CN114150123A - Method for effectively improving strength and conductivity of alloy - Google Patents
Method for effectively improving strength and conductivity of alloy Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B37/00—Control devices or methods specially adapted for metal-rolling mills or the work produced thereby
- B21B37/74—Temperature control, e.g. by cooling or heating the rolls or the product
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
- B21B2003/005—Copper or its alloys
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Abstract
The invention provides a preparation method for improving the strength and the electric conductivity of an alloy, which is particularly suitable for a Cu-Ti alloy, and realizes integrated coupling regulation and control of multiple processes of component design, fusion casting, homogenization, low-temperature hot rolling, multi-cycle ultralow-temperature cold rolling, short-time solution quenching, low-temperature short-time pre-aging treatment, multi-cycle ultralow-temperature deep cold rolling and isothermal aging by the multi-process, wherein the hardness of the alloy is more than 340HV after the short-time aging treatment, the tensile strength can reach 1110.4MPa, the electric conductivity is close to 14% IACS, the elastic modulus reaches 127GPa, the hardness is slowly reduced and a secondary peak appears after the further aging treatment, the peak hardness is close to 340HV, the tensile strength can still reach 1091.3MPa, the electric conductivity is more than 15% IACS, and the elastic modulus is 114.2 GPa. The preparation method developed by the invention is very suitable for manufacturing high-strength elastic copper alloy materials for typical parts in a plurality of high and new technical fields of electronic industry, aerospace, instruments, household appliances and the like, and especially for manufacturing parts with complex shapes which have better requirements on strength, elasticity, conductivity and the like.
Description
Technical Field
The invention belongs to the technical field of alloys, and particularly relates to a method for effectively improving the strength and the conductivity of an alloy.
Background
With the rapid development of modern electronic industry technology, electronic components are developed towards high performance, precision and miniaturization, which puts higher requirements on elasticity, strength, conductivity and reliability of used materials. Although beryllium bronze has excellent elasticity, strength, wear resistance, electrical conductivity and the like, and simultaneously has a lower stress relaxation characteristic, and has been widely applied to a plurality of high and new technical fields of electronic industry, aerospace, instruments, household appliances and the like, the alloy of the system still has the following 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, and a novel elastic copper alloy material capable of well replacing the beryllium bronze is urgently needed to be developed.
The Cu-Ti alloy belongs to aging strengthening type alloy, and has higher strength and elasticity, and good high-temperature stress relaxation resistance, heat resistance, wear resistance and fatigue resistance. A great deal of research shows that the Cu-Ti alloy with the Ti content of 2.5-5 percent has good performance of replacing beryllium bronze, and the Cu-Ti alloy which is decomposed and precipitated and strengthened by amplitude modulation can achieve the strength and elasticity equivalent to that of the beryllium bronze through proper heat treatment and heat processing treatment, but the general expression is that the electric conductivity is lower. Therefore, how to make Cu — Ti alloys capable of combining high strength, high elasticity, and high strength, and therefore, a great deal of researchers have improved the performance of Cu — Ti alloys by adding alloying elements such as Cr, Zr, Al, Cd, Mg, Ni, Sn, Co, etc. as trace addition elements. The performance of the alloy after adding Cr, Zr and Cd is good and balanced, but Cd is a toxic element and does not meet the requirements of environmental protection. Although the research finds that the Cr element can effectively improve the performance of the Cu-Ti alloy, the relevant action mechanism is not disclosed yet. In addition, compared with Cu-3Ti, the Cu-3Ti-4Al alloy added with Al can improve the electrical conductivity by 6 percent IACS after being aged at 450 ℃, but the peak hardness is reduced from 280HV to 180 HV. Structural characterization found that Cu4Ti is the main strengthening phase in the alloy and is formed based on the principle of nucleation and growth, rather than spinodal decomposition, and the precipitate phase grows along the c direction, which reduces the lattice misfit strain energy between the matrix and the precipitate phase, and in addition, forms AlCu2Ti(DO3) The dominant inertia face of the precipitated phase approaches {110} of the face-centered cubic matrix. Eventually, the solid solubility of Ti in the Cu matrix is reduced due to the formation of these phases, resulting in improved conductivity. In addition, the addition of a certain amount of Ni element to the Cu-3Ti alloy can transform the microstructure of the as-cast alloy from dendritic state to equiaxial state, and the aging process can also cause annealing twin crystals in the residual NiTi phase. The change in texture ultimately results in an increase in the electrical conductivity of the alloy, but a decrease in strength occurs.
Considering that the key to the properties of the alloy such as strength, elasticity and conductivity is still the components and the process, if the alloy as-cast structure can be regulated and controlled by proper micro-alloying and then proper process regulation and control are carried out, the solute element Ti can be precipitated from the alloy matrix as much as possible, and then the Cu-Ti alloy can show excellent comprehensive properties. Therefore, it is very necessary to develop a high-strength conductive Cu-Ti alloy material and a preparation technology thereof, which can not increase the production cost of the alloy, but also have excellent comprehensive properties, so as to better meet the urgent needs of high and new technical fields for the material. In addition, the preparation process of the novel Cu-Ti alloy material can also play an important inspiring and promoting role in the development of other novel metal materials. Electrical conductivity is the key to the further wide spread use of this material.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for effectively improving the strength and the conductivity of an alloy, which specifically comprises the following steps:
a method for effectively increasing the strength and conductivity of an alloy, comprising the steps of:
(1) preparing an alloy ingot by vacuum melting;
(2) carrying out homogenization heat treatment;
(3) low-temperature hot rolling;
(4) carrying out multi-cycle ultralow temperature deep cooling rolling deformation;
(5) short-time solution quenching treatment;
(6) low-temperature short-time pre-aging treatment;
(7) carrying out multi-cycle ultralow temperature deep cooling rolling deformation;
(8) and (5) isothermal aging treatment.
Specifically, the alloy is a Cu — Ti alloy.
Specifically, the initial rolling temperature of the low-temperature hot rolling in the step (3) is 700-; the deformation temperature of the multi-cycle ultralow-temperature deep cold rolling deformation in the step (4) is-80 ℃ to-190 ℃, and the total deformation amount is 40-70%; the solid solution temperature of the short-time solid solution quenching treatment in the step (5) is 750-; the temperature of the low-temperature short-time pre-aging treatment in the step (6) is 350-; the deformation temperature of the multi-cycle ultralow-temperature deep cooling rolling deformation in the step (7) is-80 ℃ to-190 ℃, and the deformation amount is 60-85%; the temperature of the isothermal aging treatment in the step (8) is 350-430 ℃, and the time is 0.5-10 h.
Specifically, the homogenization heat treatment process in the step (2) comprises the following steps: the temperature is 750 ℃ and 850 ℃ and the time is 15-30 h.
Specifically, the low-temperature hot rolling process in the step (3) comprises the following steps: the low-temperature hot rolling treatment process comprises the following steps: the initial rolling temperature: 710 ℃ and 750 ℃, and the heat preservation time: 0.1-1h, deformation: 45-80%, deformation mode: unidirectional rolling, pass reduction: 3-15%, finishing temperature: greater than 500 ℃.
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 30min, and then ultra-low-temperature deformation is carried out, wherein the deformation temperature is as follows: -100 ℃ to-190 ℃, deflection: 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 2-9min, wherein the deformation temperature is as follows: -100 ℃ to-190 ℃, deflection: 5-15%, modification: synchronous rolling, pass deformation: 2 to 10 percent; and repeating the process to finally enable the total deformation of the alloy plate to reach 40-70%.
Specifically, the short-time solution quenching treatment process in the step (5) comprises the following steps: solid solution temperature: 780 ℃ and 850 ℃ and solid solution time: 1.5-3h, heating rate: more than 10 ℃/s, quenching mode: water quenching, wherein the cooling rate is more than 100 ℃/s.
Specifically, the low-temperature short-time pre-aging treatment process in the step (6) comprises the following steps: the preaging temperature is 360-430 ℃, the time is 0.7-2.8h, the heating rate is as follows: greater than 6.5 deg.c/sec.
Specifically, the multi-cycle ultralow-temperature deep cold rolling deformation process in the step (7) comprises the following steps: the low-temperature deformation cycle is more than 6 times, the liquid nitrogen tank is placed for more than 30min, and then ultra-low-temperature deformation is carried out, wherein the deformation temperature is as follows: -100 ℃ to-190 ℃, deflection: 8-30%, deformation mode: synchronous rolling, wherein the pass deformation is 5-15%; then, putting the ultra-low temperature rolled plate into a liquid nitrogen tank for cooling for 2-9min, wherein the deformation temperature is as follows: -100 ℃ to-190 ℃, deflection: 8-30%, deformation mode: synchronous rolling, pass deformation: 5 to 15 percent; and repeating the process to finally enable the total deformation of the alloy plate to reach 60-85%.
Specifically, the isothermal aging treatment process in the step (8) comprises the following steps: isothermal aging temperature: 360 ℃ and 430 ℃, time: 0.6-5h, heating rate: greater than 6.5 deg.c/sec.
The invention provides a preparation method for effectively improving the strength and the electric conductivity of a Cu-Ti alloy aiming at the problems that the strength, the electric conductivity and other properties of the existing Cu-Ti alloy are not excellent enough, and the like, which can not increase the production cost of the alloy, has excellent comprehensive properties, and is suitable for being applied to a plurality of technical fields, in particular to a plurality of high and new technical fields with certain requirements on the strength, the electric conductivity, the elasticity, the processing property, the production cost and the like of copper alloy, industries such as production and manufacturing of civil products, and manufacturers already or preparing to produce similar copper alloy products.
In addition to proper homogenization heat treatment and hot rolling deformation, the method performs a certain amount of ultra-low temperature deep cooling rolling deformation treatment before solid solution in the multi-process regulation and control of hot working, so that the rapid redissolution of the precipitation phase can be effectively promoted, and the residual quantity of the CuTi precipitation phase in the alloy matrix can be remarkably reduced. In addition, in the research process, besides the multi-process coupling regulation of the hot working process, the alloy structure meets the specific requirements, the precipitation characteristic of the Cu-Ti alloy is considered to be the AM decomposition precipitation behavior, the common characteristic is that a parent phase can continuously grow up through concentration fluctuation to form a new phase without a nucleation process, a fine microstructure with periodically changed components is formed in the whole crystal grain range after the exsolution decomposition, the elastic strain field generated by the two phases with different components which are kept coherent can strongly prevent dislocation movement, thereby generating the strengthening effect, and the invention also particularly designs and develops the preparation process of the coupling regulation AM decomposition of the preaging and the ultralow temperature deformation after the solid solution and the dislocation distribution characteristic. The preaging regulation and control enables the alloy to generate slight amplitude modulation decomposition, and then the ultralow temperature deep cold rolling deformation is carried out, so that not only can the micro area generating the slight amplitude modulation decomposition be broken, but also the dislocation movement can be effectively blocked due to the amplitude modulation decomposition tissue generated by the preaging regulation and control, and the dislocation distribution formed in the ultralow temperature deep cold rolling deformation process is more uniform and dispersed. In addition, the spinodal decomposition structure crushed by the ultra-low temperature deep cold rolling deformation can be used as a nucleation point for further aging precipitation in the subsequent aging process, so that the precipitation rate and the precipitation quantity of the alloy precipitate can be remarkably increased. Significant improvements in alloy strength and conductivity are necessarily obtained due to the rapid progression of spinodal decomposition. Finally, the alloy necessarily has high strength and high conductivity based on the process regulation.
Drawings
FIG. 1 is a flow chart of the alloy preparation process of the present invention;
FIG. 2 shows the change law of the hardness and the conductivity of the Cu-Ti alloy in the implementation process of comparative example 1;
FIG. 3 shows a metallographic structure corresponding to a final state of a Cu-Ti alloy in a cold rolling process in comparative example 1;
FIG. 4 shows the corresponding hardness and conductivity change rules of Cu-Ti-La alloy in the implementation process of comparative example 2;
FIG. 5 is a comparison of the hardness and conductivity change laws of Cu-Ti alloys in the implementation of comparative example 1 and example 1;
FIG. 6 shows the final ultralow temperature deep cooling rolling state metallographic structure of the Cu-Ti alloy in the implementation process of embodiment 1;
FIG. 7 is a comparison of the hardness and conductivity change laws of Cu-Ti-La alloys in the course of the comparative example 2 and example 2.
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.
As shown in fig. 1, the preparation method of the present invention comprises the following steps: the method comprises the steps of preparing an alloy ingot by vacuum melting → homogenizing heat treatment → low-temperature hot rolling → multi-cycle ultralow-temperature deep cold rolling deformation → short-time solid solution quenching treatment → low-temperature short-time pre-aging treatment → multi-cycle ultralow-temperature deep cold rolling deformation → isothermal aging treatment, and can control the grain structure of the copper alloy, remarkably induce the precipitation quantity and density of alloy peak aging state, and finally enable the copper alloy to have high strength and high conductivity.
The raw materials respectively adopt 99.9 wt% of electrolytic high-purity Cu, sponge Ti and other intermediate alloys, pure metals and the like. Firstly, alloy is smelted by utilizing a vacuum intermediate frequency induction furnace. The specific chemical compositions of the alloys used in the examples are shown in table 1.
Then carrying out homogenization heat treatment (the temperature is 750-: firstly, carrying out low-temperature hot rolling deformation on the ingot after homogenization treatment, wherein the initial rolling temperature is as follows: 700 ℃ and 780 ℃, and the heat preservation time is as follows: 0.1-2h, deformation: 45-90 percent; then, carrying out multi-cycle ultralow-temperature deep cooling rolling deformation on the hot rolled plate, wherein the deformation temperature is as follows: -80 ℃ to-190 ℃, total deformation: 40-70 percent; then carrying out short-time solution quenching treatment on the ultra-low temperature deep-cooling rolled plate, wherein the solution temperature is as follows: 750 ℃ and 850 ℃, solid solution time: 1-3h, quenching mode: water quenching; then firstly carrying out low-temperature short-time pre-aging treatment on the alloy plate in the solid solution quenching state, wherein the treatment temperature is 350-: greater than 6 ℃/sec; then, performing multi-cycle ultralow-temperature deep cooling rolling deformation on the pre-aged alloy plate, wherein the deformation temperature is as follows: -80 ℃ to-190 ℃, deflection: 60 to 85 percent; and finally, carrying out isothermal aging treatment on the ultra-low temperature deep-cooling rolled plate, wherein the aging temperature is as follows: 350-430 ℃, time: 0.5-10 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.
The specific implementation mode is as follows:
TABLE 1 alloy chemistry for carrying out the invention
Comparative example 1
Firstly, smelting the alloy by using a vacuum intermediate frequency induction furnace according to the component design value of the alloy No. 1; then carrying out homogenization heat treatment (the temperature is 750-: firstly, carrying out low-temperature hot rolling deformation on the ingot after homogenization treatment, wherein the initial rolling temperature is as follows: 700 ℃ and 780 ℃, and the heat preservation time is as follows: 0.1-2h, deformation: 45-90 percent; then, cold rolling deformation is carried out on the hot rolled plate at room temperature, and the total deformation is as follows: 40-70%, pass reduction: 4 to 15 percent; then carrying out solution quenching treatment on the cold-rolled sheet, wherein the solution temperature is as follows: 750 ℃ and 850 ℃, solid solution time: 1-5h, quenching mode: water quenching; then firstly, cold rolling deformation is carried out on the alloy plate in the solid solution quenching state at room temperature, wherein the deformation amount is as follows: 60-85%, pass reduction: 5 to 17 percent; and finally, carrying out isothermal aging treatment on the cold-rolled sheet at room temperature at 350, 400 and 450 ℃, wherein the aging time is as follows: 0.5-10 h. Finally, the microhardness, conductivity and tensile property measurements of the alloys in different states are shown in FIG. 2 and Table 2, and the structure characterization of the alloy in a typical state is shown in FIG. 3.
Comparative example 2
Firstly, smelting the alloy by using a vacuum intermediate frequency induction furnace according to the component design value of the alloy No. 2; then carrying out homogenization heat treatment (the temperature is 750-: firstly, carrying out low-temperature hot rolling deformation on the ingot after homogenization treatment, wherein the initial rolling temperature is as follows: 700 ℃ and 780 ℃, and the heat preservation time is as follows: 0.1-2h, deformation: 45-90 percent; then, cold rolling deformation is carried out on the hot rolled plate at room temperature, and the total deformation is as follows: 40-70%, pass reduction: 4 to 15 percent; then carrying out solution quenching treatment on the cold-rolled sheet, wherein the solution temperature is as follows: 750 ℃ and 850 ℃, solid solution time: 1-5h, quenching mode: water quenching; then firstly, cold rolling deformation is carried out on the alloy plate in the solid solution quenching state at room temperature, wherein the deformation amount is as follows: 60-85%, pass reduction: 5 to 17 percent; and finally, carrying out isothermal aging treatment on the cold-rolled sheet at room temperature at 350, 400 and 450 ℃, wherein the aging time is as follows: 0.5-10 h. Finally, the microhardness, conductivity and tensile property of the alloy in different states are measured as shown in figure 4 and table 2.
Example 1
Firstly, smelting the alloy by using a vacuum intermediate frequency induction furnace according to the component design value of the alloy No. 1; then carrying out homogenization heat treatment (the temperature is 750-: firstly, carrying out low-temperature hot rolling deformation on the ingot after homogenization treatment, wherein the initial rolling temperature is as follows: 710 ℃ and 750 ℃, and the heat preservation time: 0.1-1h, deformation: 45-80%, deformation mode: unidirectional rolling, pass reduction: 3-15%, finishing temperature: greater than 500 ℃; then, carrying out multi-cycle ultralow temperature deep cold rolling deformation treatment on the hot rolled plate, wherein the low temperature deformation cycle number is more than 10, firstly placing the hot rolled plate in a liquid nitrogen tank for more than 30min, and then carrying out ultralow temperature deformation, deformation temperature: -100 ℃ to-190 ℃, deflection: 5% -15%, deformation mode: synchronously rolling, wherein the pass deformation is 2-10%; then, putting the ultra-low temperature rolled plate into a liquid nitrogen tank for cooling for 2-9min, wherein the deformation temperature is as follows: -100 ℃ to-190 ℃, deflection: 5% -15%, deformation mode: synchronous rolling, pass deformation: 2-10%; repeating the above processes to finally enable the total deformation of the alloy plate to reach 40-70%; then carrying out short-time solution quenching treatment on the multi-cycle ultralow-temperature deep-cooling rolled plate, wherein the solution temperature is as follows: 780 ℃ and 850 ℃ and solid solution time: 1.5-3h, heating rate: more than 10 ℃/s, quenching mode: water quenching, wherein the cooling rate is more than 100 ℃/s; then firstly carrying out low-temperature short-time pre-aging treatment on the alloy plate in the solid solution quenching state, wherein the pre-aging temperature is 360-430 ℃, the time is 0.7-2.8h, and the heating rate is as follows: greater than 6.5 ℃/sec; then, carrying out multi-cycle ultralow temperature deep cold rolling deformation treatment on the low-temperature pre-aged alloy plate, wherein the low-temperature deformation cycle is more than 6 times, firstly placing the plate in a liquid nitrogen tank for more than 30min, and then carrying out ultralow temperature deformation and deformation temperature: -100 ℃ to-190 ℃, deflection: 8% -30%, deformation mode: synchronously rolling, wherein the pass deformation is 5-15%; then, putting the ultra-low temperature rolled plate into a liquid nitrogen tank for cooling for 2-9min, wherein the deformation temperature is as follows: -100 ℃ to-190 ℃, deflection: 8% -30%, deformation mode: synchronous rolling, pass deformation: 5-15%; repeating the above processes to finally enable the total deformation of the alloy plate to reach 60-85%; and finally, carrying out isothermal aging treatment on the ultra-low temperature cold-rolled sheet, wherein the isothermal aging temperature is as follows: 360 ℃ and 430 ℃, time: 0.6-10h, heating rate: greater than 6.5 deg.c/sec. The microhardness, conductivity, and tensile properties of the alloys in the different states were then measured as shown in fig. 5 and table 2, and the structural characterization of the alloys in the typical state (as shown in fig. 6).
Example 2
According to the design value of the components of the alloy 2#, firstly, smelting the alloy by using a vacuum intermediate frequency induction furnace; then carrying out homogenization heat treatment (the temperature is 750-: firstly, carrying out low-temperature hot rolling deformation on the ingot after homogenization treatment, wherein the initial rolling temperature is as follows: 710 ℃ and 750 ℃, and the heat preservation time: 0.1-1h, deformation: 45-80%, deformation mode: unidirectional rolling, pass reduction: 3-15%, finishing temperature: greater than 500 ℃; then, carrying out multi-cycle ultralow temperature deep cold rolling deformation treatment on the hot rolled plate, wherein the low temperature deformation cycle number is more than 10, firstly placing the hot rolled plate in a liquid nitrogen tank for more than 30min, and then carrying out ultralow temperature deformation, deformation temperature: -100 ℃ to-190 ℃, deflection: 5% -15%, deformation mode: synchronously rolling, wherein the pass deformation is 2-10%; then, putting the ultra-low temperature rolled plate into a liquid nitrogen tank for cooling for 2-9min, wherein the deformation temperature is as follows: -100 ℃ to-190 ℃, deflection: 5% -15%, deformation mode: synchronous rolling, pass deformation: 2-10%; repeating the above processes to finally enable the total deformation of the alloy plate to reach 40-70%; then carrying out short-time solution quenching treatment on the multi-cycle ultralow-temperature deep-cooling rolled plate, wherein the solution temperature is as follows: 780 ℃ and 850 ℃ and solid solution time: 1.5-3h, heating rate: more than 10 ℃/s, quenching mode: water quenching, wherein the cooling rate is more than 100 ℃/s; then firstly carrying out low-temperature short-time pre-aging treatment on the alloy plate in the solid solution quenching state, wherein the pre-aging temperature is 360-430 ℃, the time is 0.7-2.8h, and the heating rate is as follows: greater than 6.5 ℃/sec; then, carrying out multi-cycle ultralow temperature deep cold rolling deformation treatment on the low-temperature pre-aged alloy plate, wherein the low-temperature deformation cycle is more than 6 times, firstly placing the plate in a liquid nitrogen tank for more than 30min, and then carrying out ultralow temperature deformation and deformation temperature: -100 ℃ to-190 ℃, deflection: 8% -30%, deformation mode: synchronously rolling, wherein the pass deformation is 5-15%; then, putting the ultra-low temperature rolled plate into a liquid nitrogen tank for cooling for 2-9min, wherein the deformation temperature is as follows: -100 ℃ to-190 ℃, deflection: 8% -30%, deformation mode: synchronous rolling, pass deformation: 5-15%; repeating the above processes to finally enable the total deformation of the alloy plate to reach 60-85%; and finally, carrying out isothermal aging treatment on the ultra-low temperature cold-rolled sheet, wherein the isothermal aging temperature is as follows: 360 ℃ and 430 ℃, time: 0.6-10h, heating rate: greater than 6.5 deg.c/sec. The microhardness, conductivity, and tensile properties of the alloys in the different states were then measured as shown in fig. 7 and table 2.
TABLE 2 mechanical properties of several Cu-Ti alloys in different states
Example 3
In the embodiment, a common Cu-Ti alloy is used as a processing object, and the specific operation steps and process parameters are as follows:
(1) firstly, smelting a Cu-Ti alloy by using a vacuum intermediate frequency induction furnace;
(2) homogenization heat treatment, temperature: 750 ℃, time: 15 h;
(3) low-temperature hot rolling, wherein the initial rolling temperature is as follows: 700 ℃, heat preservation time: 0.1h, deformation: 45%, deformation mode: unidirectional rolling, pass reduction: 3%, finish rolling temperature: greater than 500 ℃. (ii) a
(4) Multiple-circulation ultralow-temperature deep cooling rolling deformation, deformation temperature: the low-temperature deformation cycle is more than 10 times, the liquid nitrogen tank is placed for more than 30min, and then ultra-low-temperature deformation is carried out, wherein the deformation temperature is as follows: -80 ℃, deflection: 5%, deformation mode: synchronous rolling, wherein the pass deformation is 2%; then, putting the ultra-low temperature rolled plate into a liquid nitrogen tank for cooling for 2min, wherein the deformation temperature is as follows: -80 ℃, 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 40%;
(5) short-time solution quenching treatment, wherein the solution temperature is as follows: 750 ℃, solid solution time: 1h, heating rate: more than 10 ℃/s, quenching mode: water quenching, wherein the cooling rate is more than 100 ℃/s;
(6) low-temperature short-time pre-aging treatment, wherein the pre-aging temperature is 350 ℃, the time is 0.5h, the heating rate is as follows: greater than 6 deg.c/sec. (ii) a
(7) Multiple-circulation ultralow-temperature deep cooling rolling deformation, deformation temperature: the low-temperature deformation cycle is more than 6 times, the liquid nitrogen tank is placed for more than 30min, and then ultra-low-temperature deformation is carried out, wherein the deformation temperature is as follows: -80 ℃, deflection: 8%, 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 2min, wherein the deformation temperature is as follows: -80 ℃, deflection: 8%, deformation mode: synchronous rolling, pass deformation: 5 percent; repeating the process to finally enable the total deformation of the alloy plate to reach 60%;
(8) isothermal aging treatment, isothermal aging temperature: 350 ℃, time: 0.5h, heating rate: greater than 6.5 deg.c/sec.
Example 4
In the embodiment, a common Cu-Ti alloy is used as a processing object, and the specific operation steps and process parameters are as follows:
(1) firstly, smelting a Cu-Ti alloy by using a vacuum intermediate frequency induction furnace;
(2) homogenization heat treatment, temperature: 850 ℃, time: 30 h;
(3) low-temperature hot rolling, wherein the initial rolling temperature is as follows: 780 ℃, heat preservation time: 2h, deformation amount: 90%, deformation mode: unidirectional rolling, pass reduction: 15%, finish rolling temperature: greater than 500 ℃. (ii) a
(4) Multiple-circulation ultralow-temperature deep cooling rolling deformation, deformation temperature: the low-temperature deformation cycle is more than 10 times, the liquid nitrogen tank is placed for more than 30min, and then ultra-low-temperature deformation is carried out, wherein the deformation temperature is as follows: -190 ℃, 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 9min, wherein the deformation temperature is as follows: -190 ℃, 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 70%;
(5) short-time solution quenching treatment, wherein the solution temperature is as follows: 850 ℃, solid solution time: 3h, heating rate: more than 10 ℃/s, quenching mode: water quenching, wherein the cooling rate is more than 100 ℃/s;
(6) low-temperature short-time pre-aging treatment, wherein the pre-aging temperature is 430 ℃, the time is 3h, and the heating rate is as follows: greater than 6.5 ℃/sec;
(7) multiple-circulation ultralow-temperature deep cooling rolling deformation, deformation temperature: the low-temperature deformation cycle is more than 6 times, the liquid nitrogen tank is placed for more than 30min, and then ultra-low-temperature deformation is carried out, wherein the deformation temperature is as follows: -190 ℃, deflection: 30%, 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 9min, wherein the deformation temperature is as follows: -190 ℃, deflection: 30%, deformation mode: synchronous rolling, pass deformation: 15 percent; repeating the process to finally enable the total deformation of the alloy plate to reach 85%;
(8) isothermal aging treatment, isothermal aging temperature: 430 ℃, time: 3h, heating rate: greater than 6.5 deg.c/sec.
Example 5
In the embodiment, the Cu-Ti alloy is used as a processing object, and the specific operation steps and process parameters are as follows:
(1) firstly, smelting a Cu-Ti alloy by using a vacuum intermediate frequency induction furnace;
(2) homogenization heat treatment, temperature: 800 ℃, time: 20 h;
(3) low-temperature hot rolling, wherein the initial rolling temperature is as follows: 710 ℃, heat preservation time: 1h, deformation amount: 80%, deformation mode: unidirectional rolling, pass reduction: 5%, finish rolling temperature: greater than 500 ℃. (ii) a
(4) Multiple-circulation ultralow-temperature deep cooling rolling deformation, deformation temperature: the low-temperature deformation cycle is more than 10 times, the liquid nitrogen tank is placed for more than 30min, and then ultra-low-temperature deformation is carried out, wherein the deformation temperature is as follows: -100 ℃, deflection: 10%, deformation mode: synchronous rolling, wherein the pass deformation is 8%; 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: -100 ℃, deflection: 10%, deformation mode: synchronous rolling, pass deformation: 8 percent; repeating the process to finally enable the total deformation of the alloy plate to reach 50%;
(5) short-time solution quenching treatment, wherein the solution temperature is as follows: 780 ℃, solid solution time: 1.5h, heating rate: more than 10 ℃/s, quenching mode: water quenching, wherein the cooling rate is more than 100 ℃/s;
(6) low-temperature short-time pre-aging treatment, wherein the pre-aging temperature is 360 ℃, the time is 0.7h, and the heating rate is as follows: greater than 6 ℃/sec;
(7) multiple-circulation ultralow-temperature deep cooling rolling deformation, deformation temperature: the low-temperature deformation cycle is more than 6 times, the liquid nitrogen tank is placed for more than 30min, and then ultra-low-temperature deformation is carried out, wherein the deformation temperature is as follows: -100 ℃, deflection: 20%, 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: -100 ℃, deflection: 12%, deformation mode: synchronous rolling, pass deformation: 10 percent; repeating the process to finally enable the total deformation of the alloy plate to reach 65%;
(8) isothermal aging treatment, isothermal aging temperature: 360 ℃, time: 0.6h, heating rate: greater than 6.5 deg.c/sec.
Example 6
In the embodiment, the Cu-Ti alloy is used as a processing object, and the specific operation steps and process parameters are as follows:
(1) firstly, smelting a Cu-Ti alloy by using a vacuum intermediate frequency induction furnace;
(2) homogenization heat treatment, temperature: 800 ℃, time: 20 h;
(3) low-temperature hot rolling, wherein the initial rolling temperature is as follows: 750 ℃, heat preservation time: 0.5h, deformation: 55%, deformation mode: unidirectional rolling, pass reduction: 5%, finish rolling temperature: greater than 500 ℃. (ii) a
(4) Multiple-circulation ultralow-temperature deep cooling rolling deformation, deformation temperature: the low-temperature deformation cycle is more than 10 times, the liquid nitrogen tank is placed for more than 30min, and then ultra-low-temperature deformation is carried out, wherein the deformation temperature is as follows: -110 ℃, deflection: 10%, deformation mode: synchronous rolling, wherein the pass deformation is 8%; 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: -110 ℃, deflection: 10%, deformation mode: synchronous rolling, pass deformation: 8 percent; repeating the process to finally enable the total deformation of the alloy plate to reach 50%;
(5) short-time solution quenching treatment, wherein the solution temperature is as follows: 800 ℃, solid solution time: 2h, heating rate: more than 10 ℃/s, quenching mode: water quenching, wherein the cooling rate is more than 100 ℃/s;
(6) low-temperature short-time pre-aging treatment, wherein the pre-aging temperature is 400 ℃, the time is 2.8h, and the heating rate is as follows: greater than 6.5 ℃/sec;
(7) multiple-circulation ultralow-temperature deep cooling rolling deformation, deformation temperature: the low-temperature deformation cycle is more than 6 times, the liquid nitrogen tank is placed for more than 30min, and then ultra-low-temperature deformation is carried out, wherein the deformation temperature is as follows: -110 ℃, deflection: 20%, 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: -110 ℃, deflection: 12%, deformation mode: synchronous rolling, pass deformation: 10 percent; repeating the process to finally enable the total deformation of the alloy plate to reach 65%;
(8) isothermal aging treatment, isothermal aging temperature: 400 ℃, time: 5h, heating rate: greater than 6.5 deg.c/sec.
Example 7
In the embodiment, the Cu-Ti alloy is used as a processing object, and the specific operation steps and process parameters are as follows:
(1) firstly, smelting a Cu-Ti alloy by using a vacuum intermediate frequency induction furnace;
(2) homogenization heat treatment, temperature: 800 ℃, time: 20 h;
(3) low-temperature hot rolling, wherein the initial rolling temperature is as follows: 720 ℃, heat preservation time: 0.5h, deformation: 55%, deformation mode: unidirectional rolling, pass reduction: 5%, finish rolling temperature: greater than 500 ℃. (ii) a
(4) Multiple-circulation ultralow-temperature deep cooling rolling deformation, deformation temperature: the low-temperature deformation cycle is more than 10 times, the liquid nitrogen tank is placed for more than 30min, and then ultra-low-temperature deformation is carried out, wherein the deformation temperature is as follows: -110 ℃, deflection: 10%, deformation mode: synchronous rolling, wherein the pass deformation is 8%; 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: -110 ℃, deflection: 10%, deformation mode: synchronous rolling, pass deformation: 8 percent; repeating the process to finally enable the total deformation of the alloy plate to reach 50%;
(5) short-time solution quenching treatment, wherein the solution temperature is as follows: 800 ℃, solid solution time: 2h, heating rate: more than 10 ℃/s, quenching mode: water quenching, wherein the cooling rate is more than 100 ℃/s;
(6) low-temperature short-time pre-aging treatment, wherein the pre-aging temperature is 400 ℃, the time is 2h, and the heating rate is as follows: greater than 6.5 ℃/sec;
(7) multiple-circulation ultralow-temperature deep cooling rolling deformation, deformation temperature: the low-temperature deformation cycle is more than 6 times, the liquid nitrogen tank is placed for more than 30min, and then ultra-low-temperature deformation is carried out, wherein the deformation temperature is as follows: -110 ℃, deflection: 20%, 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: -110 ℃, deflection: 12%, deformation mode: synchronous rolling, pass deformation: 10 percent; repeating the process to finally enable the total deformation of the alloy plate to reach 65%;
(8) isothermal aging treatment, isothermal aging temperature: 400 ℃, time: 2h, heating rate: greater than 6.5 deg.c/sec.
The Cu-Ti alloy precipitation is characterized by AM decomposition precipitation behavior, and 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 without a nucleation process, a fine microstructure with periodically changed components is formed in the whole grain range after the precipitation decomposition, and an elastic strain field generated by two different components which are kept coherent can strongly prevent dislocation movement, so that a strengthening effect is generated. Therefore, the method firstly carries out multi-process coupling regulation and control before solid solution, wherein the multi-process coupling regulation and control comprises low-temperature hot rolling and multi-cycle ultralow-temperature deep cold rolling deformation, the process coupling regulation and control can ensure that the CuTi remained in the alloy matrix is more uniformly and dispersedly distributed, the size is also obviously reduced, the strain energy storage around a precipitation phase is also obviously increased, and finally compared with the traditional hot working process, the CuTi precipitation can be better melted back into the alloy matrix through short-time solid solution treatment, so that the guarantee is provided for the subsequent maximum potential improvement of the strength of the alloy. Then according to the characteristic of alloy precipitation and precipitation, namely the AM decomposition behavior, the invention also particularly designs and develops a preparation process for the characteristics of coupled regulation AM decomposition and dislocation distribution of the pre-aging and ultralow temperature deformation after solid solution. The preaging regulation and control enables the alloy to generate slight amplitude modulation decomposition, and then the ultralow temperature deep cold rolling deformation is carried out, so that not only can the micro area generating the slight amplitude modulation decomposition be broken, but also the dislocation movement can be effectively blocked due to the amplitude modulation decomposition tissue generated by the preaging regulation and control, and the dislocation distribution formed in the ultralow temperature deep cold rolling deformation process is more uniform and dispersed. In addition, the spinodal decomposition structure crushed by the ultra-low temperature deep cold rolling deformation can be used as a nucleation point for further aging precipitation in the subsequent aging process, so that the precipitation rate and the precipitation quantity of the alloy precipitate can be remarkably increased. Significant improvements in alloy strength and conductivity are necessarily obtained due to the rapid progression of spinodal decomposition. Finally, the alloy necessarily has high strength and high conductivity based on the process regulation. After the process developed in the example 1 is regulated and controlled, the aging precipitation rate of the alloy in the isothermal aging process is obviously accelerated, the corresponding aging hardness peak value is also obviously increased, and a bimodal phenomenon (mainly caused by the pre-aging regulation and control) is generated. According to the performance test results, the alloy has hardness of more than 340HV after short-time aging treatment, tensile strength of 1110.4MPa, elastic modulus of 127GPa and conductivity of 14% IACS, the hardness is slowly reduced and secondary peak occurs after further aging, the peak hardness is close to 340HV, the tensile strength still reaches 1091.3MPa, the conductivity of more than 15% IACS and the elastic modulus is 114.2GPa, and the comprehensive performance is obviously superior to that of the Cu-Ti alloy plate strip prepared by the traditional process (as shown in Table 2, figure 2 and figure 5). The above-mentioned significant improvement of the comprehensive properties is achieved, and the main reason is as mentioned above, the positive influence of the multi-cycle ultra-low temperature deep cold rolling deformation on the alloy structure before solid solution, and the precipitation can be significantly refined compared with the traditional process (as shown in fig. 3 and fig. 6).
In addition, a large number of researches find that the structure and the performance of the Cu-Ti alloy can be effectively improved by adding proper micro-alloying elements, and the invention patent also contrasts and researches the performance change condition of the Cu-Ti and the Cu-Ti-La alloy after being regulated and controlled by a new designed and developed process. It can be seen from comparative example 2 and example 2 that a proper amount of microalloyed La does have a certain influence on alloy hardness and conductivity, but the influence effect is not as significant as that of the multi-process coupling regulation process. After the alloy is subjected to the coupling regulation and control of the multiple processes, the final comprehensive performance of the alloy is also very excellent. The precipitation rate is significantly increased and the conductivity is greatly improved (as shown in fig. 7).
In conclusion, the Cu-3.0 wt% Ti- (La) alloy is subjected to multi-process coupling regulation, the corresponding AM decomposition characteristic of the alloy is obviously changed, the aging precipitation rate is obviously accelerated, and the peak hardness, the strength and the conductivity are obviously improved. The preparation method capable of effectively improving the strength and the conductivity of the Cu-Ti alloy developed by the invention can well meet the urgent requirements of manufacturing typical parts in a plurality of high and new technical fields such as electronic industry, aerospace, instruments and meters, household appliances and the like on high-strength, high-elasticity and high-conductivity copper alloys. Therefore, the preparation method is very suitable for being applied to a plurality of high and new technical fields, particularly the fields with special requirements on novel high-strength, high-elasticity and high-conductivity copper alloy, and is particularly applied and popularized to more sensitive industries for solving the problems existing in the process of applying beryllium bronze, such as harmful influence of smoke, steam and dust of beryllium and compounds of the beryllium on human health, 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 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.
Claims (10)
1. A method for effectively improving the strength and the electric conductivity of an alloy is characterized by comprising the following steps:
(1) preparing an alloy ingot by vacuum melting;
(2) carrying out homogenization heat treatment;
(3) low-temperature hot rolling;
(4) carrying out multi-cycle ultralow temperature deep cooling rolling deformation;
(5) short-time solution quenching treatment;
(6) low-temperature short-time pre-aging treatment;
(7) carrying out multi-cycle ultralow temperature deep cooling rolling deformation;
(8) and (5) isothermal aging treatment.
2. The method of claim 1, wherein the alloy is a Cu-Ti alloy.
3. The method for effectively improving the strength and the conductivity of the alloy as claimed in claim 2, wherein the low-temperature hot rolling in the step (3) has a start rolling temperature of 700-780 ℃, a holding time of 0.1-2h, and a deformation of 45-90%; the deformation temperature of the multi-cycle ultralow-temperature deep cold rolling deformation in the step (4) is-80 ℃ to-190 ℃, and the total deformation amount is 40-70%; the solid solution temperature of the short-time solid solution quenching treatment in the step (5) is 750-; the temperature of the low-temperature short-time pre-aging treatment in the step (6) is 350-; the deformation temperature of the multi-cycle ultralow-temperature deep cooling rolling deformation in the step (7) is-80 ℃ to-190 ℃, and the deformation amount is 60-85%; the temperature of the isothermal aging treatment in the step (8) is 350-430 ℃, and the time is 0.5-10 h.
4. The method for effectively improving the strength and the conductivity of the alloy according to claim 2, wherein the homogenizing heat treatment in the step (2) is carried out by the following steps: the temperature is 750 ℃ and 850 ℃ and the time is 15-30 h.
5. The method for effectively improving the strength and the electric conductivity of the alloy according to claim 2, wherein the step (3) of low-temperature hot rolling comprises the following steps: the low-temperature hot rolling treatment process comprises the following steps: the initial rolling temperature: 710 ℃ and 750 ℃, and the heat preservation time: 0.1-1h, deformation: 45-80%, deformation mode: unidirectional rolling, pass reduction: 3-15%, finishing temperature: greater than 500 ℃.
6. The method for effectively improving the strength and the conductivity of the alloy according to claim 2, wherein the step (4) of multi-cycle ultralow temperature deep cold rolling deformation process comprises the following steps: the low-temperature deformation cycle is more than 10 times, the liquid nitrogen tank is placed for more than 30min, and then ultra-low-temperature deformation is carried out, wherein the deformation temperature is as follows: -100 ℃ to-190 ℃, deflection: 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 2-9min, wherein the deformation temperature is as follows: -100 ℃ to-190 ℃, deflection: 5-15%, modification: synchronous rolling, pass deformation: 2 to 10 percent; and repeating the process to finally enable the total deformation of the alloy plate to reach 40-70%.
7. The method for effectively improving the strength and the electric conductivity of the alloy according to claim 2, wherein the short-time solution quenching treatment process of the step (5) is as follows: solid solution temperature: 780 ℃ and 850 ℃ and solid solution time: 1.5-3h, heating rate: more than 10 ℃/s, quenching mode: water quenching, wherein the cooling rate is more than 100 ℃/s.
8. The method for effectively improving the strength and the electric conductivity of the alloy according to claim 2, wherein the step (6) of low-temperature short-time pre-aging treatment comprises the following steps: the preaging temperature is 360-430 ℃, the time is 0.7-2.8h, the heating rate is as follows: greater than 6.5 deg.c/sec.
9. The method for effectively improving the strength and the conductivity of the alloy according to claim 2, wherein the step (7) of multi-cycle ultralow temperature deep cold rolling deformation process comprises the following steps: the low-temperature deformation cycle is more than 6 times, the liquid nitrogen tank is placed for more than 30min, and then ultra-low-temperature deformation is carried out, wherein the deformation temperature is as follows: -100 ℃ to-190 ℃, deflection: 8-30%, deformation mode: synchronous rolling, wherein the pass deformation is 5-15%; then, putting the ultra-low temperature rolled plate into a liquid nitrogen tank for cooling for 2-9min, wherein the deformation temperature is as follows: -100 ℃ to-190 ℃, deflection: 8-30%, deformation mode: synchronous rolling, pass deformation: 5 to 15 percent; and repeating the process to finally enable the total deformation of the alloy plate to reach 60-85%.
10. The method for effectively improving the strength and the electric conductivity of the alloy according to claim 2, wherein the step (8) of isothermal aging treatment is as follows: isothermal aging temperature: 360 ℃ and 430 ℃, time: 0.6-5h, heating rate: greater than 6.5 deg.c/sec.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101100712A (en) * | 2007-08-01 | 2008-01-09 | 苏州有色金属研究院有限公司 | Fatigue resistant Cu-Ti alloy and producing method thereof |
| CN101144128A (en) * | 2007-10-12 | 2008-03-19 | 苏州有色金属研究院有限公司 | Rare earth titanium-copper alloy and manufacture method thereof |
| KR20100056635A (en) * | 2008-11-20 | 2010-05-28 | 도와 메탈테크 가부시키가이샤 | Cu-ti-based copper alloy sheet material and method of manufacturing same |
| WO2011065188A1 (en) * | 2009-11-25 | 2011-06-03 | Jx日鉱日石金属株式会社 | Titanium-copper for electronic component |
| CN104278171A (en) * | 2014-09-16 | 2015-01-14 | 中南大学 | CuTi-series elastic copper alloy and preparation method thereof |
| CN104630556A (en) * | 2015-02-06 | 2015-05-20 | 中南大学 | Ultrahigh-strength high-toughness high corrosion-resisting CuNiSiNbSn elastic copper alloy and preparation method thereof |
| JP2015175053A (en) * | 2014-03-17 | 2015-10-05 | Ｄｏｗａメタルテック株式会社 | Cu-Ti-BASED COPPER ALLOY SHEET MATERIAL, MANUFACTURING METHOD THEREFOR AND ELECTRIC CONDUCTION COMPONENT |
| CN105039758A (en) * | 2015-06-11 | 2015-11-11 | 大连理工大学 | Precipitation strengthening type high-strength and high-conductivity CuZr alloy and preparing method thereof |
| US20180363101A1 (en) * | 2016-05-16 | 2018-12-20 | Zhejiang University | High-strength and high-conductivity copper alloy and applications of alloy as material of contact line of high-speed railway allowing speed higher than 400 kilometers per hour |
| CN110951990A (en) * | 2019-11-22 | 2020-04-03 | 福州大学 | Cu-Ni-Co-Fe-Si-Zr-Zn copper alloy material and preparation method thereof |
| CN111424224A (en) * | 2020-05-18 | 2020-07-17 | 中南大学 | Preparation method of high-strength high-toughness conductive copper alloy strip |
| CN112322926A (en) * | 2020-11-16 | 2021-02-05 | 福州大学 | Cu-Ti-Si-Co-La copper alloy material and preparation method thereof |
| CN113278844A (en) * | 2021-05-18 | 2021-08-20 | 国工恒昌新材料沧州有限公司 | High-strength high-elasticity copper-titanium alloy and manufacturing method thereof |
-
2021
- 2021-11-24 CN CN202111404375.0A patent/CN114150123B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101100712A (en) * | 2007-08-01 | 2008-01-09 | 苏州有色金属研究院有限公司 | Fatigue resistant Cu-Ti alloy and producing method thereof |
| CN101144128A (en) * | 2007-10-12 | 2008-03-19 | 苏州有色金属研究院有限公司 | Rare earth titanium-copper alloy and manufacture method thereof |
| KR20100056635A (en) * | 2008-11-20 | 2010-05-28 | 도와 메탈테크 가부시키가이샤 | Cu-ti-based copper alloy sheet material and method of manufacturing same |
| WO2011065188A1 (en) * | 2009-11-25 | 2011-06-03 | Jx日鉱日石金属株式会社 | Titanium-copper for electronic component |
| JP2015175053A (en) * | 2014-03-17 | 2015-10-05 | Ｄｏｗａメタルテック株式会社 | Cu-Ti-BASED COPPER ALLOY SHEET MATERIAL, MANUFACTURING METHOD THEREFOR AND ELECTRIC CONDUCTION COMPONENT |
| CN104278171A (en) * | 2014-09-16 | 2015-01-14 | 中南大学 | CuTi-series elastic copper alloy and preparation method thereof |
| CN104630556A (en) * | 2015-02-06 | 2015-05-20 | 中南大学 | Ultrahigh-strength high-toughness high corrosion-resisting CuNiSiNbSn elastic copper alloy and preparation method thereof |
| CN105039758A (en) * | 2015-06-11 | 2015-11-11 | 大连理工大学 | Precipitation strengthening type high-strength and high-conductivity CuZr alloy and preparing method thereof |
| US20180363101A1 (en) * | 2016-05-16 | 2018-12-20 | Zhejiang University | High-strength and high-conductivity copper alloy and applications of alloy as material of contact line of high-speed railway allowing speed higher than 400 kilometers per hour |
| CN110951990A (en) * | 2019-11-22 | 2020-04-03 | 福州大学 | Cu-Ni-Co-Fe-Si-Zr-Zn copper alloy material and preparation method thereof |
| CN111424224A (en) * | 2020-05-18 | 2020-07-17 | 中南大学 | Preparation method of high-strength high-toughness conductive copper alloy strip |
| CN112322926A (en) * | 2020-11-16 | 2021-02-05 | 福州大学 | Cu-Ti-Si-Co-La copper alloy material and preparation method thereof |
| CN113278844A (en) * | 2021-05-18 | 2021-08-20 | 国工恒昌新材料沧州有限公司 | High-strength high-elasticity copper-titanium alloy and manufacturing method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115961227A (en) * | 2022-12-21 | 2023-04-14 | 昆明冶金研究院有限公司北京分公司 | High-strength high-plasticity conductive copper alloy material and preparation method thereof |
| CN115961227B (en) * | 2022-12-21 | 2024-05-03 | 中铝科学技术研究院有限公司 | High-strength high-plastic conductive copper alloy material and preparation method thereof |
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