CN116287856B - High-strength high-elasticity quaternary copper-nickel-tin-chromium alloy and preparation method thereof - Google Patents
High-strength high-elasticity quaternary copper-nickel-tin-chromium alloy and preparation method thereof Download PDFInfo
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- 229910000599 Cr alloy Inorganic materials 0.000 title claims abstract description 28
- 239000000788 chromium alloy Substances 0.000 title claims abstract description 28
- JXEBTSYNGUDVJE-UHFFFAOYSA-N [Sn].[Cr].[Ni].[Cu] Chemical group [Sn].[Cr].[Ni].[Cu] JXEBTSYNGUDVJE-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 52
- 239000000956 alloy Substances 0.000 claims abstract description 52
- 239000010949 copper Substances 0.000 claims abstract description 32
- 229910052802 copper Inorganic materials 0.000 claims abstract description 29
- 239000011651 chromium Substances 0.000 claims abstract description 28
- 230000032683 aging Effects 0.000 claims abstract description 18
- 230000006698 induction Effects 0.000 claims abstract description 10
- 238000005096 rolling process Methods 0.000 claims abstract description 10
- 229910019192 Sn—Cr Inorganic materials 0.000 claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 42
- 239000002245 particle Substances 0.000 claims description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 23
- 229910052804 chromium Inorganic materials 0.000 claims description 21
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- 229910052718 tin Inorganic materials 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 17
- 238000010791 quenching Methods 0.000 claims description 17
- 230000000171 quenching effect Effects 0.000 claims description 17
- 238000003723 Smelting Methods 0.000 claims description 14
- 238000005266 casting Methods 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 238000005097 cold rolling Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 230000007547 defect Effects 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 238000000265 homogenisation Methods 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims description 2
- 229910000881 Cu alloy Inorganic materials 0.000 abstract description 9
- DMFGNRRURHSENX-UHFFFAOYSA-N beryllium copper Chemical compound [Be].[Cu] DMFGNRRURHSENX-UHFFFAOYSA-N 0.000 abstract description 8
- 229910017532 Cu-Be Inorganic materials 0.000 abstract 2
- 239000006104 solid solution Substances 0.000 description 13
- 229910018100 Ni-Sn Inorganic materials 0.000 description 9
- 229910018532 Ni—Sn Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 7
- 239000012459 cleaning agent Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 5
- 230000001427 coherent effect Effects 0.000 description 4
- 238000005204 segregation Methods 0.000 description 4
- 229910052790 beryllium Inorganic materials 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910000906 Bronze Inorganic materials 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000003483 aging Methods 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000001330 spinodal decomposition reaction Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- WIBSEVJFWFQGCP-UHFFFAOYSA-N [Ni].[Cr].[Sn] Chemical compound [Ni].[Cr].[Sn] WIBSEVJFWFQGCP-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
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Classifications
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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
-
- 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
-
- 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
- C22C9/02—Alloys based on copper with tin as the next major constituent
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a high-strength high-elasticity quaternary copper-nickel-tin-chromium alloy and a preparation method thereof, and belongs to the technical field of high-performance copper alloy preparation. The copper alloy consists of Cu, ni, sn, cr elements, and the content is as follows: 7-11 wt.% of Ni; 3-9 wt.% of Sn; 0.3 to 1.0wt.% of Cr, and the balance of Cu; the preparation method of the invention comprises the following steps: preparing a Cu-Ni-Sn-Cr alloy ingot by an intermediate frequency induction furnace, and homogenizing, rolling, solid-dissolving and isothermal aging the ingot; compared with Cu-Be beryllium copper alloy, the invention has the advantages that the finished product of the Cu-Ni-Sn-Cr alloy strip has high tensile strength and elastic modulus, the electric conductivity can reach 12-20 percent IASC, the preparation method is simple, the price is low, the invention is environment-friendly, and the invention can replace the current Cu-Be alloy in the application of the elastic components and the like in multiple fields.
Description
Technical Field
The invention relates to a high-strength high-elasticity quaternary copper-nickel-tin-chromium alloy and a preparation method thereof, belonging to the technical field of high-performance copper alloy preparation.
Background
The beryllium copper alloy has higher strength and elastic modulus, is a mainstream high-reliability connector and lead frame material, and is widely applied to the national important fields of aerospace, information transmission, precise instruments and the like. The Cu-2Be-0.5Co-0.3Si and Cu-2Be-0.3Ni beryllium bronze has the advantages of high strength, elasticity, wear resistance, fatigue resistance and the like, and is widely applied to products such as connectors, spring bearing bushes, shaft sleeves, gears and the like. However, the stress relaxation rate of beryllium copper in an environment higher than 150 ℃ is increased sharply, so that the contact pressure of an elastic component in an operating state is easy to change, and the connector is disabled in operation. Moreover, oxides and dust generated in the casting and processing processes of beryllium copper are extremely toxic to human bodies, so that the protection cost in the production of the beryllium copper is increased sharply.
With the need of improving the material performance requirement of high-reliability connectors and green development of human beings in the fields of aerospace and the like, cu-Ni-Sn (C72700, C72900, C19010 and the like) aging strengthening copper alloy has partially replaced the industrial application of beryllium copper alloy. The Cu-Ni-Sn alloy has high strength, high elasticity, excellent corrosion resistance, excellent wear resistance and excellent high-temperature stress relaxation resistance, and has the advantages of simple production process, low cost and no toxicity in the production process. However, since Sn has a low melting point (231.89 ℃) and is extremely segregated during casting, the resulting ingot is subject to a large number of shrinkage cavities, porosity, and precipitates of discontinuous precipitated phases that are not coherent with the matrix during aging. These defects severely degrade the mechanical properties of the Cu-Ni-Sn alloy, creating a significant barrier to "dehberyllium copper".
Disclosure of Invention
The invention aims to provide a high-strength high-elasticity quaternary copper-nickel-tin-chromium alloy, which comprises the following components in percentage by mass: 7 to 11wt.% of Ni, 3 to 9wt.% of Sn, 0.3 to 1.0wt.% of Cr, cu: the balance.
Preferably, the preparation method of the high-strength high-elasticity quaternary copper-nickel-tin-chromium alloy is characterized by comprising the following steps of:
(1) Weighing copper blocks, nickel particles, tin balls and chromium particles according to mass percentage, washing with dilute hydrochloric acid, and removing an oxide layer on the metal surface; ultrasonic cleaning with alcohol and drying.
(2) And (3) placing the copper block, the nickel particles, the tin balls and the chromium particles treated in the step (1) into a vacuum intermediate frequency induction furnace, washing the furnace for three times by using argon, then carrying out vacuum smelting, and casting to obtain the Cu-Ni-Sn-Cr alloy cast ingot.
(3) And (3) placing the alloy ingot obtained in the step (2) in a muffle furnace, homogenizing, and then quenching and cooling with water.
(4) Cleaning the surface of the homogenized compound Jin Xiqu obtained in the step (3) by surface defects; and (3) carrying out multi-pass cold rolling treatment on the homogenized alloy after treatment, wherein the total rolling deformation is 70% -85%.
(5) And (3) carrying out solid solution-aging treatment on the rolled alloy obtained in the step (4), and finally carrying out water quenching and cooling to obtain the copper-nickel-tin-chromium alloy.
Preferably, the vacuum melting conditions in step (2) of the present invention are: the vacuum degree of the cavity is 5 multiplied by 10 -3 Pa～1×10 -3 Pa, smelting current is 30A-40A, and smelting temperature is 1200-1350 ℃; after the metal is completely melted, stabilizing the current for 10-15 min, and casting the high-purity graphite mold preheated in advance to obtain the as-cast alloy with the size of 65X 30X 10mm.
Preferably, the conditions of the homogenization treatment according to the present invention are: the treatment time is 2 hours at 900 ℃.
Preferably, the single deformation amount of the cold rolling treatment in the step (4) is not more than 10%.
The high-strength high-elasticity quaternary copper-nickel-tin-chromium alloy prepared by the method can replace beryllium copper.
Microalloying is an effective way to improve segregation of Cu-Ni-Sn alloy and to produce discontinuous precipitated phases by adding alloying elements with significant differences in solid solubility with temperature change to the copper matrix to form supersaturated solid solutions, which are then aged to precipitate. The precipitated phase occupies nucleation sites of discontinuous precipitation at the grain boundaries and impedes movement of the discontinuous precipitation reaction front interface. The maximum solid solubility of Cr element in copper is 0.67wt.%, and the maximum solid solubility at room temperature is only 0.01wt.%; the addition of Cr element can effectively inhibit discontinuous precipitated phase generation and improve the mechanical property of Cu-Ni-Sn alloy.
The beneficial effects of the invention are as follows:
(1) The invention adopts a microalloying method to add Cr element and a copper matrix to generate supersaturated solid solution, and then aging is carried out to separate Cr simple substance; the precipitated phase occupies the grain boundary, so that the problems of Cu-Ni-Sn alloy segregation and discontinuous precipitation can Be well solved, the application field of Cu-Ni-Sn is expanded, and the preparation method is simple, does not use toxic elements such as Be, pb and the like, and is environment-friendly.
(2) Copper produced by the inventionThe nickel-tin-chromium alloy generates Spinodal decomposition in the early aging stage, forms a coherent structure with the matrix in the Sn-rich area and has DO 22 Gamma' phase of structure- (Cu x Ni 1－x ) 3 An Sn intermetallic compound; with increasing aging time, the gamma' phase changes to be non-coherent with the matrix and has DO 3 Gamma phase of structure- (Cu, ni) 3 An Sn intermetallic compound; the alloy hardens due to the formation and growth of the gamma prime phase and softens due to the formation of discontinuous precipitates of the gamma prime phase.
(3) The invention adopts the mode of cold rolling and then solid solution aging treatment to treat the copper-nickel-tin-chromium alloy, and the cold rolling deformation obviously changes the gamma- (Cu, ni) after aging treatment 3 The precipitation distribution of the discontinuous Sn precipitate and the optimal ageing time generate age hardening, and the synergistic effect of the two produces a linear enhancement effect on the performance of the copper-nickel-tin-chromium alloy.
(4) The copper-nickel-tin-chromium alloy prepared by the method has the characteristics of stable performance, good repeatability, high tensile strength, high elastic modulus and good conductivity.
(5) The high-strength high-elasticity quaternary copper-nickel-tin-chromium alloy has low preparation cost and is easy to produce.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the description of the embodiments will be briefly described below.
FIG. 1 is a microstructure of a high-strength high-elastic quaternary copper-nickel-tin-chromium alloy according to example 3;
FIG. 2 is a TEM microstructure of the high-strength high-elasticity quaternary copper-nickel-tin-chromium alloy of example 3;
FIG. 3 is a graph of room temperature tensile true stress-strain for the high-strength high-elastic quaternary copper nickel tin chromium alloy described in example 3;
FIG. 4 is a graph of fracture morphology of the high-strength high-elastic quaternary copper-nickel-tin-chromium alloy of example 3.
Detailed Description
The following describes the embodiments of the present invention further, but the scope of the present invention is not limited to the above description.
Example 1
(1) According to the mass percent, ni is 11 wt%, sn is 6 wt%, cr is 0.3 wt%, cu: weighing a proper amount of copper blocks, nickel particles, tin balls and chromium particles, washing with dilute hydrochloric acid, and removing an oxide layer on the metal surface; ultrasonic cleaning with alcohol and drying.
(2) And (3) placing the weighed copper blocks, nickel particles, tin balls and chromium particles into a vacuum intermediate frequency induction furnace, washing the furnace for three times by using argon, then carrying out vacuum smelting, and casting to obtain the Cu-Ni-Sn-Cr alloy cast ingot.
(3) And (3) placing the alloy ingot obtained in the step (2) in a muffle furnace, homogenizing at 900 ℃ for 2 hours, and then quenching and cooling with water.
(4) Cleaning the surface of the homogenized compound Jin Xiqu obtained in the step (3) by using WD40 cleaning agent; and (3) carrying out multi-pass cold rolling treatment on the homogenized alloy after treatment, wherein the total rolling deformation is 85%.
(5) Carrying out solid solution-aging treatment on the rolled alloy obtained in the step (4), wherein the solid solution treatment condition is that the temperature is kept at 920 ℃ for 2 hours, and the aging treatment condition is that the temperature is kept at 400 ℃ for 6 hours; and finally, quenching and cooling.
Example 2
(1) According to the mass percent, ni is 11 wt%, sn is 9 wt%, cr is 0.3 wt%, cu: weighing a proper amount of copper blocks, nickel particles, tin balls and chromium particles, washing with dilute hydrochloric acid, and removing an oxide layer on the metal surface; ultrasonic cleaning with alcohol and drying.
(2) And (3) placing the weighed copper blocks, nickel particles, tin balls and chromium particles into a vacuum intermediate frequency induction furnace, washing the furnace for three times by using argon, then carrying out vacuum smelting, and casting to obtain the Cu-Ni-Sn-Cr alloy cast ingot.
(3) And (3) placing the alloy ingot obtained in the step (2) in a muffle furnace, homogenizing at 900 ℃ for 2 hours, and then quenching and cooling with water.
(4) Cleaning the surface of the homogenized compound Jin Xiqu obtained in the step (3) by using WD40 cleaning agent; and (3) carrying out multi-pass cold rolling treatment on the homogenized alloy after treatment, wherein the total rolling deformation is 85%.
(5) Carrying out solid solution-aging treatment on the rolled alloy obtained in the step (4), wherein the solid solution treatment condition is that the temperature is kept at 920 ℃ for 2 hours, and the aging treatment condition is that the temperature is kept at 400 ℃ for 6 hours; and finally, quenching and cooling.
Example 3
(1) 9wt.% of Ni, 6wt.% of Sn, 1.0wt.% of Cr, and Cu: weighing a proper amount of copper blocks, nickel particles, tin balls and chromium particles, washing with dilute hydrochloric acid, and removing an oxide layer on the metal surface; ultrasonic cleaning with alcohol and drying.
(2) And (3) placing the weighed copper blocks, nickel particles, tin balls and chromium particles into a vacuum intermediate frequency induction furnace, washing the furnace for three times by using argon, then carrying out vacuum smelting, and casting to obtain the Cu-Ni-Sn-Cr alloy cast ingot.
(3) And (3) placing the alloy ingot obtained in the step (2) in a muffle furnace, homogenizing at 900 ℃ for 2 hours, and then quenching and cooling with water.
(4) Cleaning the surface of the homogenized compound Jin Xiqu obtained in the step (3) by using WD40 cleaning agent; and (3) carrying out multi-pass cold rolling treatment on the homogenized alloy after treatment, wherein the total rolling deformation is 75%.
(5) Carrying out solid solution-aging treatment on the rolled alloy obtained in the step (4), wherein the solid solution treatment condition is that the temperature is kept at 920 ℃ for 2 hours, and the aging treatment condition is that the temperature is kept at 400 ℃ for 8 hours; and finally, quenching and cooling.
Example 4
(1) According to mass percent, 7wt.% of Ni, 3wt.% of Sn, 0.6wt.% of Cr, and Cu: weighing a proper amount of copper blocks, nickel particles, tin balls and chromium particles, washing with dilute hydrochloric acid, and removing an oxide layer on the metal surface; ultrasonic cleaning with alcohol and drying.
(2) And (3) placing the weighed copper blocks, nickel particles, tin balls and chromium particles into a vacuum intermediate frequency induction furnace, washing the furnace for three times by using argon, then carrying out vacuum smelting, and casting to obtain the Cu-Ni-Sn-Cr alloy cast ingot.
(3) And (3) placing the alloy ingot obtained in the step (2) in a muffle furnace, homogenizing at 900 ℃ for 2 hours, and then quenching and cooling with water.
(4) Cleaning the surface of the homogenized compound Jin Xiqu obtained in the step (3) by using WD40 cleaning agent; and (3) carrying out multi-pass cold rolling treatment on the homogenized alloy after treatment, wherein the total rolling deformation is 80%.
(5) Carrying out solid solution-aging treatment on the rolled alloy obtained in the step (4), wherein the solid solution treatment condition is that the temperature is kept at 920 ℃ for 2 hours, and the aging treatment condition is that the temperature is kept at 400 ℃ for 10 hours; and finally, quenching and cooling.
Comparative example 1
(1) According to the mass percent, ni is 11 wt%, cr is 0.3 wt%, cu: weighing a proper amount of copper blocks, nickel particles, tin balls and chromium particles, washing with dilute hydrochloric acid, and removing an oxide layer on the metal surface; ultrasonic cleaning with alcohol and drying.
(2) And (3) putting the weighed copper blocks, nickel particles and chromium particles into a vacuum intermediate frequency induction furnace, washing the furnace for three times by using argon, then carrying out vacuum smelting, and casting to obtain the Cu-Ni-Cr alloy cast ingot.
(3) And (3) placing the alloy ingot obtained in the step (2) in a muffle furnace, homogenizing at 900 ℃ for 2 hours, and then quenching and cooling with water.
(4) Cleaning the surface of the homogenized compound Jin Xiqu obtained in the step (3) by using WD40 cleaning agent; and (3) carrying out multi-pass cold rolling treatment on the homogenized alloy after treatment, wherein the total rolling deformation is 70%.
(5) Carrying out solid solution-aging treatment on the rolled alloy obtained in the step (4), wherein the solid solution treatment condition is that the temperature is kept at 920 ℃ for 2 hours, and the aging treatment condition is that the temperature is kept at 400 ℃ for 10 hours; and finally, quenching and cooling.
Comparative example 2
(1) According to the mass percentage, the Ni is 11 wt%, the Sn is 6 wt%, and the Cu is as follows: weighing a proper amount of copper blocks, nickel particles, tin balls and chromium particles, washing with dilute hydrochloric acid, and removing an oxide layer on the metal surface; ultrasonic cleaning with alcohol and drying.
(2) And (3) putting the weighed copper blocks, nickel particles and tin balls into a vacuum intermediate frequency induction furnace, washing the furnace for three times by using argon, then carrying out vacuum smelting, and casting to obtain the Cu-Ni-Sn alloy cast ingot.
(3) And (3) placing the alloy ingot obtained in the step (2) in a muffle furnace, homogenizing at 900 ℃ for 2 hours, and then quenching and cooling with water.
(4) Cleaning the surface of the homogenized compound Jin Xiqu obtained in the step (3) by using WD40 cleaning agent; and (3) carrying out multi-pass cold rolling treatment on the homogenized alloy after treatment, wherein the total rolling deformation is 85%.
(5) Carrying out solid solution-aging treatment on the rolled alloy obtained in the step (4), wherein the solid solution treatment condition is that the temperature is kept at 920 ℃ for 2 hours, and the aging treatment condition is that the temperature is kept at 400 ℃ for 6 hours; and finally, quenching and cooling.
Comparative example 3
This example is identical to example 1 except that steps (4) and (5) are not performed, as follows:
(1) According to the mass percent, ni is 11 wt%, sn is 6 wt%, cr is 0.3 wt%, cu: weighing a proper amount of copper blocks, nickel particles, tin balls and chromium particles, washing with dilute hydrochloric acid, and removing an oxide layer on the metal surface; ultrasonic cleaning with alcohol and drying.
(2) And (3) placing the weighed copper blocks, nickel particles, tin balls and chromium particles into a vacuum intermediate frequency induction furnace, washing the furnace for three times by using argon, then carrying out vacuum smelting, and casting to obtain the Cu-Ni-Sn-Cr alloy cast ingot.
(3) Placing the alloy cast ingot obtained in the step (2) in a muffle furnace, homogenizing at 900 ℃ for 2h, and then performing water quenching and cooling to obtain the copper-nickel-tin-chromium alloy
The analysis and detection of the high-strength high-elasticity quaternary copper-nickel-tin-chromium alloy prepared in the above example and the comparative example are carried out, and the related data are shown in table 1:
TABLE 1 alloy compositions and alloy mechanical properties and conductivity test results
As can be seen from the examples, the comparative examples and Table 1, the copper alloy prepared by the method has high strength and high elasticity, the tensile strength can reach 889.7MPa, the elastic modulus can reach 99.1GPa, and meanwhile, the copper alloy has good conductivity. The peak tensile strength and the electric conductivity of the four embodiments are both larger than those of QBE2.0 beryllium copper, wherein the comprehensive performance of the high-strength high-elasticity quaternary copper-nickel-tin-chromium alloy of the embodiment 3 is comprehensively superior to that of QBE2.0 beryllium bronze; the root cause is that a large number of nano-scale precipitated phases are dispersed in the sample, so that the problems of Cu-Ni-Sn alloy segregation and discontinuous precipitation are solved, the nano precipitated phases have the function of preventing dislocation movement, and the tensile strength and the elastic modulus of the alloy can be improved.
It can be seen from example 1 and comparative example 3 that the peak tensile strength of comparative example 3, which is not subjected to the rolling-solid solution-aging treatment, is only 45% of the peak tensile strength of example 1; comparative example 3 the conductivity was severely degraded due to the destruction of the matrix lattice structure by a large number of solid solution atoms; therefore, the rolling-solid solution-aging treatment can effectively separate out solid solution atoms, and the time-effective separation phase of the solid solution atoms greatly improves the peak tensile strength of the alloy on the premise of keeping the integrity of the crystal structure.
FIG. 1 is a microstructure of a high-strength high-elastic quaternary copper-nickel-tin-chromium alloy according to example 3; as can be seen from the figure, the microstructure of example 3 does not observe a clear grain boundary structure, and Spinodal decomposition occurs at the aging stage to form DO coherent with the matrix 22 The structure effectively inhibits the segregation of tin element.
FIG. 2 is a TEM microstructure of the high-strength high-elasticity quaternary copper-nickel-tin-chromium alloy of example 3; the graph shows that the Cr element is distributed in a dispersion state, and is completely precipitated through rolling, solid solution and aging treatment, and intermetallic compounds are not formed with other elements.
FIG. 3 is a graph of room temperature tensile true stress-strain for the high-strength high-elastic quaternary copper nickel tin chromium alloy described in example 3; it can be seen from the figure that example 3 shows high peak tensile strength and high elastic modulus behavior during room temperature stretching, no significant yield stage, and low work hardening rate of the alloy.
Fig. 4 is a fracture morphology diagram of the high-strength and high-elasticity quaternary copper-nickel-tin-chromium alloy in example 3, and it can be seen from the figure that a larger ductile pit exists at the fracture, a small amount of Cr particles occupy the ductile pit, and no cleavage platform exists in the whole fracture.
Claims (3)
1. The preparation method of the high-strength high-elasticity quaternary copper-nickel-tin-chromium alloy is characterized by comprising the following steps of:
(1) Weighing copper blocks, nickel particles, tin balls and chromium particles according to mass percentage, washing with dilute hydrochloric acid, and removing an oxide layer on the metal surface; ultrasonic cleaning with alcohol and drying;
(2) Placing the copper block, nickel particles, tin balls and chromium particles treated in the step (1) into a vacuum intermediate frequency induction furnace, washing the furnace for three times by using argon, then carrying out vacuum smelting, and casting to obtain a Cu-Ni-Sn-Cr alloy cast ingot;
(3) Placing the alloy ingot obtained in the step (2) in a muffle furnace, homogenizing, and then quenching and cooling with water;
(4) Cleaning the surface of the homogenized compound Jin Xiqu obtained in the step (3) by surface defects; carrying out multi-pass cold rolling treatment on the homogenized alloy after treatment, wherein the total rolling deformation is 70% -85%;
(5) Carrying out solid solution-aging treatment on the rolled alloy obtained in the step (4), and finally carrying out water quenching and cooling to obtain the copper-nickel-tin-chromium alloy;
the alloy comprises the following components in percentage by mass: 7.35 to 11. wt percent of Ni, 3. wt to 9. wt percent of Sn, 0.3. wt to 1.0. wt percent of Cr, and Cu: the balance;
the conditions of the homogenization treatment were: the treatment time is 2 hours at 900 ℃; the solution treatment conditions are as follows: and (3) preserving heat at 920 ℃ for 2h, wherein the aging treatment condition is 400 ℃ for 6-10 h.
2. The method for preparing the high-strength high-elasticity quaternary copper-nickel-tin-chromium alloy is characterized by comprising the following steps of: the vacuum smelting conditions in the step (2) are as follows: the vacuum degree of the cavity is 5 multiplied by 10 -3 Pa~1×10 -3 Pa, smelting current is 30-40A, and smelting temperature is 1200-1350 ℃; after the metal is completely melted, stabilizing the current for 10-15 min, and casting the high-purity graphite mold which is preheated in advance to obtain the as-cast alloy with the size of 65 multiplied by 30 multiplied by 10mm.
3. The method for preparing the high-strength high-elasticity quaternary copper-nickel-tin-chromium alloy is characterized by comprising the following steps of: and (3) the single deformation of the cold rolling treatment in the step (4) is not more than 10%.
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