CN112301244A - Method for manufacturing high-strength and high-toughness rare earth nickel-copper alloy - Google Patents
Method for manufacturing high-strength and high-toughness rare earth nickel-copper alloy Download PDFInfo
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- CN112301244A CN112301244A CN202011049202.7A CN202011049202A CN112301244A CN 112301244 A CN112301244 A CN 112301244A CN 202011049202 A CN202011049202 A CN 202011049202A CN 112301244 A CN112301244 A CN 112301244A
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/023—Alloys based on nickel
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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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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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
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- 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
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
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Abstract
The invention discloses a method for manufacturing a high-strength and high-toughness rare earth nickel-copper alloy, which comprises the steps of purifying and smelting alloy raw materials to obtain an electroslag ingot, carrying out strong-pressure quick forging on the electroslag ingot to obtain a forged piece, and carrying out heat treatment on the forged piece, wherein alloy elements Ni and Cu and original ecological waste steel are selected as the alloy raw materials, and are subjected to EF smelting, VIM refining, ESR electroslag remelting and adding mixed rare earth elements La and Ce to obtain the nickel-copper alloy through smelting, wherein the nickel-copper alloy comprises the following components: less than or equal to 0.15 percent of C, less than or equal to 1.20 percent of Mn, less than or equal to 0.50 percent of Si, less than or equal to 0.015 percent of P, less than or equal to 0.010 percent of S, less than or equal to 33.00 percent of Cu, less than or equal to 0.85 percent of Ti, less than or equal to 3.15 percent of Al, less than or equal to 2.0 percent of Fe, less than or equal to 0.01 percent of N, less than or equal to 0.15 percent of La and less than or equal to 0.25 percent of Ce, and the balance. The invention has the advantages that: rare earth elements La and Ce are added into alloy raw materials, so that the rare earth nickel-copper alloy with high strength and high toughness is obtained.
Description
Technical Field
The invention relates to the technical field of metallurgy, in particular to a method for manufacturing a high-strength and high-toughness rare earth nickel-copper alloy.
Background
The Monel K500 (Monel) nickel-copper alloy is a foreign brand, and is a nickel-based corrosion-resistant alloy with wide application and large consumption. The method is mainly used for solving the problems of equipment and parts which are corroded by reducing corrosion media. The method is particularly suitable for reducing corrosion environment containing fluoride. It is successfully used in chemical and petrochemical industry and ocean development, and used for manufacturing various heat exchange equipment, boiler feed water heater, pipelines, containers, towers, tanks, reaction kettles, pumps, valves, shafts, fasteners, elastic parts, fixing devices and the like in chemical processing of petroleum and chemical industry and the like, but the strength is not high and the toughness is not enough. Wherein, the MonelK500 tensile strength is 700-900MPa, and the impact toughness is not checked. The tensile strength of the existing user is more than 950Mpa, and the impact toughness is more than or equal to 40J.
Disclosure of Invention
The invention aims to provide a method for manufacturing a high-strength and high-toughness rare earth nickel-copper alloy according to the defects of the prior art, wherein the high-strength and high-toughness rare earth nickel-copper alloy is obtained by adding rare earth elements La and Ce into alloy raw materials.
The purpose of the invention is realized by the following technical scheme:
a manufacturing method of a high-strength and high-toughness rare earth nickel-copper alloy comprises the steps of purifying and smelting alloy raw materials to obtain an electroslag ingot, carrying out strong pressing and rapid forging on the electroslag ingot to obtain a forged piece, and carrying out heat treatment on the forged piece, and is characterized in that: selecting alloy elements Ni and Cu and original ecological scrap steel as the alloy raw materials, carrying out EF smelting, VIM refining and ESR electroslag remelting, adding rare earth elements La and Ce, and smelting to obtain a nickel-copper alloy, wherein the nickel-copper alloy comprises the following components: less than or equal to 0.15 percent of C, less than or equal to 1.20 percent of Mn, less than or equal to 0.50 percent of Si, less than or equal to 0.015 percent of P, less than or equal to 0.010 percent of S, less than or equal to 33.00 percent of Cu, less than or equal to 0.85 percent of Ti, less than or equal to 3.15 percent of Al, less than or equal to 2.0 percent of Fe, less than or equal to 0.01 percent of N, less than or equal to 0.15 percent of La and less than or equal to 0.25 percent of Ce, and the balance.
Adding a composite deoxidizer in the EF smelting process, wherein the composite deoxidizer comprises the following components: si is more than or equal to 8 percent and less than or equal to 9 percent, Mn is more than or equal to 16 percent and less than or equal to 18 percent, Al is more than or equal to 4.5 percent and less than or equal to 5 percent, Ca is more than or equal to 3.5 percent and less than or equal to 4.5 percent, and the balance is Fe.
Degassing treatment is carried out in the VIM refining process, so that the content of a non-metal element H, O, N in the gas is reduced, and H is less than or equal to 1.6ppm, O is less than or equal to 20ppm, and N is less than or equal to 60 ppm.
And adding the rare earth elements La and Ce into a ladle in advance when the alloy raw material is tapped, uniformly mixing the rare earth elements La and Ce with the alloy raw material, and pouring to obtain the electroslag ingot.
After obtaining and refitting the electroslag ingot, heating the electroslag ingot, wherein the electroslag ingot adopts a step heating method, the first stage heating of the electroslag ingot is from 20 ℃ to 560 ℃, and the heating rate is 80 +/-10 ℃/h; the second stage heating is carried out from 560 ℃ to 850 ℃, and the heating rate is 100 +/-10 ℃/h; the third stage heating is from 850 deg.C to 1150 deg.C at a heating rate of 120 deg.C + -10 deg.C.
The forced forging adopts an FM method, the initial forging temperature is 1150 ℃, the final forging temperature is more than or equal to 900 ℃, and the forging ratio is more than or equal to 3.
The heat treatment adopts the modes of solution treatment and aging treatment, the temperature of the solution treatment is 950 +/-10 ℃, and the temperature of the aging treatment is 595 +/-10 ℃.
The invention has the advantages that: rare earth elements La and Ce are added into alloy raw materials, so that the rare earth nickel-copper alloy with high strength and high toughness is obtained.
Drawings
FIG. 1 is a table showing the mechanical properties of the MonelK500 nickel-copper alloy and the rare earth nickel-copper alloy of the present invention.
Detailed Description
The features of the present invention and other related features are described in further detail below by way of example in conjunction with the following drawings to facilitate understanding by those skilled in the art:
example (b): the method for manufacturing the rare earth nickel-copper alloy in the embodiment specifically comprises the following steps:
1. selecting high-purity clean alloy raw materials, wherein the alloy raw materials comprise: 1 # nickel plate, electrolytic copper, original ecological scrap steel (no rust, no sand, no grease, no impurity and no pollution lump material), and purifying the alloy raw materials, drying and feeding into a furnace;
2. purifying the hearth and the ladle to remove residual elements on the hearth and the ladle wall;
3. performing EF smelting, and adding a composite deoxidizer (the components of the composite deoxidizer are that Si is more than or equal to 8 percent and less than or equal to 9 percent, Mn is more than or equal to 16 percent and less than or equal to 18 percent, Al is more than or equal to 4.5 percent and less than or equal to 5 percent, Ca is more than or equal to 3.5 percent and less than or equal to 4.5 percent, and the balance is Fe) in the EF smelting process, so that the composite deoxidizer, oxides and sulfides in the molten steel are subjected to chemical combination reaction to form steel slag which floats on the molten steel, and the steel slag is removed three times before oxidation period, reduction period and tapping, so that the molten steel is purified, nonmetallic inclusions are reduced, the purity;
4. the tapping temperature is 1533 ℃, molten steel is poured into a steel ladle prepared in advance when tapping, uniformly mixed rare earth (including elements La and Ce) is added into the bottom of the steel ladle in advance, and the bottom of the steel ladle is flushed into the steel ladle by argon (1.5-2 atmospheric pressure), so that nickel and copper are better fused; specifically, in this embodiment, the rare earth is a mixed rare earth with a national standard GB/T4153-2008 and a product brand of 194020C, and the components thereof are: la is more than or equal to 30 percent, Ce is more than or equal to 60 percent, Pr is 4-8 percent, Sn is less than 0.1 percent, and the balance is impurities;
5. pouring the molten steel mixed with the rare earth elements La and Ce into a VIM vacuum induction furnace for refining the VIM vacuum induction furnace, and simultaneously performing vacuum degassing treatment to reduce the content of nonmetal elements H, O, N in the gas so that [ H ] is less than or equal to 1.6ppm, [ O ] is less than or equal to 20ppm, [ N ] is less than or equal to 60 ppm;
6. because the difference of the melting points of copper and nickel is large, the nickel and copper are homogenized by punching for many times, and the nickel and copper alloy is further homogenized by ESR electroslag remelting to be integrated, wherein the melting point of the nickel and copper alloy is 1350 ℃;
7. after the electroslag ingot is refitted, heating in a furnace, wherein a step heating method is adopted as a heating mode, the first stage heating is carried out from 20 ℃ to 560 ℃, and the heating rate is 80 +/-10 ℃/h; the second stage heating is carried out from 560 ℃ to 850 ℃, and the heating rate is 100 +/-10 ℃/h; the third stage heating from 850 deg.C to 1150 deg.C at a heating rate of 120 + -10 deg.C; specifically, the step heating method can keep the temperature of the inner part and the outer surface of the electroslag ingot consistent, and compared with the straight rapid heating, the electroslag ingot is not easy to crack;
8. carrying out strong pressing and quick forging on the electroslag ingot by adopting an FM method, wherein the initial forging temperature is 1150 ℃, the final forging temperature is more than or equal to 900 ℃, the electroslag ingot is fully forged, the forging ratio is more than or equal to 3, and finally obtaining a forged piece;
9. carrying out heat treatment on the forged piece, wherein the heat treatment adopts a solid solution treatment and an aging treatment mode, the solid solution treatment temperature is 950 +/-10 ℃, and the aging treatment temperature is 595 +/-10 ℃;
10. the rare earth nickel copper alloy of the present example was subjected to performance testing.
The rare earth nickel copper alloy of the present embodiment has the following components: less than or equal to 0.15 percent of C, less than or equal to 1.20 percent of Mn, less than or equal to 0.50 percent of Si, less than or equal to 0.015 percent of P, less than or equal to 0.010 percent of S, less than or equal to 33.00 percent of Cu, less than or equal to 0.85 percent of Ti, less than or equal to 3.15 percent of Al, less than or equal to 2.0 percent of Fe, less than or equal to 0.01 percent of N, less than or equal to 0.15 percent of La and less than or equal to 0.25 percent of Ce, and the balance. The MonelK500 nickel-copper alloy comprises the following components: 0.13% of C, 0.8% of Mn, 30.0% of Cu, 2.8% of Al, 0.6% of Ti, 1.0% of Fe and 64% of Ni. In the embodiment, the rare earth elements La and Ce are added into the alloy raw materials, so that the strength and toughness of the rare earth nickel-copper alloy can be effectively enhanced.
The rare earth nickel-copper alloy of the embodiment is mainly used for improving the strength and toughness. As shown in FIG. 1, through tests, the mechanical properties of MonelK500 nickel-copper alloy and rare earth nickel-copper alloy are compared, wherein the tensile strength of MonelK500 nickel-copper alloy is 700-. In the present embodiment, the tensile strength of the rare earth nickel-copper alloy is greater than 950Mpa, the yield strength is greater than or equal to 570Mpa, the elongation is greater than or equal to 18%, the reduction of area is greater than or equal to 30%, and the impact energy is greater than or equal to 40J, and in actual measurement, the tensile strength of the rare earth nickel-copper alloy of the present embodiment can reach 995Mpa, the yield strength can reach 672Mpa, the elongation is 20% -22.5%, the reduction of area is greater than or equal to 40% -42%, and the impact energy can. Therefore, the tensile strength and yield strength of the rare earth nickel-copper alloy of the embodiment are both greater than those of the MonelK500 nickel-copper alloy, i.e. the strength and toughness of the rare earth nickel-copper alloy are greater than those of the MonelK500 nickel-copper alloy.
Although the conception and the embodiments of the present invention have been described in detail with reference to the drawings, those skilled in the art will recognize that various changes and modifications can be made therein without departing from the scope of the appended claims, and therefore, they are not to be considered repeated herein.
Claims (7)
1. A manufacturing method of a high-strength and high-toughness rare earth nickel-copper alloy comprises the steps of purifying and smelting alloy raw materials to obtain an electroslag ingot, carrying out strong pressing and rapid forging on the electroslag ingot to obtain a forged piece, and carrying out heat treatment on the forged piece, and is characterized in that: selecting alloy elements Ni and Cu and original ecological scrap steel as the alloy raw materials, carrying out EF smelting, VIM refining and ESR electroslag remelting, adding rare earth elements La and Ce, and smelting to obtain a nickel-copper alloy, wherein the nickel-copper alloy comprises the following components: less than or equal to 0.15 percent of C, less than or equal to 1.20 percent of Mn, less than or equal to 0.50 percent of Si, less than or equal to 0.015 percent of P, less than or equal to 0.010 percent of S, less than or equal to 33.00 percent of Cu, less than or equal to 0.85 percent of Ti, less than or equal to 3.15 percent of Al, less than or equal to 2.0 percent of Fe, less than or equal to 0.01 percent of N, less than or equal to 0.15 percent of La and less than or equal to 0.25 percent of Ce, and the balance.
2. The method for producing a high-strength high-toughness rare earth nickel-copper alloy as claimed in claim 1, wherein: adding a composite deoxidizer in the EF smelting process, wherein the composite deoxidizer comprises the following components: si is more than or equal to 8 percent and less than or equal to 9 percent, Mn is more than or equal to 16 percent and less than or equal to 18 percent, Al is more than or equal to 4.5 percent and less than or equal to 5 percent, Ca is more than or equal to 3.5 percent and less than or equal to 4.5 percent, and the balance is Fe.
3. The method for producing a high-strength high-toughness rare earth nickel-copper alloy as claimed in claim 1, wherein: degassing treatment is carried out in the VIM refining process, so that the content of a non-metal element H, O, N in the gas is reduced, and H is less than or equal to 1.6ppm, O is less than or equal to 20ppm, and N is less than or equal to 60 ppm.
4. The method for producing a high-strength high-toughness rare earth nickel-copper alloy as claimed in claim 1, wherein: and adding the rare earth elements La and Ce into a ladle in advance when the alloy raw material is tapped, uniformly mixing the rare earth elements La and Ce with the alloy raw material, and pouring to obtain the electroslag ingot.
5. The method for producing a high-strength, high-toughness rare earth nickel-copper alloy as claimed in claim 1 or 4, wherein: after obtaining and refitting the electroslag ingot, heating the electroslag ingot, wherein the electroslag ingot adopts a step heating method, the first stage heating of the electroslag ingot is from 20 ℃ to 560 ℃, and the heating rate is 80 +/-10 ℃/h; the second stage heating is carried out from 560 ℃ to 850 ℃, and the heating rate is 100 +/-10 ℃/h; the third stage heating is from 850 deg.C to 1150 deg.C at a heating rate of 120 deg.C + -10 deg.C.
6. The method for producing a high-strength high-toughness rare earth nickel-copper alloy as claimed in claim 1, wherein: the forced forging adopts an FM method, the initial forging temperature is 1150 ℃, the final forging temperature is more than or equal to 900 ℃, and the forging ratio is more than or equal to 3.
7. The method for producing a high-strength high-toughness rare earth nickel-copper alloy as claimed in claim 1, wherein: the heat treatment adopts the modes of solution treatment and aging treatment, the temperature of the solution treatment is 950 +/-10 ℃, and the temperature of the aging treatment is 595 +/-10 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115418598A (en) * | 2022-09-20 | 2022-12-02 | 国网福建省电力有限公司 | Preparation method of lanthanum-doped high-manganese-silicon-content nickel-copper-based electric arc spraying coating |
| CN115652023A (en) * | 2022-10-09 | 2023-01-31 | 上海加宁新材料科技有限公司 | Method for producing and processing high-temperature alloy by adopting novel triple-linkage method EBT + VIM + VAR |
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| CN109207793A (en) * | 2018-10-19 | 2019-01-15 | 扬州丰铜业有限公司 | A kind of nickel-copper alloy material and its preparation process |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115418598A (en) * | 2022-09-20 | 2022-12-02 | 国网福建省电力有限公司 | Preparation method of lanthanum-doped high-manganese-silicon-content nickel-copper-based electric arc spraying coating |
| CN115652023A (en) * | 2022-10-09 | 2023-01-31 | 上海加宁新材料科技有限公司 | Method for producing and processing high-temperature alloy by adopting novel triple-linkage method EBT + VIM + VAR |
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