CN111979445B - Rare earth microalloyed copper alloy and preparation method thereof - Google Patents
Rare earth microalloyed copper alloy and preparation method thereof Download PDFInfo
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- CN111979445B CN111979445B CN202010668026.9A CN202010668026A CN111979445B CN 111979445 B CN111979445 B CN 111979445B CN 202010668026 A CN202010668026 A CN 202010668026A CN 111979445 B CN111979445 B CN 111979445B
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- rare earth
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- copper alloy
- yttrium
- cerium
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 44
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 39
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 59
- 229910052802 copper Inorganic materials 0.000 claims abstract description 58
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 27
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 27
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 27
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 27
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 24
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 24
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 238000003723 Smelting Methods 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 16
- 239000000956 alloy Substances 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims 8
- 230000008018 melting Effects 0.000 claims 8
- 238000005728 strengthening Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 238000001556 precipitation Methods 0.000 abstract description 4
- 239000006104 solid solution Substances 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a rare earth microalloyed copper alloy and a preparation method thereof. The rare earth microalloyed copper alloy comprises the following components in percentage by weight: 0.02-0.6% of lanthanum; 0.01 to 0.3 percent of cerium; 0.02 to 0.3 percent of yttrium; 0.01-0.2% of tellurium; 0.02-0.4% of zirconium; the balance of copper and impurities, wherein the total content of lanthanum, cerium and yttrium is not more than 1%. According to the invention, lanthanum, cerium, yttrium, tellurium and zirconium are added to exert the microalloying effect of the rare earth element, the purification and impurity removal and grain refinement of the rare earth element are utilized, and the precipitation strengthening and solid solution strengthening effects are matched, so that the mechanical property of the copper alloy is obviously improved while the electrical conductivity is ensured, and the technical problem of the copper alloy with both high electrical conductivity and high toughness is effectively solved.
Description
Technical Field
The invention relates to the technical field of alloy materials, in particular to a rare earth microalloyed copper alloy and a preparation method thereof.
Background
Copper and copper alloy have good electric conductivity, heat conduction and corrosion resistance, excellent processing performance and higher strength, so that the copper and copper alloy are widely applied to electric products such as electric wires, cables, copper bars, lapped wires and the like.
The copper for electrical purposes has the defects of high oxygen content, high wire breakage rate and the like, and particularly, the copper has the defects of difficult combination of high conductivity and high toughness, thereby seriously influencing the subsequent processing and use. With the development of industrial technology, various power transmission and transformation equipment matched with the industrial technology put higher requirements on copper alloy.
Disclosure of Invention
The invention aims to provide a rare earth microalloyed copper alloy and a preparation method thereof, which aim to solve the problem that the high conductivity and high toughness of the copper alloy in the prior art are difficult to be compatible.
The above purpose of the invention is realized by the following technical scheme:
according to one aspect of the present invention, there is provided a rare earth microalloyed copper alloy, comprising, in weight percent:
0.02-0.6% of lanthanum;
0.01 to 0.3 percent of cerium;
0.02 to 0.3 percent of yttrium;
0.01-0.2% of tellurium;
0.02-0.4% of zirconium;
the balance of copper and inevitable impurities, wherein the total content of lanthanum, cerium and yttrium is not more than 1%.
Preferably, the rare earth microalloyed copper alloy comprises the following components in percentage by weight:
0.03-0.3% of lanthanum;
0.01 to 0.2 percent of cerium;
0.02-0.05% of yttrium;
0.01-0.02% of tellurium;
0.02-0.03% of zirconium;
the balance of copper and inevitable impurities.
Preferably, the rare earth microalloyed copper alloy contains lanthanum, cerium and yttrium in a total content of not more than 0.5%.
According to another aspect of the present invention, there is provided a method for preparing a rare earth microalloyed copper alloy, comprising the steps of:
step S1, putting the electrolytic copper with the purity not less than 99.9% into a smelting furnace for smelting to obtain molten copper liquid;
step S2, rare earth elements, tellurium and zirconium are added into the molten copper, wherein the rare earth elements comprise lanthanum, cerium and yttrium; in the rare earth microalloyed copper alloy, the total content of the rare earth elements is not more than 1 percent;
step S3, heat preservation;
and step S4, pouring out and molding or leading out and molding the copper liquid after heat preservation.
Preferably, in step S1, the smelting mode includes one of medium frequency furnace smelting, up-drawing smelting and high frequency furnace smelting.
Preferably, in the step S1, the smelting temperature is 1100-1250 ℃.
Preferably, in step S1, the smelting environment is one of vacuum smelting, argon protection smelting and flake graphite covering smelting.
Preferably, in step S2, the rare earth elements lanthanum, cerium and yttrium are added in the form of copper-based binary master alloy, and tellurium is added in the form of pure tellurium or copper-based binary master alloy; the zirconium is added in the form of pure zirconium or in the form of a copper-based binary master alloy.
Preferably, in step S3, the incubation condition: the heat preservation temperature is 1080-1200 ℃, and the heat preservation time is 5-60 min.
The invention has the beneficial effects that: according to the rare earth microalloyed copper alloy, rare earth lanthanum, cerium and yttrium, tellurium and zirconium are added to exert the microalloyed effect of the rare earth elements, the purification, impurity removal and grain refinement of the rare earth elements are utilized, and the precipitation strengthening and solid solution strengthening effects are matched, so that the mechanical property of the copper alloy is obviously improved while the electrical conductivity is ensured, and the rare earth microalloyed copper alloy with high electrical conductivity and high toughness is finally obtained. Wherein, the rare earth lanthanum and cerium are added to play roles in purifying a melt, refining crystal grains and deteriorating impurity phases; rare earth yttrium is added to play a role in refining grains; tellurium elements are added to play a role in strengthening precipitation; the added zirconium element plays a role in solid solution strengthening.
According to the preparation method of the rare earth microalloyed copper alloy, the electrolytic copper is smelted, the rare earth lanthanum, cerium, yttrium, tellurium and zirconium are added, and the rare earth microalloyed copper alloy with high conductivity and high toughness is finally obtained through heat preservation and molding.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the specific embodiments of the present invention:
example 1
A rare earth microalloyed copper alloy comprises the following components in percentage by weight: 0.3% lanthanum, 0.3% cerium, 0.3% yttrium, 0.2% tellurium, 0.3% zirconium, the balance copper and unavoidable impurities.
The method comprises the following specific steps:
(1) putting electrolytic copper with the purity of 99.9% into a medium-frequency smelting furnace, and smelting under the protection of argon at the smelting temperature of 1150 ℃;
(2) after the electrolytic copper is melted, adding a copper-based lanthanum, cerium and yttrium binary intermediate alloy into the solution by using a hopper, and adding pure tellurium and pure zirconium;
(3) keeping the temperature of the copper liquid at 1150 ℃ for 10 min;
(4) and pouring the copper liquid for molding.
Example 2
A rare earth microalloyed copper alloy comprises the following components in percentage by weight: 0.2% lanthanum, 0.2% cerium, 0.05% yttrium, 0.02% tellurium, 0.02% zirconium, the balance copper and unavoidable impurities.
The method comprises the following specific steps:
(1) putting electrolytic copper with the purity of 99.95% into a high-frequency smelting furnace, and smelting at 1150 ℃ in vacuum;
(2) after the electrolytic copper is melted, adding a copper-based lanthanum, cerium, yttrium, tellurium and zirconium binary intermediate alloy into the solution by using a hopper;
(3) keeping the temperature of the copper liquid at 1140 ℃ for 5 min;
(4) and pouring the copper liquid for molding.
Example 3
A rare earth microalloyed copper alloy comprises the following components in percentage by weight: 0.1% lanthanum, 0.02% cerium, 0.03% yttrium, 0.01% tellurium, 0.03% zirconium, the balance copper and unavoidable impurities.
The method comprises the following specific steps:
(1) putting electrolytic copper with the purity of 99.95% into a high-frequency smelting furnace, and smelting at 1150 ℃ in vacuum;
(2) after the electrolytic copper is melted, adding a copper-based lanthanum, cerium, yttrium, tellurium and zirconium binary intermediate alloy into the solution by using a hopper;
(3) keeping the temperature of the copper liquid at 1140 ℃ for 5 min;
(4) and pouring the copper liquid for molding.
Example 4
A rare earth microalloyed copper alloy comprises the following components in percentage by weight: 0.03% of lanthanum, 0.01% of cerium, 0.02% of yttrium, 0.01% of tellurium, 0.02% of zirconium, and the balance of copper and inevitable impurities.
The method comprises the following specific steps:
(1) putting electrolytic copper with the purity of 99.95% into an upper-induction smelting furnace, and smelting under the covering of crystalline flake graphite, wherein the smelting temperature is 1180 ℃;
(2) after the electrolytic copper is melted, adding a copper-based lanthanum, cerium, yttrium, tellurium and zirconium binary intermediate alloy into the solution;
(3) keeping the temperature of the copper liquid at 1160 ℃ for 45 min;
(4) and (4) upward guiding and molding the copper liquid through a crystallizer.
Comparative example 1
The method comprises the following specific steps:
(1) putting electrolytic copper with the purity of 99.95% into an upper-induction smelting furnace, and smelting under the covering of crystalline flake graphite, wherein the smelting temperature is 1180 ℃;
(2) after electrolytic copper is melted, only adding a copper-based lanthanum, cerium and yttrium binary intermediate alloy into the solution, wherein the electrolytic copper comprises the following components in percentage by weight: 0.05% of lanthanum, 0.02% of cerium, 0.05% of yttrium, and the balance of copper and inevitable impurities.
(3) Keeping the temperature of the copper liquid at 1160 ℃ for 45 min;
(4) and (4) upward guiding and molding the copper liquid through a crystallizer.
Comparative example 2
The method comprises the following specific steps:
(1) putting electrolytic copper with the purity of 99.95% into an upper-induction smelting furnace, and smelting under the covering of crystalline flake graphite, wherein the smelting temperature is 1180 ℃;
(2) after the electrolytic copper is melted;
(3) keeping the temperature of the copper liquid at 1160 ℃ for 45 min;
(4) and (4) upward guiding and molding the copper liquid through a crystallizer.
The rare earth microalloyed copper alloy ingots prepared in the four embodiments and the two comparative examples are cut into round rods with the diameter of 10mm, the round rods are subjected to multi-pass drawing with the total deformation of 40 percent, annealing is carried out for 1h at 650 ℃, copper alloy rods in a completely annealed state are obtained, and conductivity measurement and tensile measurement are carried out, wherein the main performance indexes are shown in table 1.
TABLE 1
As can be seen from Table 1, the formula and the preparation method of the copper alloy with the five elements of lanthanum, cerium, yttrium, tellurium and zirconium are adopted, the microalloying effect is fully exerted, the purification and impurity removal and grain refinement of rare earth elements are utilized, and the precipitation strengthening and solid solution strengthening effects of tellurium and zirconium elements are matched, so that the electrical conductivity is ensured, and the related mechanical properties of the copper alloy are improved. The tensile strength and the yield strength of the embodiment of the invention are greatly superior to those of the comparative example 1 and the comparative example 2, and the conductivity is kept to be similar, which shows that the technical problem of the invention that the copper alloy has both high conductivity and high toughness is effectively solved.
The above embodiments of the present invention are described in detail, and the principle and the implementation of the present invention are explained by applying specific embodiments, and the above description of the embodiments is only used to help understanding the method of the present invention and the core idea thereof; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention. Based on the explanation here, those skilled in the art will be able to make equivalent changes or corresponding modifications without departing from the scope of the present invention.
Claims (4)
1. The rare earth microalloyed copper alloy is characterized by comprising the following components in percentage by weight:
0.1-0.3% of lanthanum;
0.2-0.3% of cerium;
0.05 to 0.3 percent of yttrium;
0.01-0.2% of tellurium;
0.02-0.3% of zirconium;
the balance of copper and impurities, wherein the total content of lanthanum, cerium and yttrium is not more than 0.9%;
the preparation method of the rare earth microalloyed copper alloy comprises the following steps:
step S1, putting the electrolytic copper with the purity not less than 99.9% into a smelting furnace for smelting to obtain molten copper liquid; the smelting temperature is 1100-1250 ℃;
step S2, rare earth elements, tellurium and zirconium are added into the molten copper, wherein the rare earth elements comprise lanthanum, cerium and yttrium; in the rare earth microalloyed copper alloy, the total content of the rare earth elements is not more than 0.9 percent;
step S3, preserving heat at 1080-1200 ℃ for 5-60 min;
step S4, pouring out and molding or leading out and molding the copper liquid after heat preservation;
the rare earth microalloyed copper alloy has the conductivity of more than or equal to 99.75 percent, the tensile strength of more than or equal to 231.10MPa, the yield strength of more than or equal to 121.06MPa and the elongation of more than or equal to 38 percent.
2. A rare earth microalloyed copper alloy as set forth in claim 1,
in step S2, rare earth elements lanthanum, cerium and yttrium are added in the form of copper-based binary master alloy, and tellurium is added in the form of pure tellurium or copper-based binary master alloy; the zirconium is added in the form of pure zirconium or in the form of a copper-based binary master alloy.
3. The rare earth microalloyed copper alloy according to claim 1, wherein the melting mode in the step S1 includes one of medium frequency furnace melting, up-drawing method melting and high frequency furnace melting.
4. The rare earth microalloyed copper alloy according to claim 1, wherein, in the step S1, the melting atmosphere is one of vacuum melting, argon-shielded melting, and flake graphite-covered melting.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010668026.9A CN111979445B (en) | 2020-07-13 | 2020-07-13 | Rare earth microalloyed copper alloy and preparation method thereof |
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| CN202010668026.9A CN111979445B (en) | 2020-07-13 | 2020-07-13 | Rare earth microalloyed copper alloy and preparation method thereof |
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| CN111979445B true CN111979445B (en) | 2022-05-03 |
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| CN113737050B (en) * | 2021-08-25 | 2023-01-03 | 湖南稀土金属材料研究院有限责任公司 | Copper alloy and preparation method and application thereof |
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| CN1019882C (en) * | 1989-10-12 | 1993-02-03 | 北京有色金属研究总院 | Copper alloy for composite electric contact substrate |
| JP2004244672A (en) * | 2003-02-13 | 2004-09-02 | Dowa Mining Co Ltd | Copper-based alloy with excellent dezincing resistance |
| JP5873618B2 (en) * | 2009-08-18 | 2016-03-01 | 新日鐵住金株式会社 | Method for producing copper alloy |
| JP6311299B2 (en) * | 2013-12-11 | 2018-04-18 | 三菱マテリアル株式会社 | Copper alloy for electronic / electric equipment, copper alloy plastic working material for electronic / electric equipment, manufacturing method of copper alloy plastic working material for electronic / electric equipment, electronic / electric equipment parts and terminals |
| CN106086511B (en) * | 2016-08-10 | 2018-09-14 | 安徽晋源铜业有限公司 | A kind of high-performance copper conducting wire and preparation method thereof |
| CN111254313B (en) * | 2020-01-21 | 2021-11-16 | 中国兵器科学研究院宁波分院 | Preparation method of multi-element microalloyed copper alloy material |
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