolytic copper, copper-chromium intermediate alloy, copper-zirconium intermediate alloy, pure magnesium and pure tin into a vacuum induction furnace, heating to 1230 ℃ after the materials are all melted, uniformly stirring after the melt is completely melted, controlling the casting temperature at 1200 ℃, and casting after heat preservation for 20 min.
b. Homogenization and hot extrusion: heating the alloy cast ingot in a stepping box type furnace at 920 ℃ for 8h, then carrying out hot extrusion on the cast ingot, controlling the temperature after extrusion to be 825 ℃, carrying out extrusion ratio to be 20, and then carrying out water cooling.
c. Solution treatment: and (3) carrying out solid solution treatment on the extruded copper rod, wherein the solid solution treatment temperature is 950 ℃, the heat preservation time is 6h, and the cooling mode is water cooling.
d. Cold drawing: the bar after the solution treatment was cold-drawn at a working rate of 65%.
e. Aging treatment: and placing the cold-drawn wire in a bell-type annealing furnace for aging treatment, wherein the aging temperature is 450 ℃, the heat preservation time is 6h, and the cooling mode is air cooling.
f. Cold drawing: and (3) performing cold drawing on the alloy subjected to the aging treatment, wherein the processing rate is 30%.
g. And (3) online annealing treatment: and carrying out on-line annealing treatment on the alloy wire rod after drawing, wherein the annealing temperature is 525 ℃, the annealing speed is 15cm/s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
The microstructure and properties of the alloy treated by the above procedure are shown in table 2 and table 3 for example 5.
Example 6:
the alloy in the embodiment is smelted by adopting the following raw materials: electrolytic copper, copper chromium master alloy, copper zirconium master alloy, pure silver and pure tin, the composition of the alloys is given in table 1, example 6.
a. Smelting: adding electrolytic copper, copper-chromium intermediate alloy, copper-zirconium intermediate alloy, pure magnesium and pure tin into a vacuum induction furnace, heating to 1250 ℃ after the materials are all melted, uniformly stirring after the melt is completely melted, controlling the casting temperature to be 1175 ℃, and carrying out heat preservation for 20min before casting.
b. Homogenization and hot extrusion: heating the alloy cast ingot in a stepping box type furnace at 900 ℃ for 8h, then carrying out hot extrusion on the cast ingot, controlling the temperature after extrusion to be 825 ℃, carrying out extrusion ratio to be 30, and then carrying out water cooling.
c. Solution treatment: and (3) carrying out solid solution treatment on the extruded copper rod, wherein the solid solution treatment temperature is 950 ℃, the heat preservation time is 4h, and the cooling mode is water cooling.
d. Cold drawing: and (3) performing cold drawing on the bar subjected to the solution treatment, wherein the processing rate is 60%.
e. Aging treatment: and placing the cold-drawn wire in a bell-type annealing furnace for aging treatment, wherein the aging temperature is 500 ℃, the heat preservation time is 10 hours, and the cooling mode is air cooling.
f. Cold drawing: and (3) performing cold drawing on the alloy subjected to the aging treatment, wherein the processing rate is 40%.
g. And (3) online annealing treatment: and carrying out on-line annealing treatment on the alloy wire rod after drawing, wherein the annealing temperature is 500 ℃, the annealing speed is 10cm/s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
The microstructure and properties of the alloy treated by the above procedure are shown in table 2 and table 3 for example 6.
Example 7:
the alloy in the embodiment is smelted by adopting the following raw materials: electrolytic copper, copper chromium master alloy, copper zirconium master alloy and pure tin, the composition of the alloys is shown in table 1, example 7.
a. Smelting: adding electrolytic copper, copper-chromium intermediate alloy, copper-zirconium intermediate alloy and pure tin into a vacuum induction furnace, heating to 1250 ℃ after the materials are all melted, uniformly stirring after the melt is completely melted, controlling the casting temperature to 1150 ℃, and casting after heat preservation for 20 min.
b. Homogenization and hot extrusion: heating the alloy cast ingot in a stepping box type furnace at 950 ℃ for 8h, then carrying out hot extrusion on the cast ingot, controlling the temperature to be 800 ℃ after extrusion, carrying out extrusion ratio to be 30, and then carrying out water cooling.
c. Solution treatment: and (3) carrying out solid solution treatment on the extruded copper rod, wherein the solid solution treatment temperature is 950 ℃, the heat preservation time is 4h, and the cooling mode is water cooling.
d. Cold drawing: and (5) performing cold drawing on the bar subjected to the solution treatment, wherein the processing rate is 80%.
e. Aging treatment: and placing the cold-drawn wire in a bell-type annealing furnace for aging treatment, wherein the aging temperature is 500 ℃, the heat preservation time is 6h, and the cooling mode is air cooling.
f. Cold drawing: and (3) performing cold drawing on the alloy subjected to the aging treatment, wherein the processing rate is 50%.
g. And (3) online annealing treatment: and carrying out on-line annealing treatment on the alloy wire rod after drawing, wherein the annealing temperature is 475 ℃, the annealing speed is 10cm/s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
The microstructure and properties of the alloy treated by the above procedure are shown in table 2 and table 3 for example 7.
Example 8:
the alloy in the embodiment is smelted by adopting the following raw materials: electrolytic copper, copper chromium master alloy, copper zirconium master alloy and pure magnesium, the composition of the alloy is shown in table 1, example 8.
a. Smelting: adding electrolytic copper, copper-chromium intermediate alloy, copper-zirconium intermediate alloy and pure magnesium into a vacuum induction furnace, heating to 1280 ℃ after the materials are all melted, uniformly stirring after the melt is completely melted, controlling the casting temperature to 1170 ℃, and casting after heat preservation for 20 min.
b. Homogenization and hot extrusion: heating the alloy cast ingot in a stepping box type furnace at 930 ℃ for 10h, then carrying out hot extrusion on the cast ingot, controlling the temperature after extrusion to be 800 ℃, carrying out extrusion ratio to be 20, and then carrying out water cooling.
c. Solution treatment: and (3) carrying out solid solution treatment on the extruded copper rod, wherein the solid solution treatment temperature is 950 ℃, the heat preservation time is 2 hours, and the cooling mode is water cooling.
d. Cold drawing: and (4) performing cold drawing on the bar subjected to the solution treatment, wherein the processing rate is 70%.
e. Aging treatment: and placing the cold-drawn wire in a bell-type annealing furnace for aging treatment, wherein the aging temperature is 500 ℃, the heat preservation time is 6h, and the cooling mode is air cooling.
f. Cold drawing: and (3) performing cold drawing on the alloy subjected to the aging treatment, wherein the processing rate is 50%.
g. And (3) online annealing treatment: and carrying out on-line annealing treatment on the alloy wire rod after drawing, wherein the annealing temperature is 475 ℃, the annealing speed is 10cm/s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
The microstructure and properties of the alloy treated by the above procedure are shown in table 2 and table 3 for example 8.
Example 9:
the alloy in the embodiment is smelted by adopting the following raw materials: electrolytic copper, copper chromium master alloy, copper zirconium master alloy and pure titanium, the composition of the alloy is shown in table 1, example 9.
a. Smelting: adding electrolytic copper, copper-chromium intermediate alloy, copper-zirconium intermediate alloy and pure titanium into a vacuum induction furnace, heating to 1240 ℃ after the materials are all melted, uniformly stirring after the melt is completely melted, controlling the casting temperature at 1200 ℃, and carrying out heat preservation for 20min before casting.
b. Homogenization and hot extrusion: heating the alloy cast ingot in a stepping box type furnace at 900 ℃ for 10h, then carrying out hot extrusion on the cast ingot, controlling the temperature after extrusion at 820 ℃, carrying out extrusion ratio at 20, and then carrying out water cooling.
c. Solution treatment: and (3) carrying out solid solution treatment on the extruded copper rod, wherein the solid solution treatment temperature is 1000 ℃, the heat preservation time is 4h, and the cooling mode is water cooling.
d. Cold drawing: and (4) performing cold drawing on the bar subjected to the solution treatment, wherein the processing rate is 70%.
e. Aging treatment: and placing the cold-drawn wire in a bell-type annealing furnace for aging treatment, wherein the aging temperature is 500 ℃, the heat preservation time is 6h, and the cooling mode is air cooling.
f. Cold drawing: and (3) performing cold drawing on the alloy subjected to the aging treatment, wherein the processing rate is 50%.
g. And (3) online annealing treatment: and carrying out on-line annealing treatment on the alloy wire rod after drawing, wherein the annealing temperature is 500 ℃, the annealing speed is 10cm/s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
The microstructure and properties of the alloy treated by the above procedure are shown in Table 2 and Table 3 for example 9.
Example 10:
the alloy in the embodiment is smelted by adopting the following raw materials: electrolytic copper, copper chromium master alloy, copper zirconium master alloy, pure titanium and pure tin, the composition of the alloys is given in table 1, example 10.
a. Smelting: adding electrolytic copper, copper-chromium intermediate alloy, copper-zirconium intermediate alloy, pure titanium and pure tin into a vacuum induction furnace, heating to 1250 ℃ after the materials are all melted, uniformly stirring after the melt is completely melted, controlling the casting temperature at 1200 ℃, and carrying out casting after heat preservation for 20 min.
b. Homogenization and hot extrusion: heating the alloy cast ingot in a stepping box type furnace at 900 ℃ for 10h, then carrying out hot extrusion on the cast ingot, controlling the temperature after extrusion to be 850 ℃ and the extrusion ratio to be 30, and then carrying out water cooling.
c. Solution treatment: and (3) carrying out solid solution treatment on the extruded copper rod, wherein the solid solution treatment temperature is 1000 ℃, the heat preservation time is 4h, and the cooling mode is water cooling.
d. Cold drawing: and (5) performing cold drawing on the bar subjected to the solution treatment, wherein the processing rate is 80%.
e. Aging treatment: and placing the cold-drawn wire in a bell-type annealing furnace for aging treatment, wherein the aging temperature is 500 ℃, the heat preservation time is 6h, and the cooling mode is air cooling.
f. Cold drawing: and (3) performing cold drawing on the alloy subjected to the aging treatment, wherein the processing rate is 30%.
g. And (3) online annealing treatment: and carrying out on-line annealing treatment on the alloy wire rod after drawing, wherein the annealing temperature is 500 ℃, the annealing speed is 20cm/s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
The microstructure and properties of the alloy treated by the above steps are shown in Table 2 and Table 3 for example 10.
Example 11:
the alloy in the embodiment is smelted by adopting the following raw materials: electrolytic copper, copper chromium master alloy, copper zirconium master alloy, pure silver and pure tin, the composition of the alloys is given in table 1, example 11.
a. Smelting: adding electrolytic copper, copper-chromium intermediate alloy, copper-zirconium intermediate alloy, pure silver and pure tin into a vacuum induction furnace, heating to 1230 ℃ after the materials are all melted, uniformly stirring after the melt is completely melted, controlling the casting temperature to 1170 ℃, and casting after heat preservation for 20 min.
b. Homogenization and hot extrusion: heating the alloy cast ingot in a stepping box type furnace at 930 ℃ for 10h, then carrying out hot extrusion on the cast ingot, controlling the temperature after extrusion to be 800 ℃, carrying out extrusion ratio to be 30, and then carrying out water cooling.
c. Solution treatment: and (3) carrying out solid solution treatment on the extruded copper rod, wherein the solid solution treatment temperature is 900 ℃, the heat preservation time is 4h, and the cooling mode is water cooling.
d. Cold drawing: and (3) performing cold drawing on the bar subjected to the solution treatment, wherein the processing rate is 60%.
e. Aging treatment: and (3) placing the cold-drawn wire in a bell-type annealing furnace for aging treatment, wherein the aging temperature is 400 ℃, the heat preservation time is 6h, and the cooling mode is air cooling.
f. Cold drawing: and (3) performing cold drawing on the alloy subjected to the aging treatment, wherein the processing rate is 30%.
g. And (3) online annealing treatment: and carrying out on-line annealing treatment on the alloy wire rod after drawing, wherein the annealing temperature is 450 ℃, the annealing speed is 20cm/s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
The microstructure and properties of the alloy treated by the above steps are shown in Table 2 and Table 3 for example 11.
Example 12:
the alloy in the embodiment is smelted by adopting the following raw materials: electrolytic copper, copper chromium master alloy, copper zirconium master alloy, pure silver and pure magnesium, the composition of the alloy is shown in table 1, example 12.
a. Smelting: adding electrolytic copper, copper-chromium intermediate alloy, copper-zirconium intermediate alloy, pure silver and pure magnesium into a vacuum induction furnace, heating to 1250 ℃ after the materials are all melted, uniformly stirring after the melt is completely melted, controlling the casting temperature to 1170 ℃, and casting after heat preservation for 20 min.
b. Homogenization and hot extrusion: heating the alloy cast ingot in a stepping box type furnace at 900 ℃ for 10h, then carrying out hot extrusion on the cast ingot, controlling the temperature after extrusion to be 850 ℃, carrying out extrusion ratio to be 20, and then carrying out water cooling.
c. Solution treatment: and (3) carrying out solid solution treatment on the extruded copper rod, wherein the solid solution treatment temperature is 1000 ℃, the heat preservation time is 4h, and the cooling mode is water cooling.
d. Cold drawing: and (4) performing cold drawing on the bar subjected to the solution treatment, wherein the processing rate is 70%.
e. Aging treatment: and (3) placing the cold-drawn wire in a bell-type annealing furnace for aging treatment, wherein the aging temperature is 400 ℃, the heat preservation time is 6h, and the cooling mode is air cooling.
f. Cold drawing: and (3) performing cold drawing on the alloy subjected to the aging treatment, wherein the processing rate is 50%.
g. And (3) online annealing treatment: and carrying out on-line annealing treatment on the alloy wire rod after drawing, wherein the annealing temperature is 450 ℃, the annealing speed is 10cm/s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
The microstructure and properties of the alloy treated by the above procedure are shown in Table 2 and Table 3 for example 12.
TABLE 1 alloy composition recipes (wt%) for examples 1-12
TABLE 2 alloy structure of examples 1-12
TABLE 3 alloy Properties of examples 1-12
Remarking: the repeated bending times of the alloy material adopt a GBT 4909.5-2009 bare wire test method.
Claims (3)
1. The multi-scale multi-element high-strength high-conductivity copper-chromium-zirconium alloy material is characterized by comprising 0.75% of Cr, 0.11-0.15% of Zr and the balance of Cu in percentage by weight;
the alloy material has bean-shaped Cr phase with 2-10 nm grain size and 1 x 10 density21～5×1022m-3；
The alloy material has Moire fringe-shaped Cr phase with body-centered cubic structure with grain diameter of 5-10 nm on transverse and longitudinal sections, and the precipitation density is 5 x 1022～2×1023m-3；
The alloy material has a disc-shaped Cu with a face-centered cubic structure and a grain diameter of 50-100 nm on the transverse and longitudinal sections5Zr phase with a precipitation density of 1X 1017～5×1018m-3；
The alloy material has CuCrZr phase with 20-50 nm grain size and face-centered cubic structure in the transverse and longitudinal sections and has precipitation density of 1 x 1017～5×1017m-3；
In the alloy material, 15-25% of alloy <100> texture, 15-25% of alloy <110> texture, 25-45% of alloy <111> texture and 13-30% of alloy <112> texture are contained;
the alloy material at least comprises one or two of Ti, Ag, Mg and Sn, wherein the content of Ti, Ag, Mg and Sn is 0.05-0.2%, and the total content of alloy elements is 0.1-0.4%;
the preparation method of the alloy material comprises the following steps:
a. the method comprises the following steps of proportioning, feeding, smelting and casting according to mass percent, wherein the smelting and casting process comprises the following steps: adding electrolytic copper, copper-chromium intermediate alloy and copper-zirconium intermediate alloy into a vacuum induction furnace before smelting, adding one or two of pure titanium, pure silver, pure tin and pure magnesium after the materials are all molten, raising the temperature to 1230-1280 ℃, uniformly stirring after the melt is completely molten, controlling the casting temperature at 1150-1200 ℃, and casting after heat preservation for 20 min; the smelting and casting adopt a vacuum intermediate frequency induction furnace, the smelting temperature is 1230-1280 ℃, and the casting temperature is 1150-1200 ℃;
b. carrying out homogenization annealing treatment, wherein the homogenization annealing treatment is to heat the alloy ingot in a stepping box type furnace at 900-950 ℃ for 6-12 h;
c. hot extrusion, wherein the extrusion finishing temperature of the hot extrusion is 800-850 ℃, and the extrusion ratio is 15-30;
d. carrying out solution treatment, wherein the temperature of the solution treatment is 900-1000 ℃, the heat preservation time is 2-6 h, and the cooling mode is water cooling;
e. cold drawing, wherein the processing rate of the cold drawing is 60-80%;
f. aging treatment, wherein the temperature of the aging treatment is 400-500 ℃, the heat preservation time is 6-10 h, and the cooling mode is air cooling;
g. cold drawing, wherein the processing rate of the cold drawing is 30-50%;
h. and (3) carrying out on-line annealing treatment, wherein the temperature of the on-line annealing treatment is 450-550 ℃, the annealing speed is 10-20 cm/s, the cooling mode is air cooling, and the protective gas is pure hydrogen.
2. The multi-scale multielement high-strength high-conductivity copper chromium zirconium alloy material as claimed in claim 1, wherein the total content of alloying elements in the alloy is 0.15-0.3%.
3. The multi-scale multi-element high-strength high-conductivity copper-chromium-zirconium alloy material as claimed in claim 1, wherein the alloy material has a tensile strength of 300-700 MPa, a yield strength of 150-600 MPa, an elongation of 10-30%, an electrical conductivity of 70-95% IACS, a softening temperature of 500-600 ℃, and a repeated bending frequency of 1 x 105～1×108Next, the process is carried out.
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