Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a high-strength conductive anti-softening Cu-Ti alloy for an elastic component and a preparation method thereof, and the preparation method specifically comprises the following steps:
a high-strength conductive softening-resistant Cu-Ti alloy for elastic components comprises the following chemical components: 2.8 to 3.9 weight percent of Ti, 0 to 0.2 weight percent of Mg, 0 to 0.09 weight percent of La, 0 to 0.05 weight percent of B, less than or equal to 0.01 weight percent of Al, less than or equal to 0.01 weight percent of Si, less than or equal to 0.01 weight percent of Ni, less than or equal to 0.01 weight percent of Zn, and the balance of Cu.
A preparation method of a high-strength conductive anti-softening Cu-Ti alloy for an elastic component comprises the following steps:
(1) preparing an alloy ingot by vacuum melting;
(2) homogenization heat treatment, temperature: 760 and 820 ℃, time: 2-12 h;
(3) low-temperature hot rolling, wherein the initial rolling temperature is as follows: 720-750 ℃ and the heat preservation time: 0.5-1.5h, deformation: 65-85%;
(4) multi-cycle ultralow-temperature deep cooling rolling deformation: deformation temperature: (-180 ℃ C.) - (-140 ℃ C.), total deformation amount: 30-50%;
(5) short-time solution quenching treatment, wherein the solution temperature is as follows: 720-750 ℃, solid solution time: 0.5-2h, quenching mode: water quenching;
(6) multiple-circulation ultralow-temperature deep cooling rolling deformation, deformation temperature: (-150 ℃ C.) - (-130 ℃ C.), deformation: 70-80%;
(7) low-temperature short-time pre-aging treatment at the temperature of 360 ℃ and 420 ℃ for 0.1-2.5 h;
(8) multiple-circulation ultralow-temperature deep cooling rolling deformation, deformation temperature: (-150 ℃ C.) - (-130 ℃ C.), deformation: 40-55 percent;
(9) isothermal aging treatment, temperature: 360 ℃ and 420 ℃, time: 0.1-12 h.
Specifically, the pass reduction in the low-temperature hot rolling treatment process in the step (3) is as follows: 5 to 20 percent.
Specifically, the multi-cycle ultralow-temperature deep cold rolling deformation process in the step (4) comprises the following steps: the low-temperature deformation cycle is more than 10 times, the liquid nitrogen tank is placed for more than 35min, and then ultra-low-temperature deformation is carried out, wherein the deformation temperature is as follows: (-180 ℃) to (-140 ℃), deformation: 5-15%, modification: synchronous rolling, wherein the pass deformation is 2-10%; then, putting the ultra-low temperature rolled plate into a liquid nitrogen tank for cooling for 4-6min, wherein the deformation temperature is as follows: (-180 ℃) to (-140 ℃), deformation: 5% -15%, deformation mode: synchronous rolling, pass deformation: 2 to 10 percent; and repeating the process to finally enable the total deformation of the alloy plate to reach 30-50%.
Specifically, the multi-cycle ultralow-temperature deep cold rolling deformation process in the step (6) comprises the following steps: the low-temperature deformation cycle number is more than or equal to 12, the liquid nitrogen tank is placed for more than 1h, then the ultra-low-temperature deformation is carried out, the deformation temperature is as follows: (-150 ℃ C.) - (-130 ℃ C.), deformation: 10-20%, pass deformation: 5 to 15 percent; then, putting the ultra-low temperature rolled plate into a liquid nitrogen tank for cooling for 5-10min, wherein the deformation temperature is as follows: (-150 ℃ C.) - (-130 ℃ C.), deformation: 15% -25%, pass deformation: 5 to 15 percent; and repeating the process to finally enable the total deformation of the alloy plate to reach 70-80%.
Specifically, the multi-cycle ultralow-temperature deep cold rolling deformation process in the step (8) comprises the following steps: the low-temperature deformation cycle number is more than or equal to 5, the liquid nitrogen tank is placed for more than 1h, then the ultra-low-temperature deformation is carried out, the deformation temperature is as follows: (-150 ℃ C.) - (-130 ℃ C.), deformation: 5-15% and pass deformation of 7-10%; then, putting the ultra-low temperature rolled plate into a liquid nitrogen tank for cooling for 5min, wherein the deformation temperature is as follows: (-150 ℃ C.) - (-130 ℃ C.), deformation: 5-15%, modification: synchronous rolling, pass deformation: 7 to 10 percent; and repeating the process to finally enable the total deformation of the alloy plate to reach 40-55%.
Aiming at overcoming the defects of the prior art and solving the problems that the strength, the electric conductivity, the softening resistance and other properties of the existing Cu-Ti alloy are not excellent enough, the invention firstly influences the cast-state grain structure of the alloy based on the multi-component composite micro-alloying regulation and control, and simultaneously can introduce fine dispersion particles consisting of the multi-components into a matrix. And further, the method not only has important influence on the tissue evolution of the alloy hot processing process, but also plays an important role in promoting the uniform and dispersed distribution of dislocation in the subsequent multi-cycle ultralow temperature deformation process and the slow and long rapid nucleation and growth of a precipitation phase. Finally, the developed Cu-Ti alloy has the characteristics of high strength, high elasticity, high-temperature softening resistance, high conductivity and the like, so that the urgent requirements of various high and new technical fields such as electronic industry, aerospace, instruments and meters, household appliances and the like on the high-performance elastic copper alloy can be met.
According to the invention, the Cu-Ti alloy as-cast structure is regulated and controlled by adding a proper amount of multi-component composite microalloying elements, and on the basis of effectively improving the as-cast structure, the Cu-Ti alloy is further subjected to integrated regulation and control of multiple processes of hot working, including homogenization, hot rolling, ultralow temperature deformation, solid solution, ultralow temperature deformation, pre-aging, secondary ultralow temperature deformation, aging and the like, so that the alloy can rapidly generate amplitude modulation decomposition, the precipitation rate, the precipitation quantity and the uniform dispersion distribution degree of a precipitate phase are increased, the strength, the elasticity and the conductivity are improved, the characteristic of lower coarsening rate of the precipitate phase can be shown, and the high-temperature softening resistance of the alloy is improved. Specifically, low-temperature hot rolling after homogenization can not only enable the structure to evolve from an as-cast structure to a deformed structure, increase the deformability of the alloy, but also avoid oxidation in the high-temperature hot rolling process of the alloy and promote the uniform dispersion degree of fine particles formed after the addition of the composite microalloying elements. On the basis, if multi-cycle ultralow temperature deep cooling rolling deformation is further introduced, the uniform dispersion distribution degree of fine particles formed by the composite microalloying elements can be effectively promoted, and the strain energy storage around the dispersed particles and residual precipitated phases can be greatly increased. Therefore, the subsequent solid solution process not only can better dissolve the precipitation phase back into the alloy matrix, but also can effectively reduce the solid solution temperature and the solid solution time and reduce the actual production cost of the alloy. In addition, considering that the precipitation characteristic of the Cu-Ti alloy is an amplitude-modulated decomposition precipitation behavior, the Cu-Ti alloy has the common characteristic that a new phase can be formed by continuous growth of a parent phase through concentration fluctuation without a nucleation process, a fine microstructure with periodically changed components is formed in the whole crystal grain range after the precipitation decomposition, and an elastic strain field generated by keeping two phases with different components coherent can strongly prevent dislocation movement, thereby generating a strengthening effect. Therefore, if the multi-cycle ultra-low temperature deep cold rolling deformation treatment with a certain deformation is firstly carried out after the solution quenching, a large number of dislocation lines are uniformly dispersed and distributed around the dispersed particles in the alloy matrix under the action of the fine dispersed particles introduced after the composite micro-alloying elements are added, and the dislocation lines not only can remarkably promote the speed of the spinodal decomposition in the subsequent pre-aging process, but also can remarkably reduce the periodic fluctuation range of the components in the alloy matrix. And then if the alloy subjected to the multi-cycle ultralow temperature deformation and pre-aging regulation and control is further subjected to multi-cycle ultralow temperature deep cold rolling deformation treatment with proper deformation, the alloy which has generated composition fluctuation can be re-crushed, but the alloy can be used as a core point of subsequent further aging, and amplitude modulation decomposition can be generated again in the further aging process. Meanwhile, the fluctuation range of components in the alloy micro-area is smaller, so that the precipitation rate and the precipitation quantity of a precipitate phase are obviously increased, and the corresponding strength, elasticity and conductivity can be greatly improved. In addition, the precipitation rate of the precipitated phase is greatly improved, and meanwhile, due to the influence of fine dispersed particles formed after the composite microalloying elements are added on the precipitated phase, the growth rate of the formed precipitated phase in the subsequent aging process can be maintained at a lower level, and the excellent high-temperature softening resistance is shown.
The Cu-Ti alloy plate prepared by the invention not only has the characteristics of high strength, high elasticity and high conductivity, but also can obviously improve the high-temperature softening resistance, and can be better used as a substitute material of the traditional beryllium bronze. The alloy and the preparation technology thereof are very suitable for being applied to the processing and production of products related to the high and new technical fields of electronic industry, aerospace, instruments, household appliances and the like which have certain requirements on the strength, elasticity, conductivity, softening resistance, processing performance, production cost and the like of the copper alloy, and are also more suitable for being applied to industries which are more sensitive to problems (such as harmful influence of smoke, steam and dust of beryllium and compounds thereof on human health, high production cost, high price and the like) in the application process of beryllium bronze.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments. The embodiments shown below do not limit the inventive content described in the claims. The entire contents of the configurations shown in the following embodiments are not limited to those required as solutions of the inventions described in the claims.
The preparation method comprises the following steps: the method comprises the steps of preparing an alloy ingot subjected to composite microalloying regulation and control through vacuum melting → homogenizing heat treatment → low-temperature hot rolling → multi-cycle ultralow-temperature cryogenic rolling deformation → short-time solid solution quenching treatment → multi-cycle ultralow-temperature cryogenic rolling deformation → low-temperature short-time pre-aging treatment → multi-cycle ultralow-temperature cryogenic rolling deformation → isothermal aging treatment, wherein the grain structure of the copper alloy can be controlled, the amount and density of precipitation and precipitation of an alloy peak aging state can be remarkably induced, and finally the copper alloy has high strength, high conductivity and excellent high-temperature softening resistance (as shown in figure 1).
The raw materials respectively adopt 99.9 wt% of electrolytic high-purity Cu, sponge Ti and other microalloying elements. Firstly, the alloy is smelted in a vacuum intermediate frequency induction furnace to implement the invention. The specific chemical compositions of the alloys described in the examples and comparative examples are shown in table 1. Then carrying out homogenization heat treatment (the temperature is 760 and 820 ℃, and the time is 2-12h) on the alloy ingot; then carrying out low-temperature hot rolling deformation on the ingot after the homogenization treatment, wherein the initial rolling temperature is as follows: 720-750 ℃ and the heat preservation time: 0.5-1.5h, deformation: 65-85%; then, carrying out multi-cycle ultralow-temperature deep cooling rolling deformation on the hot rolled plate, wherein the deformation temperature is as follows: (-180 ℃ C.) - (-140 ℃ C.), total deformation amount: 30-50%; then short-time solution quenching treatment is carried out, wherein the solution temperature is as follows: 720-750 ℃, solid solution time: 0.5-2h, quenching mode: water quenching; and then carrying out multi-cycle ultralow temperature deep cooling rolling deformation on the hot rolled plate, wherein the deformation temperature is as follows: (-150 ℃ C.) - (-130 ℃ C.), deformation: 70-80%; then low-temperature short-time pre-aging treatment is carried out at the temperature of 360 ℃ and 420 ℃ for 0.1-2.5 h; then, carrying out multi-cycle ultralow temperature deep cooling rolling deformation on the pre-aged alloy plate, wherein the deformation is (-150 ℃) to (-130 ℃): 40-55 percent; and finally, carrying out isothermal aging treatment on the ultralow-temperature cold-rolled plate at the temperature of 360 ℃ and 420 ℃, wherein the time is as follows: 0.1-12 h. And finally, measuring the microhardness, the conductivity and the tensile property of the alloy in different states, and characterizing the structure of the alloy in a typical state.
TABLE 1 chemical composition of alloy in examples and comparative examples
Comparative example 1
The alloy components are mixed according to a comparative example 1 in a table 1, firstly, 99.9 wt% of electrolytic high-purity Cu, sponge Ti, microalloying elements and the like are cut to prepare an alloy, and then the alloy is smelted in a vacuum intermediate frequency induction furnace; then carrying out homogenization heat treatment (temperature: 800 ℃, time: 8h) on the alloy cast ingot, and then carrying out hot working; then carrying out low-temperature hot rolling deformation on the ingot after the homogenization treatment, wherein the initial rolling temperature is as follows: 740 ℃, heat preservation time 1h, deformation: 80%, pass reduction: 10 percent; then carrying out short-time solution quenching treatment, wherein the solution temperature is as follows: 740 ℃, solid solution time: 1h, quenching mode: water quenching; then, cold rolling deformation is carried out on the hot rolled plate at room temperature, and the total deformation is as follows: 75%, pass reduction: 10 percent; then carrying out low-temperature short-time pre-aging treatment at 390 ℃ for 2 h; and then, carrying out cold rolling deformation on the alloy plate at room temperature again, wherein the deformation is as follows: 50%, pass reduction: 8 percent; finally, carrying out isothermal aging treatment at 360, 390 and 420 ℃ on the cold-rolled sheet at room temperature, wherein the aging time is as follows: 0.1-12 h. Finally, the microhardness, the conductivity and the tensile property of the alloy in different states are measured (as shown in figure 2 and table 2), and the structure of the alloy in a typical state is characterized (as shown in figure 3).
Comparative example 2
The alloy components are mixed according to a comparative example 2 in a table 1, firstly, 99.9 wt% of electrolytic high-purity Cu, sponge Ti, microalloying elements and the like are cut into raw materials to prepare an alloy, and then the alloy is smelted in a vacuum intermediate frequency induction furnace to implement the invention; then carrying out homogenization heat treatment (temperature: 820 ℃, time: 12h) on the alloy ingot; then carrying out low-temperature hot rolling deformation on the ingot after the homogenization treatment, wherein the initial rolling temperature is as follows: 750 ℃, heat preservation time of 1.5h, deformation: 65 percent, pass reduction: 8 percent; then carrying out short-time solution quenching treatment, wherein the solution temperature is as follows: 720 ℃, solid solution time: 2h, quenching mode: water quenching; then, cold rolling deformation is carried out on the hot rolled plate at room temperature, and the total deformation is as follows: 80%, pass reduction: 12 percent; then carrying out low-temperature short-time pre-aging treatment at 420 ℃ for 1.5 h; and then, carrying out cold rolling deformation on the alloy plate at room temperature again, wherein the deformation is as follows: 45%, pass reduction: 10 percent; finally, carrying out isothermal aging treatment at 360, 390 and 420 ℃ on the cold-rolled sheet at room temperature, wherein the aging time is as follows: 0.1-12 h. Finally, the microhardness, conductivity and tensile property measurements of the alloys in different states are shown in fig. 4 and table 2, and the structural characterization of the alloy in a typical state is shown in fig. 5.
Example 1
The alloy components were compounded according to example 1 in table 1, with the following specific implementation steps:
(1) firstly, cutting 99.9 wt% of electrolytic high-purity Cu, sponge Ti, microalloying elements and the like as raw materials to prepare an alloy, and then smelting the alloy in a vacuum medium-frequency induction furnace;
(2) then carrying out homogenization heat treatment on the alloy ingot, wherein the temperature is as follows: 800 ℃, time: 8 h;
(3) then carrying out low-temperature hot rolling deformation on the ingot after the homogenization treatment, wherein the initial rolling temperature is as follows: 740 ℃, heat preservation time 1h, deformation: 80%, pass reduction: 10 percent;
(4) and then, carrying out multi-cycle ultralow temperature deep cold rolling deformation treatment, wherein the cycle number of low temperature deformation is more than 10, firstly placing the steel plate in a liquid nitrogen tank for 40min, and then carrying out ultralow temperature deformation, wherein the deformation temperature is as follows: -180 ℃, deflection: 5-15%, modification: synchronous rolling, wherein the pass deformation is 2%; then, putting the ultra-low temperature rolled plate into a liquid nitrogen tank for cooling for 4min, wherein the deformation temperature is as follows: -180 ℃, deflection: 5%, deformation mode: synchronous rolling, pass deformation: 2 percent; repeating the process to finally enable the total deformation of the alloy plate to reach 30%;
(5) then carrying out short-time solution quenching treatment, wherein the solution temperature is as follows: 740 ℃, solid solution time: 1h, quenching mode: water quenching;
(6) then, carrying out multi-cycle ultralow temperature deep cooling rolling deformation treatment on the alloy, wherein the low temperature deformation cycle number is 13, firstly placing the alloy in a liquid nitrogen tank for more than 1h, and then carrying out ultralow temperature deformation, deformation temperature: -150 ℃, deflection: 10%, deformation mode: synchronous rolling, wherein the pass deformation is 6%; then, the ultra-low temperature rolled plate is put into a liquid nitrogen tank to be cooled for 7min, and the deformation temperature is as follows: 130 ℃, deflection: 15%, deformation mode: synchronous rolling, pass deformation: 5 percent; repeating the process to finally enable the total deformation of the alloy plate to reach 75%;
(7) then carrying out low-temperature short-time pre-aging treatment at 390 ℃ for 2 h;
(8) then, carrying out multi-cycle ultralow temperature deep cold rolling deformation treatment on the low-temperature pre-aged alloy plate for 5 times, firstly placing the plate in a liquid nitrogen tank for more than 1h, and then carrying out ultralow temperature deformation and deformation temperature: 130 ℃, deflection: 15%, deformation mode: synchronous rolling, wherein the pass deformation is 9%; then, putting the ultra-low temperature rolled plate into a liquid nitrogen tank for cooling for 6min, wherein the deformation temperature is as follows: 130 ℃, deflection: 5%, deformation mode: synchronous rolling, pass deformation: 10 percent; repeating the process to finally enable the total deformation of the alloy plate to reach 50%;
(9) and finally, carrying out isothermal aging treatment on the ultra-low temperature cold-rolled sheet, wherein the isothermal aging temperature is as follows: 360. 390, 420 ℃, time: 0.1-12 h.
The measurements of microhardness, electrical conductivity, tensile properties were performed on the alloys in different states (as shown in fig. 6 and table 2), and the metallographic structure of the alloy in a typical state was characterized (as shown in fig. 7).
Example 2
The alloy components were compounded according to example 2 of table 1, with the following specific implementation steps:
(1) firstly, cutting 99.9 wt% of electrolytic high-purity Cu, sponge Ti, microalloying elements and the like as raw materials to prepare an alloy, and then smelting the alloy in a vacuum medium-frequency induction furnace;
(2) then carrying out homogenization heat treatment on the alloy ingot, wherein the temperature is as follows: 820 ℃, time: 12 h;
(3) then carrying out low-temperature hot rolling deformation on the ingot after the homogenization treatment, wherein the initial rolling temperature is as follows: 750 ℃, heat preservation time of 1.5h, deformation: 65 percent, pass reduction: 8 percent;
(4) then, carrying out multi-cycle ultralow-temperature deep cold rolling deformation, wherein the specific process comprises the following steps: the low-temperature deformation cycle is more than 10 times, the liquid nitrogen tank is placed for 1h, and then ultra-low-temperature deformation is carried out, wherein the deformation temperature is as follows: 140 ℃, deflection: 15%, deformation mode: synchronous rolling, wherein the pass deformation is 10%; then, putting the ultra-low temperature rolled plate into a liquid nitrogen tank for cooling for 6min, wherein the deformation temperature is as follows: 140 ℃, deflection: 15%, deformation mode: synchronous rolling, pass deformation: 10 percent; repeating the process to finally enable the total deformation of the alloy plate to reach 50%;
(5) then carrying out short-time solution quenching treatment, wherein the solution temperature is as follows: 720 ℃, solid solution time: 2h, quenching mode: water quenching;
(6) then, carrying out multi-cycle ultralow temperature deep cold rolling deformation treatment on the alloy plate, wherein the low temperature deformation cycle times are 12, firstly placing the alloy plate in a liquid nitrogen tank for more than 1h, and then carrying out ultralow temperature deformation, deformation temperature: 130 ℃, deflection: 10%, deformation mode: synchronous rolling, wherein the pass deformation is 9%; then, putting the ultra-low temperature rolled plate into a liquid nitrogen tank for cooling for 8min, wherein the deformation temperature is as follows: 140 ℃, deflection: 17%, deformation mode: synchronous rolling, pass deformation: 5 percent; repeating the process to finally enable the total deformation of the alloy plate to reach 80%;
(7) then carrying out low-temperature short-time pre-aging treatment at 390 ℃ for 2 h;
(8) then, carrying out multi-cycle ultralow temperature deep cold rolling deformation treatment on the low-temperature pre-aged alloy plate for 5 times, firstly placing the plate in a liquid nitrogen tank for more than 1h, and then carrying out ultralow temperature deformation and deformation temperature: -150 ℃, deflection: 15%, deformation mode: synchronous rolling, wherein the pass deformation is 10%; then, putting the ultra-low temperature rolled plate into a liquid nitrogen tank for cooling for 8min, wherein the deformation temperature is as follows: 140 ℃, deflection: 15%, deformation mode: synchronous rolling, pass deformation: 7 percent; repeating the process to finally enable the total deformation of the alloy plate to reach 45%;
(9) and finally, carrying out isothermal aging treatment on the ultra-low temperature cold-rolled sheet, wherein the isothermal aging temperature is as follows: 360. 390, 420 ℃, time: 0.1-12 h.
Measurements of microhardness, electrical conductivity, and tensile properties for alloys in different states are shown in fig. 8 and table 2, and structural characterization of alloys in typical states is shown in fig. 9.
Example 3
The alloy components were compounded according to example 3 of table 1, with the following specific implementation steps:
(1) firstly, cutting 99.9 wt% of electrolytic high-purity Cu, sponge Ti, microalloying elements and the like as raw materials to prepare an alloy, and then smelting the alloy in a vacuum medium-frequency induction furnace;
(2) then carrying out homogenization heat treatment on the alloy ingot, wherein the temperature is as follows: 760 ℃, time: 2 h;
(3) then carrying out low-temperature hot rolling deformation on the ingot after the homogenization treatment, wherein the initial rolling temperature is as follows: the heat preservation time is 0.5h at 720 ℃, and the deformation is as follows: 85%, pass reduction: 5 percent;
(4) then, carrying out multi-cycle ultralow-temperature deep cold rolling deformation, wherein the specific process comprises the following steps: the low-temperature deformation cycle is more than 10 times, the liquid nitrogen tank is placed for 2 hours, and then ultra-low-temperature deformation is carried out, wherein the deformation temperature is as follows: -155 ℃, deflection: 9%, deformation mode: synchronous rolling, wherein the pass deformation is 8%; then, putting the ultra-low temperature rolled plate into a liquid nitrogen tank for cooling for 5min, wherein the deformation temperature is as follows: -155 ℃, deflection: 9%, deformation mode: synchronous rolling, pass deformation: 8 percent; repeating the process to finally enable the total deformation of the alloy plate to reach 38%;
(5) then carrying out short-time solution quenching treatment, wherein the solution temperature is as follows: 750 ℃, solid solution time: 0.5h, quenching mode: water quenching;
(6) then, carrying out multi-cycle ultralow temperature deep cold rolling deformation treatment on the alloy plate for 14 times, firstly placing the alloy plate in a liquid nitrogen tank for more than 1h, and then carrying out ultralow temperature deformation at the deformation temperature: -145 ℃, deflection: 20%, deformation mode: synchronous rolling, wherein the pass deformation is 5%; then, putting the ultra-low temperature rolled plate into a liquid nitrogen tank for cooling for 5min, wherein the deformation temperature is as follows: -150 ℃, deflection: 25%, deformation mode: synchronous rolling, pass deformation: 15 percent; repeating the process to finally enable the total deformation of the alloy plate to reach 70%;
(7) then carrying out low-temperature short-time pre-aging treatment at 360 ℃ for 2.5 h;
(8) then, carrying out multi-cycle ultralow temperature deep cold rolling deformation treatment on the low-temperature pre-aged alloy plate for 6 times, firstly placing the plate in a liquid nitrogen tank for more than 1h, and then carrying out ultralow temperature deformation and deformation temperature: -150 ℃, deflection: 5%, deformation mode: synchronous rolling, wherein the pass deformation is 7%; then, putting the ultra-low temperature rolled plate into a liquid nitrogen tank for cooling for 5min, wherein the deformation temperature is as follows: -150 ℃, deflection: 15%, deformation mode: synchronous rolling, pass deformation: 6 percent; repeating the process to finally enable the total deformation of the alloy plate to reach 55%;
(9) and finally, carrying out isothermal aging treatment on the ultra-low temperature cold-rolled sheet, wherein the isothermal aging temperature is as follows: 360. 390, 420 ℃, time: 0.1-12 h.
Example 4
The alloy components were compounded according to example 4 of table 1, with the following specific implementation steps:
(1) firstly, cutting 99.9 wt% of electrolytic high-purity Cu, sponge Ti, microalloying elements and the like as raw materials to prepare an alloy, and then smelting the alloy in a vacuum medium-frequency induction furnace;
(2) then carrying out homogenization heat treatment on the alloy ingot, wherein the temperature is as follows: 790 ℃, time: 8 h;
(3) then carrying out low-temperature hot rolling deformation on the ingot after the homogenization treatment, wherein the initial rolling temperature is as follows: 740 ℃, heat preservation time 1h, deformation: 85%, pass reduction: 20 percent;
(4) then, carrying out multi-cycle ultralow-temperature deep cold rolling deformation, wherein the specific process comprises the following steps: the low-temperature deformation cycle is more than 10 times, the liquid nitrogen tank is placed for 45min, and then ultra-low-temperature deformation is carried out, wherein the deformation temperature is as follows: -165 ℃, deflection: 12%, deformation mode: synchronous rolling, wherein the pass deformation is 4%; then, putting the ultra-low temperature rolled plate into a liquid nitrogen tank for cooling for 6min, wherein the deformation temperature is as follows: -165 ℃, deflection: 12%, deformation mode: synchronous rolling, pass deformation: 4 percent; repeating the process to finally enable the total deformation of the alloy plate to reach 42%;
(5) then carrying out short-time solution quenching treatment, wherein the solution temperature is as follows: 740 ℃, solid solution time: 2h, quenching mode: water quenching;
(6) then, carrying out multi-cycle ultralow temperature deep cold rolling deformation treatment on the alloy plate, wherein the low temperature deformation cycle times are 12, firstly placing the alloy plate in a liquid nitrogen tank for more than 1h, and then carrying out ultralow temperature deformation, deformation temperature: 130 ℃, deflection: 15%, deformation mode: synchronous rolling, wherein the pass deformation is 15%; then, putting the ultra-low temperature rolled plate into a liquid nitrogen tank for cooling for 10min, wherein the deformation temperature is as follows: -150 ℃, deflection: 20%, deformation mode: synchronous rolling, pass deformation: 10 percent; repeating the process to finally enable the total deformation of the alloy plate to reach 75%;
(7) then carrying out low-temperature short-time pre-aging treatment at the temperature of 420 ℃ for 0.1 h;
(8) then, carrying out multi-cycle ultralow temperature deep cold rolling deformation treatment on the low-temperature pre-aged alloy plate for 6 times, firstly placing the plate in a liquid nitrogen tank for more than 1h, and then carrying out ultralow temperature deformation and deformation temperature: 140 ℃, deflection: 10%, deformation mode: synchronous rolling, wherein the pass deformation is 8%; then, putting the ultra-low temperature rolled plate into a liquid nitrogen tank for cooling for 10min, wherein the deformation temperature is as follows: 130 ℃, deflection: 15%, deformation mode: synchronous rolling, pass deformation: 8 percent; repeating the process to finally enable the total deformation of the alloy plate to reach 40%;
(9) and finally, carrying out isothermal aging treatment on the ultra-low temperature cold-rolled sheet, wherein the isothermal aging temperature is as follows: 360. 390, 420 ℃, time: 0.1-12 h.
Example 5
The alloy components were compounded according to example 5 of table 1, with the following specific implementation steps:
(1) firstly, cutting 99.9 wt% of electrolytic high-purity Cu, sponge Ti, microalloying elements and the like as raw materials to prepare an alloy, and then smelting the alloy in a vacuum medium-frequency induction furnace;
(2) then carrying out homogenization heat treatment on the alloy ingot, wherein the temperature is as follows: 800 ℃, time: 8 h;
(3) then carrying out low-temperature hot rolling deformation on the ingot after the homogenization treatment, wherein the initial rolling temperature is as follows: 740 ℃, heat preservation time of 1.5h, deformation: 85%, pass reduction: 20 percent;
(4) then, carrying out multi-cycle ultralow-temperature deep cold rolling deformation, wherein the specific process comprises the following steps: the low-temperature deformation cycle is more than 10 times, the liquid nitrogen tank is placed for 40min, and then ultra-low-temperature deformation is carried out, wherein the deformation temperature is as follows: 170 ℃, deflection: 13%, deformation mode: synchronous rolling, wherein the pass deformation is 6%; then, the ultra-low temperature rolled plate is put into a liquid nitrogen tank to be cooled for 5.5min, and the deformation temperature is as follows: 170 ℃, deflection: 13%, deformation mode: synchronous rolling, pass deformation: 6 percent; repeating the process to finally enable the total deformation of the alloy plate to reach 35%;
(5) then carrying out short-time solution quenching treatment, wherein the solution temperature is as follows: 740 ℃, solid solution time: 1h, quenching mode: water quenching;
(6) then, carrying out multi-cycle ultralow temperature deep cold rolling deformation treatment on the alloy plate for 14 times of low temperature deformation cycle, firstly placing the alloy plate in a liquid nitrogen tank for more than 0.5h, and then carrying out ultralow temperature deformation at the deformation temperature: 130 ℃, deflection: 12%, deformation mode: synchronous rolling, wherein the pass deformation is 11%; then, putting the ultra-low temperature rolled plate into a liquid nitrogen tank for cooling for 9min, wherein the deformation temperature is as follows: 130 ℃, deflection: 15%, deformation mode: synchronous rolling, pass deformation: 15 percent; repeating the process to finally enable the total deformation of the alloy plate to reach 75%;
(7) then carrying out low-temperature short-time pre-aging treatment at 420 ℃ for 2 h;
(8) then, carrying out multi-cycle ultralow temperature deep cold rolling deformation treatment on the low-temperature pre-aged alloy plate for 7 times, firstly placing the plate in a liquid nitrogen tank for more than 1h, and then carrying out ultralow temperature deformation and deformation temperature: 130 ℃, deflection: 10%, deformation mode: synchronous rolling, wherein the pass deformation is 8%; then, putting the ultra-low temperature rolled plate into a liquid nitrogen tank for cooling for 5min, wherein the deformation temperature is as follows: -135 ℃, deflection: 15%, deformation mode: synchronous rolling, pass deformation: 8 percent; repeating the process to finally enable the total deformation of the alloy plate to reach 50%;
(9) and finally, carrying out isothermal aging treatment on the ultra-low temperature cold-rolled sheet, wherein the isothermal aging temperature is as follows: 360. 390, 420 ℃, time: 0.1-12 h.
Example 6
The alloy components were compounded according to example 6 of table 1, with the following specific implementation steps:
(1) firstly, cutting 99.9 wt% of electrolytic high-purity Cu, sponge Ti, microalloying elements and the like as raw materials to prepare an alloy, and then smelting the alloy in a vacuum medium-frequency induction furnace;
(2) then carrying out homogenization heat treatment on the alloy ingot, wherein the temperature is as follows: 780 ℃, time: 12 h;
(3) then carrying out low-temperature hot rolling deformation on the ingot after the homogenization treatment, wherein the initial rolling temperature is as follows: the heat preservation time is 1.5h at 720 ℃, and the deformation is as follows: 70 percent, pass reduction: 15 percent;
(4) then, carrying out multi-cycle ultralow-temperature deep cold rolling deformation, wherein the specific process comprises the following steps: the low-temperature deformation cycle is more than 10 times, the liquid nitrogen tank is placed for 38min, and then ultra-low-temperature deformation is carried out, wherein the deformation temperature is as follows: -145 ℃, deflection: 14%, deformation mode: synchronous rolling, wherein the pass deformation is 9%; then, the ultra-low temperature rolled plate is put into a liquid nitrogen tank to be cooled for 5.5min, and the deformation temperature is as follows: -145 ℃, deflection: 14%, deformation mode: synchronous rolling, pass deformation: 9 percent; repeating the process to finally enable the total deformation of the alloy plate to reach 48 percent;
(5) then carrying out short-time solution quenching treatment, wherein the solution temperature is as follows: 730 ℃, solid solution time: 2h, quenching mode: water quenching;
(6) then, carrying out multi-cycle ultralow temperature deep cold rolling deformation treatment on the alloy plate, wherein the low temperature deformation cycle times are 12, firstly placing the alloy plate in a liquid nitrogen tank for more than 1h, and then carrying out ultralow temperature deformation, deformation temperature: 130 ℃, deflection: 6%, deformation mode: synchronous rolling, wherein the pass deformation is 11%; then, putting the ultra-low temperature rolled plate into a liquid nitrogen tank for cooling for 9min, wherein the deformation temperature is as follows: 140 ℃, deflection: 15%, deformation mode: synchronous rolling, pass deformation: 10 percent; repeating the process to finally enable the total deformation of the alloy plate to reach 75%;
(7) then carrying out low-temperature short-time pre-aging treatment at 360 ℃ for 2.5 h;
(8) then, carrying out multi-cycle ultralow temperature deep cold rolling deformation treatment on the low-temperature pre-aged alloy plate for 5 times, firstly placing the plate in a liquid nitrogen tank for more than 1h, and then carrying out ultralow temperature deformation and deformation temperature: -150 ℃, deflection: 10%, deformation mode: synchronous rolling, wherein the pass deformation is 10%; then, the ultra-low temperature rolled plate is put into a liquid nitrogen tank to be cooled for 7min, and the deformation temperature is as follows: 130 ℃, deflection: 15%, deformation mode: synchronous rolling, pass deformation: 8 percent; repeating the process to finally enable the total deformation of the alloy plate to reach 55%;
(9) and finally, carrying out isothermal aging treatment on the ultra-low temperature cold-rolled sheet, wherein the isothermal aging temperature is as follows: 360. 390, 420 ℃, time: 0.1-12 h.
The mechanical properties of the alloys in the above different states were tested, as shown in table 2.
TABLE 2 mechanical properties corresponding to the peak aging states of Cu-Ti alloys in examples and comparative examples
Considering that the Cu-Ti alloy precipitation characteristic is an amplitude-modulated decomposition precipitation behavior, the method is mainly characterized in that a new phase can be formed by continuous growth of a parent phase through concentration fluctuation in the precipitation process, a nucleation process is not needed, a fine microstructure with periodically changed components is formed in the whole grain range after the precipitation decomposition, and the elastic strain field generated by two different components which are kept coherent can strongly prevent dislocation movement, so that the strengthening effect is generated.
In order to greatly improve the strength, elasticity, conductivity and high-temperature softening resistance of the alloy, the invention firstly regulates and controls the structure characteristics of the casting process of the alloy based on multi-component composite microalloying, and then further regulates and controls the alloy in a multi-process integration manner through hot processing on the basis of effectively improving the as-cast structure, wherein the regulation and control includes homogenization, low-temperature hot rolling, solid solution, ultralow-temperature deformation, pre-aging, secondary ultralow-temperature deformation, aging and the like, so that the alloy can rapidly generate amplitude modulation decomposition, the precipitation rate, the precipitation quantity and the uniform dispersion distribution degree of a precipitation phase are increased, the strength, the elasticity and the conductivity are improved, the characteristic of lower coarsening rate of the precipitation phase can be shown, and the high-temperature softening resistance of the alloy is improved. Specifically, the low-temperature hot rolling after homogenization can not only transform the structure from an as-cast structure to a deformed structure to increase the deformability of the alloy, but also avoid oxidation in the high-temperature hot rolling process of the alloy and promote the uniform dispersion distribution degree of fine particles formed after the addition of the composite micro-alloying elements. On the basis, multi-cycle ultralow temperature deep cooling rolling deformation is further introduced, so that the uniform dispersion distribution degree of fine particles formed by the composite microalloying elements can be effectively promoted, and the strain energy storage around dispersed particles and residual precipitated phases can be greatly increased. This is reflected in the metallographic structure of the alloy of comparative example 1 and comparative example 2, and a large number of coarse precipitated phases (as shown in fig. 3 and fig. 5) remain, and these precipitated phases are not only difficult to be well redissolved in the subsequent solid solution process, so as to affect the solid solution effect, but also further reduce the subsequent age hardening capacity of the alloy, and significantly affect the great improvement of the comprehensive properties of the alloy. In contrast, if the alloy is further subjected to multi-cycle ultralow temperature deep cold rolling deformation treatment after low-temperature hot rolling, not only can the precipitation phase in the matrix be remarkably crushed and uniformly dispersed in the alloy matrix (as shown in fig. 7 and 9), but also the strain energy storage around the dispersed precipitation phase can be increased, so that the residual precipitation phase of the alloy can be quickly redissolved in the subsequent solid solution process, the solid solution temperature and the solid solution time are reduced, and the actual production cost of the alloy is effectively reduced.
In addition, considering that the precipitation characteristic of the Cu-Ti alloy is an amplitude-modulated decomposition precipitation behavior, the Cu-Ti alloy has the common characteristic that a new phase can be formed by continuous growth of a parent phase through concentration fluctuation without a nucleation process, a fine microstructure with periodically changed components is formed in the whole crystal grain range after the precipitation decomposition, and an elastic strain field generated by keeping two phases with different components coherent can strongly prevent dislocation movement, thereby generating a strengthening effect. Therefore, if the multi-cycle ultra-low temperature deep cold rolling deformation treatment with a certain deformation is firstly carried out after the solution quenching, a large number of dislocation lines are uniformly dispersed and distributed around the dispersed particles in the alloy matrix due to the action of the fine dispersed particles introduced after the composite micro-alloying elements are added. The dislocation line not only can obviously promote the speed of the AM decomposition in the subsequent pre-aging process, but also can obviously reduce the periodic fluctuation range of the components in the alloy matrix. And then if the alloy after the multi-cycle ultralow temperature deformation and pre-aging regulation is further subjected to multi-cycle ultralow temperature deep cold rolling deformation treatment with proper deformation, the generated component fluctuation can be crushed again. However, the metal can be used as a core point of subsequent further aging, spinodal decomposition can occur again in the further aging process, and the fluctuation range of components in the alloy micro-region can be smaller, so that the precipitation rate and the amount of subsequent precipitation phases are remarkably increased, and the corresponding strength, elasticity and conductivity can be greatly improved (as shown in fig. 6 and 8).
In addition, the precipitation rate and the amount of the precipitate phase are greatly improved, and the positive influence of fine dispersed particles formed after the composite microalloying elements are added on the precipitate phase is added, so that the growth rate of the formed precipitate phase in the subsequent aging process can be maintained at a lower level, and finally the developed alloy can show excellent high-temperature softening resistance. This is shown in fig. 6 and 8, and the hardness of both alloys rapidly peaked at the initial aging stage during aging at 390 c, and then decreased very slowly with further increase in aging time, showing excellent high temperature softening resistance. From the performance test results, it can be seen that the alloys of examples 1 and 2, after reaching the peak hardness (-330 HV) by isothermal aging at 390 ℃, both maintained the higher level of alloy hardness with increasing aging time, with a very slow rate of decrease (as shown in FIGS. 6 and 8), while the conductivity increased rapidly. In contrast, the alloys of comparative examples 1 and 2, prepared by the conventional process, both rapidly decreased after reaching peak hardness, while the conductivity increased at a very slow rate with a small increase. In addition, the electrical conductivity of the alloys developed using the newly developed manufacturing process is also significantly higher than the electrical conductivity of the alloys prepared using the conventional process for the aged state (as shown in FIGS. 6 and 8). Further, tensile property tests on the two alloys show that the tensile strength of the two alloys can reach more than 1021.3MPa, which is much higher than the tensile strength (900-917 MPa) corresponding to the alloys of comparative examples 1 and 2 prepared by the traditional process, and the elastic modulus is more than 115.3, as shown in Table 2. Therefore, after the integrated regulation and control of multiple processes of composite microalloying and hot working, the Cu-Ti alloy has high strength, high elasticity, high conductivity and excellent high-temperature softening resistance.
In conclusion, after the Cu-Ti alloy structure evolution is integrally regulated and controlled through multiple processes of composite microalloying and hot working, the spinodal decomposition characteristics corresponding to the alloy are obviously changed, the aging precipitation rate is obviously accelerated, and the peak hardness, the strength and the conductivity are obviously improved. More importantly, the developed alloy also has excellent high-temperature softening resistance. The design scheme and the preparation method of the components capable of effectively improving the strength, the conductivity, the elasticity and the high-temperature softening resistance of the Cu-Ti alloy can well meet the urgent requirements of high-strength, high-elasticity, high-conductivity and softening resistance of copper alloys for manufacturing typical parts in various high and new technical fields of electronic industry, aerospace, instruments, household appliances and the like. Therefore, the preparation method is not only very suitable for being applied to a plurality of high and new technical fields, especially the fields with special requirements on novel high-strength, high-elasticity and high-conductivity copper alloy, but also is particularly applied and popularized to more sensitive industries for solving the problems existing in the process of applying beryllium bronze, such as the harmful influence of smoke, steam and dust of beryllium and compounds thereof on the health of human bodies, high production cost, high price and the like. In addition, the preparation technology has certain guiding significance for further development, processing and application of high-strength conductive softening-resistant copper alloy and other similar metal materials in other fields, and copper alloy processing enterprises are worthy of paying attention to the alloy and the preparation process thereof, so that the alloy and the preparation process thereof can be popularized and applied as soon as possible.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.