CN113817932A - High-strength heat-resistant stress relaxation-resistant copper alloy material and preparation method thereof - Google Patents
High-strength heat-resistant stress relaxation-resistant copper alloy material and preparation method thereof Download PDFInfo
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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
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
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- 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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- 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
- C21D8/0236—Cold rolling
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- 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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- 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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- 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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- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
Abstract
The invention relates to a high-strength heat-resistant stress relaxation-resistant copper alloy material and a preparation method thereof, and the high-strength heat-resistant stress relaxation-resistant copper alloy material is characterized in that: the alloy comprises the following components in percentage by mass: 1.5-2.2 wt.%, Si: 0.4-0.6 wt.%, Co: 0.2-0.3 wt.%, Hf: 0.4-0.7 wt.%, and the balance of Cu. By adding Hf element, the high temperature stability of the copper alloy is improved while the conductivity is ensured, the requirements of various conductive elastic devices are met, and the conductive elastic heat-resistant device is suitable for conductive elastic heat-resistant devices required by electronic components, automobile industry and ocean transportation industry.
Description
Technical Field
The invention belongs to the technical field of copper alloy materials, and particularly relates to a high-strength heat-resistant stress relaxation-resistant copper alloy material and a preparation method thereof.
Background
The high-strength and high-conductivity copper alloy has high strength and excellent electric conduction and heat conduction performance, is a necessary key base material in national key fields of manned aerospace and lunar exploration engineering, satellite navigation systems, core electronic devices, 5G and the like, and is widely applied to elastic elements in precise plug-in terminals of electronic components, new energy automobile connectors, large-scale integrated circuit lead frames, electrified railway contact network systems, shipborne weaponry and instruments and meters for aerospace.
Most of high-end high-strength high-conductivity copper alloys in China rely on import, and Cu-Ni-Si series alloys with excellent performance are core components of related components in the fields. At present, as the chinese invention patent "a new copper-nickel-silicon alloy material for lead frame and its preparation method", its patent number ZL201610872819.6 discloses a copper-nickel-silicon alloy material for lead frame, which comprises the following components (mass fraction): ni: 0.8 to 1.8, Si: 0.15-0.35, P: 0.01 to 0.05, Mg: 0.10 to 0.15, Fe: 0.05-0.1, Cr: 0.2-0.4, Zn: 0.07-0.15, and at least one or two of V, Mn and Ti, wherein the total content of the elements is 0.02-0.5, and the balance is copper. Compared with a high-end lead frame material C70250, the alloy obtained by the process treatments of smelting, casting, hot rolling, aging treatment, face milling, initial rolling, intermediate rolling, on-line solid solution, finish rolling, aging treatment and the like has the advantages of low alloy cost and excellent electric and thermal conductivity, but the mechanical property is relatively insufficient and is about 600 MPa.
For another example, patent number ZL201610874673.9 discloses a high-strength high-elasticity copper-nickel-silicon alloy material, which comprises the following components in percentage by weight: ni: 0.5 to 3.0, Co: 0.3 to 3.0, Si: 0.25 to 1.5, Mg: 0.01-0.05, B: 0.002-0.005, 0.02-0.05 of mixed rare earth (Sc: Y: La ═ 1:3:5), wherein the mass ratio of nickel to cobalt is 0.5-6.0, the balance is Cu, and the mixed rare earth also at least comprises one or two of Cr, Ti, Ag and Zr, the total content of alloy elements is 0.02-0.5, the alloy material is prepared by smelting, casting, hot rolling, surface milling, rough rolling, intermediate annealing, intermediate rolling, high-temperature rapid solid solution treatment, finish rolling and aging treatment, the mechanical property of the alloy material is excellent, the softening temperature of the Cu-3.0Ni-0.75Si-0.5Co alloy is 430 ℃ from the literature that the Co element affects the softening temperature of the Cu-3.0Ni-0.75Si-0.5Co alloy, the softening temperature of the Cu-Ag-Cr (Re) alloy is not more than 500 ℃, the softening temperature of the Cu-Ag-Cr (Ce) alloy for high conductivity is not more than 500 ℃, the contact line is good, the softening property of the CuCr (395: 1-0.5 wt), zr: 0.02-0.2 wt.%) has a softening resistance of about 550 deg.C, so that the improvement of the softening resistance of the alloy by trace amounts of misch metal (0.02-0.05) and trace amounts of Ti, Ag, Cr and Zr (0.02-0.5) is limited to less than 550 deg.C. For another example, the preparation method disclosed in the chinese invention patent "preparation method of CuNiSiAl series elastic copper alloy" with patent number ZL201010571290.7 includes: the alloy produced by the steps of casting, homogenizing treatment, hot rolling, solution treatment, cold rolling, aging treatment, re-rolling and the like has excellent mechanical properties, but the conductivity is relatively common and is about 26.8-30.8% IACS.
The application of the CuNiSi alloy in elastic elements is very wide, and with the progress of engineering technology, higher requirements are put forward on the comprehensive performance of materials, the performance indexes under the conditions of high temperature and high pressure become more and more important, and the existing high-strength heat-resistant copper alloy needs to be further improved.
Disclosure of Invention
The first technical problem to be solved by the present invention is to provide a high-strength heat-resistant stress relaxation-resistant copper alloy material with high strength, stress relaxation resistance and softening resistance, in view of the current situation of the prior art.
The second technical problem to be solved by the invention is to provide a preparation method of the high-strength heat-resistant stress relaxation-resistant copper alloy material.
The technical scheme adopted by the invention for solving the first technical problem is as follows: a high-strength heat-resistant stress relaxation-resistant copper alloy material is characterized in that: the alloy comprises the following components in percentage by mass: 1.5-2.2 wt.%, Si: 0.4-0.6 wt.%, Co: 0.2-0.3 wt.%, Hf: 0.4-0.7 wt.%, and the balance of Cu.
Preferably, the Hf element is Hf in a Cu-8Hf intermediate alloy.
The technical scheme adopted by the invention for solving the second technical problem is as follows: the preparation method of the high-strength heat-resistant copper alloy material is characterized by comprising the following steps of: the method sequentially comprises the following steps:
(1) semi-continuous casting: placing the prepared high-purity oxygen-free copper, pure Ni, pure Si and pure Co into a medium-frequency induction furnace, then adding sufficient dehydrating parts, adding Cu-8Hf wt.% of intermediate alloy after the metal is completely melted, and carrying out heat preservation for a period of time to cast to obtain an alloy ingot;
(2) hot rolling treatment: placing the alloy ingot obtained in the step (1) in a heat preservation furnace for homogenization treatment, preserving heat for a period of time, and then performing hot rolling treatment to obtain an alloy plate;
(3) solution treatment: placing the alloy plate obtained in the step (2) in a heat preservation furnace for heat preservation for a period of time, and immediately carrying out water cooling treatment;
(4) cold rolling treatment: rolling the alloy plate obtained in the step (3) at room temperature for multiple times, wherein the deformation amount of each time is controlled to be 20-40%, and the total cold deformation amount is 60-80%;
(5) aging treatment: carrying out aging treatment on the alloy plate obtained in the step (4), and then carrying out acid washing treatment on the alloy plate;
(6) cold rolling treatment: and (5) rolling the alloy plate obtained in the step (5) at room temperature for multiple times, wherein the deformation of each time is controlled to be 25-30%, and the total cold deformation is 50-60%.
The form of the dehydrating member is various, and preferably, the dehydrating member in the step (1) is dehydrated charcoal.
Preferably, in the step (2), the homogenization treatment temperature is 950-980 ℃, the treatment time is 6-10 h, and the hot rolling deformation is not less than 95%. The primary NiSi phase, CoSi phase and Hf-rich phase of larger size are sufficiently dissolved.
Preferably, in the step (3), the temperature of the solution treatment is 960-980 ℃, and the heat preservation time is 0.5-1 h. The solid solution effect of solute atoms is ensured, and simultaneously, the coarsening of recrystallized grains is avoided.
Preferably, in the step (5), the temperature of the aging treatment is 420-450 ℃, and the aging time is 1-3 h. The precipitation of the NiSi phase, the CoSi phase and the Hf-rich phase is ensured.
The smelting temperature in the step (1) is 1180-1220 ℃, and the heat preservation time is 4-6 min. Fully melting each micro-alloying element.
The tensile strength of the prepared high-strength heat-resistant copper alloy is 840-1070 Mpa, the conductivity is 39-52% IACS, the stress relaxation is less than or equal to 5% in 100 hours, and the softening temperature is more than or equal to 550 ℃. Thus, the copper alloy has good stress relaxation resistance and softening resistance while having high tensile strength and excellent electrical conductivity.
Compared with the prior art, the invention has the advantages that: hf element in Cu in matrix5Hf exists in the form of less influence on the conductivity of the alloy, and Cu5Hf is a heat-resistant phase, so that the softening resistance temperature of the CuNiSiCo alloy is improved, the high-temperature stability of the copper alloy is improved while the electrical conductivity is ensured by adding Hf element, the softening resistance temperature is improved by about 120 ℃ or more, and the high-temperature stability of the Hf element is superior to that of C70350 (Ni: 1.0-2.0, Si: 0.4-1.5, Co: 0.5 ℃; E)1.0) and C7035 (Ni: 1.0 to 2.0, Si: 0.4-1.5), meets the requirements of various conductive elastic devices, and is applicable to conductive elastic heat-resistant devices required by electronic components, automobile industry and ocean transportation industry.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1:
the copper alloy material of the embodiment comprises the following components in percentage by weight: 1.5 wt.%; si: 0.4 wt.%; co: 0.3 wt.%; hf: 0.4 wt.%; the balance being Cu.
The preparation method of the high-strength heat-resistant stress-relaxation-resistant copper alloy material of the embodiment sequentially comprises the following steps of:
(1) semi-continuous casting: placing prepared high-purity oxygen-free copper (99.99 wt.%), pure Ni (99.99 wt.%), pure Si (99.99 wt.%), pure Co (99.95 wt.%) into a medium-frequency induction furnace, adding sufficient dehydrated charcoal, adding Cu-8Hf wt.% intermediate alloy after the metal is completely melted, and casting at 1200 ℃ for 5 min.
(2) Hot rolling treatment: placing the alloy ingot obtained in the step (1) in a heat preservation furnace for homogenization treatment at 950 ℃ for 8h, and then performing hot rolling treatment with the hot rolling deformation of 95%;
(3) solution treatment: placing the alloy plate obtained in the step (2) in a heat preservation furnace, preserving heat for a period of time, wherein the temperature of solid solution treatment is 960 ℃, the heat preservation time is 0.5h, and then immediately carrying out water cooling treatment;
(4) cold rolling treatment: rolling the alloy plate obtained in the step (3) at room temperature for multiple times, wherein the deformation amount of each time is controlled to be 30%, and the total cold deformation amount is 60%;
(5) aging treatment: carrying out aging treatment on the alloy plate obtained in the step (4), wherein the aging treatment temperature is 420 ℃, the aging time is 2 hours, and then carrying out acid washing treatment on the alloy plate;
(6) cold rolling treatment: and (5) rolling the alloy plate obtained in the step (5) at room temperature for multiple times, wherein the deformation amount of each time is controlled to be 30%, and the total cold deformation amount is 60%.
The alloy plate obtained in the embodiment has the tensile strength of 840MPa, the electric conductivity of 52% IACS, the stress relaxation of 5% at room temperature for 100 hours and the softening resistance temperature of 550 ℃.
The influence of Co on the softening temperature of Cu-3.0Ni-0.75Si alloy is known from the literature: the softening resistance temperature of the C70350 (Ni: 1.0-2.0, Si: 0.4-1.5, Co: 0.5-1.0) alloy is 430 degrees, the softening resistance of the embodiment is superior to that of C70350, and the softening resistance temperature is increased by 120 ℃. Therefore, the copper alloy of the present embodiment has good stress relaxation resistance and softening resistance while achieving high tensile strength and high electrical conductivity.
Example 2:
the copper alloy material of the embodiment comprises the following components in percentage by weight: 1.8 wt.%; si: 0.5 wt.%; co: 0.2 wt.%; hf: 0.4 wt.%; the balance being Cu.
The preparation method of the high-strength heat-resistant copper stress-relaxation-resistant alloy material sequentially comprises the following steps of:
(1) semi-continuous casting: placing prepared high-purity oxygen-free copper (99.99 wt.%), pure Ni (99.99 wt.%), pure Si (99.99 wt.%), pure Co (99.95 wt.%) into a medium-frequency induction furnace, then adding sufficient dehydrated charcoal, adding Cu-8Hf wt.% intermediate alloy after the metal is completely melted, and carrying out heat preservation at 1200 ℃ for 5min for casting;
(2) hot rolling treatment: placing the alloy ingot obtained in the step (1) in a heat preservation furnace for homogenization treatment at 960 ℃ for 8h, and then performing hot rolling treatment with the hot rolling deformation of 95%;
(3) solution treatment: placing the alloy plate obtained in the step (2) in a heat preservation furnace, preserving heat for a period of time, wherein the temperature of solid solution treatment is 960 ℃, the heat preservation time is 0.5h, and then immediately carrying out water cooling treatment;
(4) cold rolling treatment: rolling the alloy plate obtained in the step (3) at room temperature for multiple times, wherein the deformation amount of each time is controlled to be 30%, and the total cold deformation amount is 60%;
(5) aging treatment: carrying out aging treatment on the alloy plate obtained in the step (4), wherein the aging treatment temperature is 420 ℃, the aging time is 2 hours, and then carrying out acid washing treatment on the alloy plate;
(6) cold rolling treatment: and (5) rolling the alloy plate obtained in the step (5) at room temperature for multiple times, wherein the deformation amount of each time is controlled to be 30%, and the total cold deformation amount is 60%.
The alloy plate obtained in the embodiment has the tensile strength of 890MPa, the electric conductivity of 44% IACS, the stress relaxation of 5% at room temperature for 100 hours and the softening resistance temperature of 550 ℃.
The influence of Co on the softening temperature of Cu-3.0Ni-0.75Si alloy is known from the literature: the softening resistance temperature of the C70350 (Ni: 1.0-2.0, Si: 0.4-1.5, Co: 0.5-1.0) alloy is 430 degrees, the softening resistance of the embodiment is superior to that of C70350, and the softening resistance temperature is increased by 120 ℃. Therefore, the copper alloy of the present embodiment has good stress relaxation resistance and softening resistance while achieving high tensile strength and high electrical conductivity.
Example 3:
the copper alloy material of the embodiment comprises the following components in percentage by weight: 2.2 wt.%; si: 0.6 wt.%; co: 0.3 wt.%; hf: 0.4 wt.%; the balance being Cu.
The preparation method of the high-strength heat-resistant stress-relaxation-resistant copper alloy material of the embodiment sequentially comprises the following steps of:
(1) semi-continuous casting: placing prepared high-purity oxygen-free copper (99.99 wt.%), pure Ni (99.99 wt.%), pure Si (99.99 wt.%), pure Co (99.95 wt.%) into a medium-frequency induction furnace, adding sufficient dehydrated charcoal, adding Cu-8Hf wt.% intermediate alloy after the metal is completely melted, and casting at 1200 ℃ for 5 min.
(2) Hot rolling treatment: placing the alloy ingot obtained in the step (1) in a heat preservation furnace for homogenization treatment at 960 ℃ for 8h, and then performing hot rolling treatment with the hot rolling deformation of 95%;
(3) solution treatment: placing the alloy plate obtained in the step (2) in a heat preservation furnace, preserving heat for a period of time, wherein the temperature of solid solution treatment is 960 ℃, the heat preservation time is 0.5h, and then immediately carrying out water cooling treatment;
(4) cold rolling treatment: rolling the alloy plate obtained in the step (3) at room temperature for multiple times, wherein the deformation amount of each time is controlled to be 30%, and the total cold deformation amount is 60%;
(5) aging treatment: carrying out aging treatment on the alloy plate obtained in the step (4), wherein the aging treatment temperature is 420 ℃, the aging time is 2 hours, and then carrying out acid washing treatment on the alloy plate;
(6) cold rolling treatment: and (5) rolling the alloy plate obtained in the step (5) at room temperature for multiple times, wherein the deformation amount of each time is controlled to be 30%, and the total cold deformation amount is 60%.
The alloy plate obtained in the embodiment has the tensile strength of 1030MPa, the conductivity of 42% IACS, the stress relaxation of 4% at room temperature for 100 hours and the softening resistance temperature of 550 ℃.
The influence of Co on the softening temperature of Cu-3.0Ni-0.75Si alloy is known from the literature: the softening resistance temperature of the C70350 (Ni: 1.0-2.0, Si: 0.4-1.5, Co: 0.5-1.0) alloy is 430 degrees, the softening resistance of the embodiment is superior to that of C70350, and the softening resistance temperature is increased by 120 ℃. Therefore, the copper alloy of the present embodiment has good stress relaxation resistance and softening resistance while achieving high tensile strength and high electrical conductivity.
Example 4:
the copper alloy material of the embodiment comprises the following components in percentage by weight: 1.5 wt.%; si: 0.4 wt.%; co: 0.3 wt.%; hf: 0.6 wt.%; the balance being Cu.
The preparation method of the high-strength heat-resistant stress-relaxation-resistant copper alloy material of the embodiment sequentially comprises the following steps of:
(1) semi-continuous casting: placing prepared high-purity oxygen-free copper (99.99 wt.%), pure Ni (99.99 wt.%), pure Si (99.99 wt.%), pure Co (99.95 wt.%) into a medium-frequency induction furnace, adding sufficient dehydrated charcoal, adding Cu-8Hf wt.% intermediate alloy after the metal is completely melted, and casting at 1200 ℃ for 5 min.
(2) Hot rolling treatment: placing the alloy ingot obtained in the step (1) in a heat preservation furnace for homogenization treatment at 960 ℃ for 7h, and then performing hot rolling treatment with the hot rolling deformation of 95%;
(3) solution treatment: placing the alloy plate obtained in the step (2) in a heat preservation furnace, preserving heat for a period of time, wherein the solution treatment temperature is 980 ℃, the heat preservation time is 0.5h, and then immediately carrying out water cooling treatment;
(4) cold rolling treatment: rolling the alloy plate obtained in the step (3) at room temperature for multiple times, wherein the deformation amount of each time is controlled to be 35%, and the total cold deformation amount is 70%;
(5) aging treatment: carrying out aging treatment on the alloy plate obtained in the step (4), wherein the aging treatment temperature is 420 ℃, the aging time is 3 hours, and then carrying out acid washing treatment on the alloy plate;
(6) cold rolling treatment: and (5) rolling the alloy plate obtained in the step (5) at room temperature for multiple times, wherein the deformation amount of each time is controlled to be 30%, and the total cold deformation amount is 60%.
The tensile strength of the alloy plate obtained in the embodiment reaches 865MPa, the conductivity is 50% IACS, the stress relaxation is 5% at room temperature for 100 hours, and the softening resistance temperature is 570 ℃. The influence of Co on the softening temperature of Cu-3.0Ni-0.75Si alloy is known from the literature: the softening resistance temperature of the C70350 (Ni: 1.0-2.0, Si: 0.4-1.5, Co: 0.5-1.0) alloy is 430 degrees, the softening resistance of the embodiment is superior to that of C70350, and the softening resistance temperature is increased by 140 degrees. Therefore, the copper alloy of the present embodiment has good stress relaxation resistance and softening resistance while achieving high tensile strength and high electrical conductivity.
Example 5:
the copper alloy material of the embodiment comprises the following components in percentage by weight: 1.8 wt.%; si: 0.5 wt.%; co: 0.2 wt.%; hf: 0.6 wt.%; the balance being Cu.
The preparation method of the high-strength heat-resistant stress-relaxation-resistant copper alloy material of the embodiment sequentially comprises the following steps of:
(1) semi-continuous casting: placing prepared high-purity oxygen-free copper (99.99 wt.%), pure Ni (99.99 wt.%), pure Si (99.99 wt.%), pure Co (99.95 wt.%) into a medium-frequency induction furnace, adding sufficient dehydrated charcoal, adding Cu-8Hf wt.% intermediate alloy after the metal is completely melted, and casting at 1200 ℃ for 5 min.
(2) Hot rolling treatment: placing the alloy ingot obtained in the step (1) in a heat preservation furnace for homogenization treatment at 980 ℃ for 7h, and then performing hot rolling treatment with the hot rolling deformation of 95%;
(3) solution treatment: placing the alloy plate obtained in the step (2) in a heat preservation furnace, preserving heat for a period of time, wherein the solution treatment temperature is 980 ℃, the heat preservation time is 0.5h, and then immediately carrying out water cooling treatment;
(4) cold rolling treatment: rolling the alloy plate obtained in the step (3) at room temperature for multiple times, wherein the deformation amount of each time is controlled to be 35%, and the total cold deformation amount is 70%;
(5) aging treatment: carrying out aging treatment on the alloy plate obtained in the step (4), wherein the aging treatment temperature is 420 ℃, the aging time is 3 hours, and then carrying out acid washing treatment on the alloy plate;
(6) cold rolling treatment: and (5) rolling the alloy plate obtained in the step (5) at room temperature for multiple times, wherein the deformation amount of each time is controlled to be 30%, and the total cold deformation amount is 60%.
The alloy plate obtained in the embodiment has the tensile strength of 930MPa, the conductivity of 42% IACS, the stress relaxation of 5% at room temperature for 100 hours and the softening resistance temperature of 550 ℃. The influence of Co on the softening temperature of Cu-3.0Ni-0.75Si alloy is known from the literature: the softening resistance temperature of the C70350 (Ni: 1.0-2.0, Si: 0.4-1.5, Co: 0.5-1.0) alloy is 430 degrees, the softening resistance of the embodiment is superior to that of C70350, and the softening resistance temperature is increased by 140 degrees. Therefore, the copper alloy of the present embodiment has good stress relaxation resistance and softening resistance while achieving high tensile strength and high electrical conductivity.
Example 6:
the copper alloy material of the embodiment comprises the following components in percentage by weight: 2.2 wt.%; si: 0.6 wt.%; co: 0.3 wt.%; hf: 0.6 wt.%; the balance being Cu.
The preparation method of the high-strength heat-resistant stress-relaxation-resistant copper alloy material of the embodiment sequentially comprises the following steps of:
(1) semi-continuous casting: placing prepared high-purity oxygen-free copper (99.99 wt.%), pure Ni (99.99 wt.%), pure Si (99.99 wt.%), pure Co (99.95 wt.%) into a medium-frequency induction furnace, adding sufficient dehydrated charcoal, adding Cu-8Hf wt.% intermediate alloy after the metal is completely melted, and casting at 1200 ℃ for 5 min.
(2) Hot rolling treatment: placing the alloy ingot obtained in the step (1) in a heat preservation furnace for homogenization treatment at 960 ℃ for 8h, and then performing hot rolling treatment with the hot rolling deformation of 95%;
(3) solution treatment: placing the alloy plate obtained in the step (2) in a heat preservation furnace, preserving heat for a period of time, wherein the solution treatment temperature is 980 ℃, the heat preservation time is 0.5h, and then immediately carrying out water cooling treatment;
(4) cold rolling treatment: rolling the alloy plate obtained in the step (3) at room temperature for multiple times, wherein the deformation amount of each time is controlled to be 30%, and the total cold deformation amount is 60%;
(5) aging treatment: carrying out aging treatment on the alloy plate obtained in the step (4), wherein the aging treatment temperature is 450 ℃, the aging time is 1h, and then carrying out acid pickling treatment on the alloy plate;
(6) cold rolling treatment: and (5) rolling the alloy plate obtained in the step (5) at room temperature for multiple times, wherein the deformation amount of each time is controlled to be 30%, and the total cold deformation amount is 60%.
The alloy plate obtained in the embodiment has the tensile strength of 1045MPa, the electric conductivity of 40% IACS, the stress relaxation of 4% at room temperature for 100 hours and the softening resistance temperature of 570 ℃. The influence of Co on the softening temperature of Cu-3.0Ni-0.75Si alloy is known from the literature: the softening resistance temperature of the C70350 (Ni: 1.0-2.0, Si: 0.4-1.5, Co: 0.5-1.0) alloy is 430 degrees, the softening resistance of the embodiment is superior to that of C70350, and the softening resistance temperature is increased by 140 degrees. Therefore, the copper alloy of the present embodiment has good stress relaxation resistance and softening resistance while achieving high tensile strength and high electrical conductivity.
Example 7:
the copper alloy material of the embodiment comprises the following components in percentage by weight: 1.5 wt.%; si: 0.4 wt.%; co: 0.3 wt.%; hf: 0.7 wt.%; the balance being Cu.
The preparation method of the high-strength heat-resistant stress-relaxation-resistant copper alloy material of the embodiment sequentially comprises the following steps of:
(1) semi-continuous casting: the prepared high-purity oxygen-free copper (99.99 wt.%), pure Ni (99.99 wt.%), pure Si (99.99 wt.%), pure Co (99.95 wt.%) are put in a medium-frequency induction furnace, then sufficient dehydrated charcoal is added, after the metal is completely melted, a Cu-8Hf wt.% intermediate alloy is added, and the casting is carried out by keeping the temperature at 1200 ℃ for 5 min.
(2) Hot rolling treatment: placing the alloy ingot obtained in the step (1) in a heat preservation furnace for homogenization treatment at 960 ℃ for 7h, and then performing hot rolling treatment with the hot rolling deformation of 95%;
(3) solution treatment: placing the alloy plate obtained in the step (2) in a heat preservation furnace, preserving heat for a period of time, wherein the solution treatment temperature is 980 ℃, the heat preservation time is 0.5h, and then immediately carrying out water cooling treatment;
(4) cold rolling treatment: rolling the alloy plate obtained in the step (3) at room temperature for multiple times, wherein the deformation amount of each time is controlled to be 35%, and the total cold deformation amount is 70%;
(5) aging treatment: carrying out aging treatment on the alloy plate obtained in the step (4), wherein the aging treatment temperature is 420 ℃, the aging time is 3 hours, and then carrying out acid washing treatment on the alloy plate;
(6) cold rolling treatment: and (5) rolling the alloy plate obtained in the step (5) at room temperature for multiple times, wherein the deformation amount of each time is controlled to be 30%, and the total cold deformation amount is 60%.
The tensile strength of the alloy plate obtained in the embodiment reaches 882MPa, the conductivity is 48% IACS, the stress is relaxed by 5% at room temperature for 100 hours, and the softening resistance temperature is 580 ℃. The influence of Co on the softening temperature of Cu-3.0Ni-0.75Si alloy is known from the literature: the softening resistance temperature of the C70350 (Ni: 1.0-2.0, Si: 0.4-1.5, Co: 0.5-1.0) alloy is 430 degrees, the softening resistance of the embodiment is superior to that of C70350, and the softening resistance temperature is improved by 150 degrees. Therefore, the copper alloy of the present embodiment has good stress relaxation resistance and softening resistance while achieving high tensile strength and high electrical conductivity.
Example 8:
the copper alloy material of the embodiment comprises the following components in percentage by weight: 1.8 wt.%; si: 0.5 wt.%; co: 0.2 wt.%; hf: 0.7 wt.%; the balance being Cu.
The preparation method of the high-strength heat-resistant stress-relaxation-resistant copper alloy material of the embodiment sequentially comprises the following steps of:
(1) semi-continuous casting: placing prepared high-purity oxygen-free copper (99.99 wt.%), pure Ni (99.99 wt.%), pure Si (99.99 wt.%), pure Co (99.95 wt.%) into a medium-frequency induction furnace, adding sufficient dehydrated charcoal, adding Cu-8Hf wt.% intermediate alloy after the metal is completely melted, and casting at 1200 ℃ for 5 min.
(2) Hot rolling treatment: placing the alloy ingot obtained in the step (1) in a heat preservation furnace for homogenization treatment at 960 ℃ for 9h, and then performing hot rolling treatment with the hot rolling deformation of 95%;
(3) solution treatment: placing the alloy plate obtained in the step (2) in a heat preservation furnace, preserving heat for a period of time, wherein the solution treatment temperature is 980 ℃, the heat preservation time is 0.5h, and then immediately carrying out water cooling treatment;
(4) cold rolling treatment: rolling the alloy plate obtained in the step (3) at room temperature for multiple times, wherein the deformation amount of each time is controlled to be 35%, and the total cold deformation amount is 70%;
(5) aging treatment: carrying out aging treatment on the alloy plate obtained in the step (4), wherein the aging treatment temperature is 420 ℃, the aging time is 3 hours, and then carrying out acid washing treatment on the alloy plate;
(6) cold rolling treatment: and (5) rolling the alloy plate obtained in the step (5) at room temperature for multiple times, wherein the deformation amount of each time is controlled to be 30%, and the total cold deformation amount is 60%.
The alloy plate obtained in the embodiment has the tensile strength of 930MPa, the conductivity of 41 percent IACS, the stress relaxation of 5 percent at room temperature for 100 hours and the softening resistance temperature of 580 ℃. The influence of Co on the softening temperature of Cu-3.0Ni-0.75Si alloy is known from the literature: the softening resistance temperature of the C70350 (Ni: 1.0-2.0, Si: 0.4-1.5, Co: 0.5-1.0) alloy is 430 degrees, the softening resistance of the embodiment is superior to that of C70350, and the softening resistance temperature is improved by 150 degrees. Therefore, the copper alloy of the present embodiment has good stress relaxation resistance and softening resistance while achieving high tensile strength and high electrical conductivity.
Example 9:
the copper alloy material of the embodiment comprises the following components in percentage by weight: 2.2 wt.%; si: 0.6 wt.%; co: 0.3 wt.%; hf: 0.7 wt.%; the balance being Cu.
The preparation method of the high-strength heat-resistant stress-relaxation-resistant copper alloy material of the embodiment sequentially comprises the following steps of:
(1) semi-continuous casting: placing prepared high-purity oxygen-free copper (99.99 wt.%), pure Ni (99.99 wt.%), pure Si (99.99 wt.%), pure Co (99.95 wt.%) into a medium-frequency induction furnace, adding sufficient dehydrated charcoal, adding Cu-8Hf wt.% intermediate alloy after the molten metal is completely melted, and casting at 1200 ℃ for 5 min.
(2) Hot rolling treatment: placing the alloy ingot obtained in the step (1) in a heat preservation furnace for homogenization treatment at 960 ℃ for 10h, and then performing hot rolling treatment with the hot rolling deformation of 95%;
(3) solution treatment: placing the alloy plate obtained in the step (2) in a heat preservation furnace, preserving heat for a period of time, wherein the temperature of solid solution treatment is 960 ℃, preserving heat for 1h, and then immediately carrying out water cooling treatment;
(4) cold rolling treatment: rolling the alloy plate obtained in the step (3) at room temperature for multiple times, wherein the deformation amount of each time is controlled to be 20%, and the total cold deformation amount is 80%;
(5) aging treatment: carrying out aging treatment on the alloy plate obtained in the step (4), wherein the aging treatment temperature is 440 ℃, the aging time is 2 hours, and then carrying out acid washing treatment on the alloy plate;
(6) cold rolling treatment: and (5) rolling the alloy plate obtained in the step (5) at room temperature for multiple times, wherein the deformation amount of each time is controlled to be 30%, and the total cold deformation amount is 60%.
The alloy plate obtained in the embodiment has the tensile strength of 1070MPa, the electric conductivity of 39% IACS, the stress relaxation of 4% at room temperature for 100 hours and the softening resistance temperature of 580 ℃. The influence of Co on the softening temperature of Cu-3.0Ni-0.75Si alloy is known from the literature: the softening resistance temperature of the C70350 (Ni: 1.0-2.0, Si: 0.4-1.5, Co: 0.5-1.0) alloy is 430 degrees, the softening resistance of the embodiment is superior to that of C70350, and the softening resistance temperature is improved by 150 degrees. Therefore, the copper alloy of the present embodiment has good stress relaxation resistance and softening resistance while achieving high tensile strength and high electrical conductivity.
Example 10:
the copper alloy material of the embodiment comprises the following components in percentage by weight: 1.0 wt.%; si: 1.0 wt.%; co: 0.1 wt.%; hf: 0.9 wt.%; the balance being Cu.
The preparation method of the high-strength heat-resistant stress-relaxation-resistant copper alloy material of the embodiment sequentially comprises the following steps of:
(1) semi-continuous casting: placing prepared high-purity oxygen-free copper (99.99 wt.%), pure Ni (99.99 wt.%), pure Si (99.99 wt.%), pure Co (99.95 wt.%) into a medium-frequency induction furnace, adding sufficient dehydrated charcoal, adding Cu-8Hf wt.% intermediate alloy after molten metal is completely melted, and casting at 1180 ℃ for 4 min.
(2) Hot rolling treatment: placing the alloy ingot obtained in the step (1) in a heat preservation furnace for homogenization treatment at 960 ℃ for 6h, and then performing hot rolling treatment with the hot rolling deformation of 95%;
(3) solution treatment: placing the alloy plate obtained in the step (2) in a heat preservation furnace, preserving heat for a period of time, wherein the solution treatment temperature is 970 ℃, the heat preservation time is 0.8h, and then immediately carrying out water cooling treatment;
(4) cold rolling treatment: rolling the alloy plate obtained in the step (3) at room temperature for multiple times, wherein the deformation amount of each time is controlled to be 40%, and the total cold deformation amount is 80%;
(5) aging treatment: carrying out aging treatment on the alloy plate obtained in the step (4), wherein the aging treatment temperature is 440 ℃, the aging time is 2 hours, and then carrying out acid washing treatment on the alloy plate;
(6) cold rolling treatment: and (5) rolling the alloy plate obtained in the step (5) at room temperature for multiple times, wherein the deformation of each time is controlled to be 25%, and the total cold deformation is 50%.
The alloy plate obtained in the embodiment has the tensile strength of 850MPa, the conductivity of 52% IACS, the stress relaxation of 5% at room temperature for 100 hours and the softening resistance temperature of 580 ℃. The influence of Co on the softening temperature of Cu-3.0Ni-0.75Si alloy is known from the literature: the softening resistance temperature of the C70350 (Ni: 1.0-2.0, Si: 0.4-1.5, Co: 0.5-1.0) alloy is 430 degrees, the softening resistance of the embodiment is superior to that of C70350, and the softening resistance temperature is improved by 150 degrees. Therefore, the copper alloy of the present embodiment has good stress relaxation resistance and softening resistance while achieving high tensile strength and high electrical conductivity.
Example 11:
the copper alloy material of the embodiment comprises the following components in percentage by weight: 2.5 wt.%; si: 0.2 wt.%; co: 0.5 wt.%; hf: 0.8 wt.%; the balance being Cu.
The preparation method of the high-strength heat-resistant stress-relaxation-resistant copper alloy material of the embodiment sequentially comprises the following steps of:
(1) semi-continuous casting: the prepared high-purity oxygen-free copper (99.99 wt.%), pure Ni (99.99 wt.%), pure Si (99.99 wt.%), pure Co (99.95 wt.%) are put in a medium-frequency induction furnace, then sufficient dehydrated charcoal is added, after the molten metal is completely melted, a Cu-8Hf wt.% intermediate alloy is added, and the casting is carried out by keeping the temperature at 1220 ℃ for 6 min.
(2) Hot rolling treatment: placing the alloy ingot obtained in the step (1) in a heat preservation furnace for homogenization treatment at 960 ℃ for 6h, and then performing hot rolling treatment with the hot rolling deformation of 95%;
(3) solution treatment: placing the alloy plate obtained in the step (2) in a heat preservation furnace, preserving heat for a period of time, wherein the solution treatment temperature is 970 ℃, the heat preservation time is 0.6h, and then immediately carrying out water cooling treatment;
(4) cold rolling treatment: rolling the alloy plate obtained in the step (3) at room temperature for multiple times, wherein the deformation amount of each time is controlled to be 40%, and the total cold deformation amount is 80%;
(5) aging treatment: carrying out aging treatment on the alloy plate obtained in the step (4), wherein the aging treatment temperature is 440 ℃, the aging time is 2 hours, and then carrying out acid washing treatment on the alloy plate;
(6) cold rolling treatment: and (5) rolling the alloy plate obtained in the step (5) at room temperature for multiple times, wherein the deformation of each time is controlled to be 27%, and the total cold deformation is 55%.
The alloy plate obtained in the embodiment has the tensile strength of 1030MPa, the electric conductivity of 40% IACS, the stress relaxation of 4% at room temperature for 100 hours and the softening resistance temperature of 580 ℃. The influence of Co on the softening temperature of Cu-3.0Ni-0.75Si alloy is known from the literature: the softening resistance temperature of the C70350 (Ni: 1.0-2.0, Si: 0.4-1.5, Co: 0.5-1.0) alloy is 430 degrees, the softening resistance of the embodiment is superior to that of C70350, and the softening resistance temperature is improved by 150 degrees. Therefore, the copper alloy of the present embodiment has good stress relaxation resistance and softening resistance while achieving high tensile strength and high electrical conductivity.
The above embodiments are further detailed descriptions of the present invention, and it is not intended that the embodiments of the present invention be limited thereto, and that suitable composition adjustments and improvements can be made without departing from the scope of the alloy composition and the thermomechanical treatment process set forth in the present invention, but all should be considered to fall within the scope of the claims as filed with the present invention.
Claims (9)
1. A high-strength heat-resistant stress relaxation-resistant copper alloy material is characterized in that: the alloy comprises the following components in percentage by mass: 1.5-2.2 wt.%, Si: 0.4-0.6 wt.%, Co: 0.2-0.3 wt.%, Hf: 0.4-0.7 wt.%, and the balance of Cu.
2. The high strength, heat resistant, stress relaxation resistant copper alloy material of claim 1, wherein: the tensile strength of the high-strength heat-resistant copper alloy is 840-1070 Mpa, the conductivity is 39-52% IACS, the stress relaxation is less than or equal to 5% in 100 hours, and the softening temperature is more than or equal to 550 ℃.
3. A high strength heat resistant stress relaxation resistant copper alloy material according to claim 1 or 2, characterized in that: the Hf element adopts Hf in a Cu-8Hf intermediate alloy.
4. A method for preparing the high-strength heat-resistant stress relaxation-resistant copper alloy material as recited in claim 3, characterized in that: the method sequentially comprises the following steps:
(1) semi-continuous casting: placing the prepared high-purity oxygen-free copper, pure Ni, pure Si and pure Co into a medium-frequency induction furnace, then adding sufficient dehydrating parts, adding Cu-8Hf wt.% of intermediate alloy after the metal is completely melted, and carrying out heat preservation for a period of time to cast to obtain an alloy ingot;
(2) hot rolling treatment: placing the alloy ingot obtained in the step (1) in a heat preservation furnace for homogenization treatment, preserving heat for a period of time, and then performing hot rolling treatment to obtain an alloy plate;
(3) solution treatment: placing the alloy plate obtained in the step (2) in a heat preservation furnace for heat preservation for a period of time, and immediately carrying out water cooling treatment;
(4) cold rolling treatment: rolling the alloy plate obtained in the step (3) at room temperature for multiple times, wherein the deformation amount of each time is controlled to be 20-40%, and the total cold deformation amount is 60-80%;
(5) aging treatment: carrying out aging treatment on the alloy plate obtained in the step (4), and then carrying out acid washing treatment on the alloy plate;
(6) cold rolling treatment: and (5) rolling the alloy plate obtained in the step (5) at room temperature for multiple times, wherein the deformation of each time is controlled to be 25-30%, and the total cold deformation is 50-60%.
5. The method of claim 4, wherein: the dewatering member in step (1) is dewatered charcoal.
6. The method of claim 4, wherein: in the step (2), the homogenization treatment temperature is 950-980 ℃, the treatment time is 6-10 h, and the hot rolling deformation is not less than 95%.
7. The method of claim 4, wherein: in the step (3), the temperature of the solution treatment is 960-980 ℃, and the heat preservation time is 0.5-1 h.
8. The method of claim 4, wherein: in the step (5), the temperature of the aging treatment is 420-450 ℃, and the aging time is 1-3 h.
9. The method of claim 4, wherein: the smelting temperature in the step (1) is 1180-1220 ℃, and the heat preservation time is 4-6 min.
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