CN114892013B - Cobalt-containing nickel-chromium-based superalloy, and preparation method and application thereof - Google Patents
Cobalt-containing nickel-chromium-based superalloy, and preparation method and application thereof Download PDFInfo
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- 239000010941 cobalt Substances 0.000 title claims abstract description 50
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 50
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910000601 superalloy Inorganic materials 0.000 title claims abstract description 37
- 229910018487 Ni—Cr Inorganic materials 0.000 title claims abstract description 30
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000005242 forging Methods 0.000 claims abstract description 51
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 34
- 239000000956 alloy Substances 0.000 claims abstract description 34
- 239000010936 titanium Substances 0.000 claims abstract description 29
- 239000011651 chromium Substances 0.000 claims abstract description 27
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 13
- 238000003723 Smelting Methods 0.000 claims abstract description 10
- 230000006698 induction Effects 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 79
- 238000001816 cooling Methods 0.000 claims description 39
- 230000032683 aging Effects 0.000 claims description 22
- 238000004321 preservation Methods 0.000 claims description 22
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 238000005266 casting Methods 0.000 claims description 12
- 239000006104 solid solution Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- 239000004615 ingredient Substances 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 4
- 238000005070 sampling Methods 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 3
- 238000005275 alloying Methods 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000000265 homogenisation Methods 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 abstract description 27
- 229910052719 titanium Inorganic materials 0.000 abstract description 25
- 229910052796 boron Inorganic materials 0.000 abstract description 24
- 229910052742 iron Inorganic materials 0.000 abstract description 24
- 229910052804 chromium Inorganic materials 0.000 abstract description 22
- 229910052748 manganese Inorganic materials 0.000 abstract description 22
- 229910052710 silicon Inorganic materials 0.000 abstract description 22
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 abstract description 14
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 38
- 239000011572 manganese Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 17
- 229910000831 Steel Inorganic materials 0.000 description 15
- 239000010959 steel Substances 0.000 description 15
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 12
- 244000046052 Phaseolus vulgaris Species 0.000 description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 10
- 238000005498 polishing Methods 0.000 description 8
- 238000003754 machining Methods 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000003466 welding Methods 0.000 description 5
- 238000007664 blowing Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 206010039509 Scab Diseases 0.000 description 3
- SZMZREIADCOWQA-UHFFFAOYSA-N chromium cobalt nickel Chemical compound [Cr].[Co].[Ni] SZMZREIADCOWQA-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005496 tempering Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000032544 Cicatrix Diseases 0.000 description 1
- 238000007550 Rockwell hardness test Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 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
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 230000037387 scars Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
- B21J5/00—Methods for forging, hammering, or pressing; Special equipment or accessories therefor
- B21J5/002—Hybrid process, e.g. forging following casting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/16—Remelting metals
- C22B9/18—Electroslag remelting
-
- 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
- C22C1/023—Alloys based on nickel
-
- 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
- C22F1/10—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
-
- 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)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Forging (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a cobalt-containing nickel-chromium-based superalloy, a preparation method and application thereof, wherein the cobalt-containing nickel-chromium-based superalloy comprises the following elements in percentage by weight: 0.03 to 0.08 percent of C, 0 to 0.65 percent of Si, 0 to 0.35 percent of Mn, 0 to 0.001 percent of S, 0 to 0.001 percent of P, 19.0 to 22.0 percent of Cr, 0 to 4 percent of Fe, 0.6 to 1.0 percent of Al, 2.4 to 2.8 percent of Ti, 0 to 0.01 percent of B, 0.75 to 1.3 percent of Co, and the balance of nickel and unavoidable impurity elements. The invention improves the impact load bearing capacity and plastic deformation resistance of the high-temperature alloy through the processes of vacuum induction smelting, secondary vacuum electroslag smelting and two-pier two-pulling and re-forging, and improves the red hardness of the alloy through adding cobalt and controlling the content of Al and Ti elements, the prepared cobalt-containing nickel-chromium-based high-temperature alloy can be used as a die for forging titanium alloy, the forging life is longer than 1500, the service cycle of the die is greatly prolonged, and meanwhile, the reject ratio of the produced titanium alloy is reduced.
Description
Technical Field
The invention relates to the technical field of alloys, in particular to a cobalt-containing nickel-chromium-based superalloy, a preparation method and application thereof.
Background
The die steel adopted in the forging process of the titanium alloy is 5CrMnMo steel, and the 5CrMnMo steel is the hot forging die steel which is most widely applied, and the hot forging die is required to bear the periodical change of load and the periodical rapid cooling and heating action of high temperature in the use process, so that the die has the defects of cracks, chipping, scab and the like after being used for a period of time. And the 5CrMnMo steel has high carbon content, poor weldability, unsatisfactory surfacing effect and short service cycle. The forging efficiency is seriously affected, and the ingot is often waited in a heating furnace due to the defect of a die in the forging process; and pits appear in the forging piece in the rolling process. The titanium alloy is extremely easy to react with oxygen, hydrogen and the like in the air under the high temperature condition, so that the surface of an ingot is increased in hydrogen and the oxide skin is thickened, the phenomenon can only be slowly cooled to the room temperature, and the titanium alloy is reheated after the die is repaired, thereby greatly influencing the production efficiency and the manufacturing yield of the titanium alloy.
At present, the performance of hot work die steel is improved by fine adjustment of chemical elements of 5CrMnMo steel, and the service life of a die is prolonged. However, the improvement effect is limited because factors such as plastic deformation resistance, red hardness and the like of the mold material are not comprehensively considered.
Disclosure of Invention
The invention aims to solve the technical problem of providing a cobalt-containing nickel-chromium-based superalloy, a preparation method and application thereof, and the cobalt-containing nickel-chromium-based superalloy with high plastic deformation resistance, red hardness and compressive yield strength is prepared through improvement of a process, introduction of cobalt element and control of batching elements, and can be used for forging titanium alloy, and has the advantages of long service life, high forging yield and the like.
In order to solve the technical problems, the invention provides the following technical scheme:
The first aspect of the invention provides a cobalt-containing nickel-chromium-based superalloy comprising the following elements in weight percent: 0.03 to 0.08 percent of C, 0 to 0.65 percent of Si, 0 to 0.35 percent of Mn, 0 to 0.001 percent of S, 0 to 0.001 percent of P, 19.0 to 22.0 percent of Cr, 0 to 4 percent of Fe, 0.6 to 1.0 percent of Al, 2.4 to 2.8 percent of Ti, 0 to 0.01 percent of B, 0.75 to 1.3 percent of Co, and the balance of Ni and unavoidable impurity elements.
Further, in the cobalt-containing nickel-chromium-based superalloy, the content of Co element is 0.9% -1.2%.
The solubility of cobalt in nickel is very large, the atomic radius of nickel is 0.062nm, the atomic radius of cobalt is 0.063 nm, the two elements are very close, the cobalt has good compatibility, the solid solution strengthening effect is enhanced by introducing Co element, thereby improving the property of matrix phase, improving the plasticity of matrix phase, increasing the interface binding force, and improving the alloy strength and plasticity after solid solution aging treatment. The strength of the alloy is increased along with the temperature rise, and meanwhile, the plasticity is higher, so that the phenomenon of severe embrittlement does not occur, and the red hardness of the alloy is effectively improved.
The second aspect of the invention provides a preparation method of the cobalt-containing nickel-chromium-based superalloy according to the first aspect, which comprises the following steps:
s1: the ingredients were dosed according to the following elemental ratios: 0.03 to 0.08 percent of C, 0 to 0.65 percent of Si, 0 to 0.35 percent of Mn, 0 to 0.001 percent of S, 0 to 0.001 percent of P, 19.0 to 22.0 percent of Cr, 0 to 4 percent of Fe, 0.6 to 1.1 percent of Al, 2.4 to 2.85 percent of Ti, 0 to 0.01 percent of B, 0.75 to 1.3 percent of Co and the balance of nickel;
S2: smelting the ingredients by adopting vacuum induction smelting, casting to obtain an electrode ingot after alloying uniformly, and then carrying out secondary electroslag remelting to prepare an electroslag ingot;
S3: homogenizing the electroslag ingot prepared by the method to obtain an alloy ingot;
s4: carrying out two-pier two-drawing re-forging treatment on the high-temperature alloy cast ingot, wherein the deformation of each pass is controlled within the range of 10-20%;
S5: and sequentially carrying out solution heat treatment and aging heat treatment on the cast ingot after forging to obtain the cobalt-containing nickel-chromium-based superalloy.
In the step S1, raw materials of the ingredients comprise electrolytic nickel plates, high-purity chromium blocks, silicon blocks, manganese blocks, iron blocks, aluminum beans, titanium plates, cobalt blocks and boron blocks.
Further, considering the burning loss of Al and Ti sources, the added ingredients are slightly higher than the element content in the formula. The Al and Ti elements are partially burnt in the process, and the elements cannot be improved by subsequent heat treatment after being burnt, so that the control is needed in the process of batching.
Further, the Cr source is a high purity chromium block.
Further, the Fe source is a high-purity iron block, and the surface oxide skin is polished by adopting manual polishing before entering a furnace.
Further, in S2, during vacuum induction smelting, the vacuum degree is less than or equal to 1.0 x 10 -4 MPa, and during feeding, firstly a Fe source and a Ni source are added, and then a Cr source is added for refining; heating to 1480-1500 ℃ after refining sampling and measuring main elements, preserving heat for 15-20 minutes, and adding Si source, mn source and Co source; and (3) after the heat preservation is carried out for 15-20 minutes, adding an Al source, a Ti source and a B source, homogenizing the temperature for 12-15 minutes after the raw materials are completely melted, and heating to the casting temperature of 1520-1550 ℃ for casting.
Further, the main elements are Fe, ni and Cr.
Further, before the vacuum induction smelting starts to feed, magnesia is adopted for furnace charging, and after furnace charging, a pure nickel plate is used for cleaning and protecting.
In S2, secondary electroslag remelting is carried out under argon atmosphere, 4Ti slag system (proper amount of calcium oxide and aluminum beans are added into slag) accounting for 5% -6% of the weight of the electrode ingot is adopted, and the melting speed is 5.9-6.3 Kg/min.
Further, in S3, the homogenizing treatment specifically includes: heating the cast ingot to 1045-1055 ℃, preserving heat for 1-2 hours, continuously heating to 1120-1150 ℃ and preserving heat for 22-24 hours; wherein, the temperature is raised to 1045-1055 ℃ from the furnace temperature, the temperature raising rate is not higher than 10 ℃/min, the temperature is continuously raised to 1120-1150 ℃, and the temperature raising rate is not higher than 5 ℃/min.
Further, in S4, the temperature system of the forging treatment is: charging Wen Zhuding to below 700 ℃ into a furnace, heating to 995-1005 ℃ for 4 hours, homogenizing for 2 hours, heating to 1145-1155 ℃ for 3 hours, and preserving heat for 3-4 hours, wherein the final forging temperature is 950-960 ℃.
Further, the forging ratio is > 3.
Further, in S5, the temperature system of the solution heat treatment is: the solid solution temperature is 1020-1030 ℃, the heat preservation time is 8-9 hours, and the cooling mode is air cooling.
Further, in S5, the temperature system of the aging heat treatment is: the aging temperature is 750-755 ℃, the heat preservation time is 8-9 hours, the furnace cooling is carried out at 50 ℃/h to 620-625 ℃, the heat preservation time is 8-9 hours, and the cooling mode is air cooling.
According to a third aspect of the invention, there is provided a mould machined from the cobalt-containing nickel-chromium-based superalloy of the first aspect.
In a fourth aspect, the invention provides the use of a die according to the third aspect in forging of titanium alloys.
The invention has the beneficial effects that:
1. According to the invention, a proper amount of cobalt element and control of aluminum and titanium element are added into GH4033A, a process of vacuum induction smelting and secondary vacuum electroslag smelting is adopted, and a process of two-pier two-drawing and re-forging is combined, so that the impact load bearing capacity, red hardness and plastic deformation resistance of the alloy are effectively improved.
2. The synthesized cobalt-containing nickel-chromium-based superalloy can be used for preparing a die of a titanium alloy forging, the die of the superalloy does not find the phenomena of scab and chipping in the use process, and does not generate plastic deformation under the periodical load effect, so that the accuracy of the dimension of the forging can be ensured, the yield of the forging is improved, and the production cost of the titanium alloy forging is effectively reduced; meanwhile, the service life of the high-temperature alloy die prepared by the method is longer than 1500 cast ingots, and the service life of the high-temperature alloy die is far longer than that of the existing die based on 5CrMnMo steel.
Detailed Description
The present invention will be further described with reference to specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the present invention and practice it.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Example 1
The embodiment relates to preparation of a cobalt-containing nickel-chromium-based superalloy mold, which comprises the following elements ：C：0.051％、Si：0.152％、Mn：0.1％、Cr：21.04％、 S：≤0.001％、P：≤0.001％、Fe：2.258％、Al：0.772％、Ti：2.724％、B：0.006％、 Co：0.95％、 in percentage by weight and the balance of Ni; the preparation method comprises the following steps:
(1) Weighing raw materials such as electrolytic nickel plates, high-purity chromium blocks, silicon blocks, manganese blocks, iron blocks, aluminum beans, titanium plates, cobalt blocks and boron blocks according to the proportion of C：0.051％、Si：0.152％、Mn：0.1％、Cr：21.04％、S：≤0.001％、 P：≤0.001％、Fe：2.258％、Al：0.772％、Ti：2.724％、B：0.006％、Co：0.95％、 and the balance of Ni;
(2) Under the condition that the vacuum degree is less than or equal to 1.0 x 10 -4 MPa, using magnesia to blow a furnace, using a pure nickel plate to wash the furnace after finishing the furnace blowing, adding iron blocks and nickel plates, adding high-purity chromium blocks to refine, measuring main elements after the materials are completely melted, heating to 1480-1500 ℃, preserving heat for 15-20 minutes, adding silicon blocks, manganese blocks and cobalt blocks, preserving heat for 15-20 minutes, adding aluminum beans, titanium plates and boron blocks, preserving heat for 12-15 minutes after the materials are completely melted, heating to a casting temperature of 1520-1550 ℃ to cast, rolling and polishing the obtained electrode ingot, welding a false electrode, and carrying out secondary electroslag remelting to obtain an electroslag ingot;
(3) Heating the electroslag ingot to 1050+/-5 ℃ and preserving heat for 1-2 hours, continuously heating to 1120-1150 ℃ and preserving heat for 22-24 hours to obtain a high-temperature alloy ingot;
(4) Forging a high-temperature alloy cast ingot, drawing two piers, cogging to 340 x 520mm plate blanks, and controlling the deformation of each pass within a range of 10-20%; the forging temperature system is as follows: charging Wen Zhuding into a furnace at the temperature below 700 ℃ for 4 hours, heating to 995-1005 ℃, homogenizing for 2 hours, heating to 1145-1155 ℃ for 3 hours, and preserving heat for 3-4 hours, wherein the final forging temperature is 950-960 ℃;
(5) Sequentially carrying out solution heat treatment and aging heat treatment on the cast ingot treated in the step (4); the temperature system of the solution heat treatment is as follows: the solid solution temperature is 1020-1030 ℃, the heat preservation time is 8-9 hours, and the cooling mode is air cooling; the temperature system of the aging heat treatment is as follows: the aging temperature is 750-755 ℃, the heat preservation time is 8-9 hours, the furnace cooling is carried out at 50 ℃/h to 620-625 ℃, the heat preservation time is 8-9 hours, and the cooling mode is air cooling.
(6) And machining the prepared cobalt-containing nickel-chromium-based superalloy according to a drawing to prepare a die, and electropolishing the use surface of the die to obtain the superalloy die.
Example 2
The embodiment relates to preparation of a cobalt-containing nickel-chromium-based superalloy mold, which comprises the following elements ：C：0.051％、Si：0.152％、Mn：0.1％、Cr：21.04％、 S：≤0.001％、P：≤0.001％、Fe：2.258％、Al：0.772％、Ti：2.724％、B：0.006％、 Co：1.2％、 in percentage by weight and the balance of Ni; the preparation method comprises the following steps:
(1) Weighing raw materials such as electrolytic nickel plates, high-purity chromium blocks, silicon blocks, manganese blocks, iron blocks, aluminum beans, titanium plates, cobalt blocks and boron blocks according to the proportion of C：0.051％、Si：0.152％、Mn：0.1％、Cr：21.04％、S：≤0.001％、 P：≤0.001％、Fe：2.258％、Al：0.772％、Ti：2.724％、B：0.006％、Co：1.2％、 and the balance of Ni;
(2) Under the condition that the vacuum degree is less than or equal to 1.0 x 10 -4 MPa, using magnesia to blow a furnace, using a pure nickel plate to wash the furnace after finishing the furnace blowing, adding iron blocks and nickel plates, adding high-purity chromium blocks to refine, measuring main elements after the materials are completely melted, heating to 1480-1500 ℃, preserving heat for 15-20 minutes, adding silicon blocks, manganese blocks and cobalt blocks, preserving heat for 15-20 minutes, adding aluminum beans, titanium plates and boron blocks, preserving heat for 12-15 minutes after the materials are completely melted, heating to a casting temperature of 1520-1550 ℃ to cast, rolling and polishing the obtained electrode ingot, welding a false electrode, and carrying out secondary electroslag remelting to obtain an electroslag ingot;
(3) Heating the electroslag ingot to 1050+/-5 ℃ and preserving heat for 1-2 hours, continuously heating to 1120-1150 ℃ and preserving heat for 22-24 hours to obtain a high-temperature alloy ingot;
(4) Forging a high-temperature alloy cast ingot, drawing two piers, cogging to 340 x 520mm plate blanks, and controlling the deformation of each pass within a range of 10-20%; the forging temperature system is as follows: charging Wen Zhuding into a furnace at the temperature below 700 ℃ for 4 hours, heating to 995-1005 ℃, homogenizing for 2 hours, heating to 1145-1155 ℃ for 3 hours, and preserving heat for 3-4 hours, wherein the final forging temperature is 950-960 ℃;
(5) Sequentially carrying out solution heat treatment and aging heat treatment on the cast ingot treated in the step (4); the temperature system of the solution heat treatment is as follows: the solid solution temperature is 1020-1030 ℃, the heat preservation time is 8-9 hours, and the cooling mode is air cooling; the temperature system of the aging heat treatment is as follows: the aging temperature is 750-755 ℃, the heat preservation time is 8-9 hours, the furnace cooling is carried out at 50 ℃/h to 620-625 ℃, the heat preservation time is 8-9 hours, and the cooling mode is air cooling.
(6) And machining the prepared cobalt-containing nickel-chromium-based superalloy according to a drawing to prepare a die, and electropolishing the use surface of the die to obtain the superalloy die.
Comparative example 1
The comparative example used a commercially available 5CrMnMo steel in the form of a 310 x 510mm square billet as hot forging die steel, the 5CrMnMo steel comprising the following elements in weight percent: c:0.52%, si:0.39%, mn:1.40%, cr:0.75%, mo:0.21%, S:0.011%, P:0.012% and the balance of Fe. The 5CrMnMo steel was treated according to the following process:
(1) The quenching process comprises the following steps: heating to 580-620 ℃ along with a furnace, preserving heat for 30 minutes, continuously heating to 830-850 ℃, preserving heat for 1-2 hours, and cooling with oil;
(2) Tempering: secondary tempering, heating to 490+/-5 ℃ along with a furnace, preserving heat for 2.5-3 hours, air cooling, then heating to 510+/-5 ℃ along with the furnace, preserving heat for 2.5-3 hours, and air cooling;
(3) And machining the treated 5CrMnMo steel according to a drawing to prepare a die.
Comparative example 2
The comparative example uses GH4033 superalloy to prepare a mold, the superalloy mold comprising the following elements in weight percent: c:0.051%, si:0.152%, mn:0.1%, cr:21.04%, S less than or equal to 0.001%, P less than or equal to 0.001%, fe:2.258%, al:0.772%, ti:2.724%, B:0.006% Ni in balance; the preparation method comprises the following steps:
(1) According to C:0.051%, si:0.152%, mn:0.1%, cr:21.04%, S less than or equal to 0.001%, P less than or equal to 0.001%, fe:2.258%, al:0.772%, ti:2.724%, B: weighing raw materials such as electrolytic nickel plates, silicon blocks, manganese blocks, iron blocks, aluminum beans, titanium plates and boron blocks according to the proportion of 0.006% and the balance of Ni;
(2) Under the condition that the vacuum degree is less than or equal to 1.0 x 10 -4 MPa, using magnesia to blow a furnace, using a pure nickel plate to wash the furnace after finishing the furnace, then adding iron blocks and nickel plates, measuring main elements after all materials are melted, heating to 1480-1500 ℃, preserving heat for 15-20 minutes, adding silicon blocks and manganese blocks, preserving heat for 15-20 minutes, adding aluminum beans, titanium plates and boron blocks, after all materials are melted, homogenizing temperature for 12-15 minutes, heating to the casting temperature of 1520-1550 ℃ for casting, rolling and polishing the whole body of the obtained electrode ingot, welding a false electrode, and carrying out secondary electroslag remelting to obtain an electroslag ingot;
(3) Heating the electroslag ingot to 1050+/-5 ℃ and preserving heat for 1-2 hours, continuously heating to 1120-1150 ℃ and preserving heat for 22-24 hours to obtain a high-temperature alloy ingot;
(4) Forging a high-temperature alloy cast ingot, drawing two piers, cogging to 340 x 520mm plate blanks, and controlling the deformation of each pass within a range of 10-20%; the forging temperature system is as follows: charging Wen Zhuding into a furnace at the temperature below 700 ℃ for 4 hours, heating to 995-1005 ℃, homogenizing for 2 hours, heating to 1145-1155 ℃ for 3 hours, and preserving heat for 3-4 hours, wherein the final forging temperature is 950-960 ℃;
(5) Sequentially carrying out solution heat treatment and aging heat treatment on the cast ingot treated in the step (4); the temperature system of the solution heat treatment is as follows: the solid solution temperature is 1020-1030 ℃, the heat preservation time is 8-9 hours, and the cooling mode is air cooling; the temperature system of the aging heat treatment is as follows: the aging temperature is 750-755 ℃, the heat preservation time is 8-9 hours, the furnace cooling is carried out at 50 ℃/h to 620-625 ℃, the heat preservation time is 8-9 hours, and the cooling mode is air cooling.
(6) And machining the prepared GH4033 high-temperature alloy according to a drawing to prepare a die, and electropolishing the use surface of the die to obtain the alloy die.
Comparative example 3
The comparative example relates to the preparation of a cobalt-containing nickel-chromium-based superalloy mold comprising the following elements ：C：0.051％、Si：0.152％、Mn：0.1％、Cr：21.04％、 S：≤0.001％、P：≤0.001％、Fe：2.258％、Al：0.772％、Ti：2.724％、B：0.006％、 Co：0.42％、 in weight percent, the balance being Ni; the preparation method comprises the following steps:
(1) Weighing raw materials such as electrolytic nickel plates, high-purity chromium blocks, silicon blocks, manganese blocks, iron blocks, aluminum beans, titanium plates, cobalt blocks and boron blocks according to the proportion of C：0.051％、Si：0.152％、Mn：0.1％、Cr：21.04％、S：≤0.001％、P：≤0.001％、Fe：2.258％、Al：0.772％、Ti：2.724％、B：0.006％、Co：0.42％、 and the balance of Ni;
(2) Under the condition that the vacuum degree is less than or equal to 1.0 x 10 -4 MPa, using magnesia to blow a furnace, using a pure nickel plate to wash the furnace after finishing the furnace blowing, adding iron blocks and nickel plates, adding high-purity chromium blocks to refine, measuring main elements after the materials are completely melted, heating to 1480-1500 ℃, preserving heat for 15-20 minutes, adding silicon blocks, manganese blocks and cobalt blocks, preserving heat for 15-20 minutes, adding aluminum beans, titanium plates and boron blocks, preserving heat for 12-15 minutes after the materials are completely melted, heating to a casting temperature of 1520-1550 ℃ to cast, rolling and polishing the obtained electrode ingot, welding a false electrode, and carrying out secondary electroslag remelting to obtain an electroslag ingot;
(3) Heating the electroslag ingot to 1050+/-5 ℃ and preserving heat for 1-2 hours, continuously heating to 1120-1150 ℃ and preserving heat for 22-24 hours to obtain a high-temperature alloy ingot;
(4) Forging a high-temperature alloy cast ingot, drawing two piers, cogging to 340 x 520mm plate blanks, and controlling the deformation of each pass within a range of 10-20%; the forging temperature system is as follows: charging Wen Zhuding into a furnace at the temperature below 700 ℃ for 4 hours, heating to 995-1005 ℃, homogenizing for 2 hours, heating to 1145-1155 ℃ for 3 hours, and preserving heat for 3-4 hours, wherein the final forging temperature is 950-960 ℃;
(5) Sequentially carrying out solution heat treatment and aging heat treatment on the cast ingot treated in the step (4); the temperature system of the solution heat treatment is as follows: the solid solution temperature is 1020-1030 ℃, the heat preservation time is 8-9 hours, and the cooling mode is air cooling; the temperature system of the aging heat treatment is as follows: the aging temperature is 750-755 ℃, the heat preservation time is 8-9 hours, the furnace cooling is carried out at 50 ℃/h to 620-625 ℃, the heat preservation time is 8-9 hours, and the cooling mode is air cooling.
(6) And machining the prepared cobalt-nickel-chromium-containing base superalloy according to a drawing to prepare a die, and electropolishing the use surface of the die to obtain the alloy die.
Comparative example 4
The comparative example relates to the preparation of a cobalt-containing nickel-chromium-based superalloy mold comprising the following elements ：C：0.051％、Si：0.152％、Mn：0.1％、Cr：21.04％、 S：≤0.001％、P：≤0.001％、Fe：2.258％、Al：0.772％、Ti：2.724％、B：0.006％、Co：1.32％、 in weight percent, the balance being Ni; the preparation method comprises the following steps:
(1) Weighing raw materials such as electrolytic nickel plates, high-purity chromium blocks, silicon blocks, manganese blocks, iron blocks, aluminum beans, titanium plates, cobalt blocks and boron blocks according to the proportion of C：0.051％、Si：0.152％、Mn：0.1％、Cr：21.04％、S：≤0.001％、 P：≤0.001％、Fe：2.258％、Al：0.772％、Ti：2.724％、B：0.006％、Co：1.32％、 and the balance of Ni;
(2) Under the condition that the vacuum degree is less than or equal to 1.0 x 10 -4 MPa, using magnesia to blow a furnace, using a pure nickel plate to wash the furnace after finishing the furnace blowing, adding iron blocks and nickel plates, adding high-purity chromium blocks to refine, measuring main elements after the materials are completely melted, heating to 1480-1500 ℃, preserving heat for 15-20 minutes, adding silicon blocks, manganese blocks and cobalt blocks, preserving heat for 15-20 minutes, adding aluminum beans, titanium plates and boron blocks, preserving heat for 12-15 minutes after the materials are completely melted, heating to a casting temperature of 1520-1550 ℃ to cast, rolling and polishing the obtained electrode ingot, welding a false electrode, and carrying out secondary electroslag remelting to obtain an electroslag ingot;
(3) Heating the electroslag ingot to 1050+/-5 ℃ and preserving heat for 1-2 hours, continuously heating to 1120-1150 ℃ and preserving heat for 22-24 hours to obtain a high-temperature alloy ingot;
(4) Forging a high-temperature alloy cast ingot, drawing two piers, cogging to 340 x 520mm plate blanks, and controlling the deformation of each pass within a range of 10-20%; the forging temperature system is as follows: charging Wen Zhuding into a furnace at the temperature below 700 ℃ for 4 hours, heating to 995-1005 ℃, homogenizing for 2 hours, heating to 1145-1155 ℃ for 3 hours, and preserving heat for 3-4 hours, wherein the final forging temperature is 950-960 ℃;
(5) Sequentially carrying out solution heat treatment and aging heat treatment on the cast ingot treated in the step (4); the temperature system of the solution heat treatment is as follows: the solid solution temperature is 1020-1030 ℃, the heat preservation time is 8-9 hours, and the cooling mode is air cooling; the temperature system of the aging heat treatment is as follows: the aging temperature is 750-755 ℃, the heat preservation time is 8-9 hours, the furnace cooling is carried out at 50 ℃/h to 620-625 ℃, the heat preservation time is 8-9 hours, and the cooling mode is air cooling.
(6) And machining the prepared cobalt-nickel-chromium-containing base superalloy according to a drawing to prepare a die, and electropolishing the use surface of the die to obtain the alloy die.
Performance comparison
The alloy molds prepared in the above examples and comparative examples were subjected to performance tests, and the test criteria are as follows:
rockwell hardness test standard: GB/T230.1-2004;
mechanical property experiment sampling position and sample preparation standard: GB/T2975-2018;
room temperature tensile test standard: GB/T228.1-2010;
High temperature tensile test standard: GB/T4338-2006.
The test results are shown in table 1 below:
TABLE 1 results of related Performance tests for different alloys
| Sample of | Alloy hardness/HRC | Tensile strength/MPa | High temperature tensile strength/MPa at 700 DEG C | Service life of the product |
| Example 1 | 35-37 | 790 | 830 | More than 1500 counts |
| Example 2 | 34-36 | 800 | 840 | More than 1500 counts |
| Comparative example 1 | 42-44 | 1500 | - | 6-100 Pieces |
| Comparative example 2 | 29-32 | 680 | 690 | 120-200 Pieces |
| Comparative example 3 | 29-33 | 690 | 740 | 120-200 Pieces |
| Comparative example 4 | 34-36 | 780 | 815 | More than 1500 counts |
The 5CrMnMo steel die prepared in the comparative example 1 is used for forging titanium alloy, and the surface of the 5CrMnMo steel is easy to oxidize at high temperature, so that grinding is needed after forging 6 cast ingots, and when the number of cast ingots reaches about 100, surfacing grinding is needed; and adopting the GH4033 high-temperature alloy die prepared in the comparative examples 2 and 3 and the GH4033 high-temperature alloy die with low cobalt content as titanium alloy forging dies, when 120 titanium alloy ingots are forged, forming fine cracks on the surfaces of the dies, polishing to remove the fine cracks on the surfaces, continuously using, and when the number of the forged ingots reaches about 200, forming scars, pits and other defects on the surfaces of the dies, and performing surfacing and polishing operations.
The cobalt-nickel-chromium-based superalloy dies prepared in examples 1 and 2 and comparative example 4 are used for forging titanium alloy, defects such as chipping, cracking and scab are not observed after 1500 cast ingots are forged, UT flaw detection is carried out in the dies, internal defects are not found, and the condition that the dimension is out of tolerance is not found when the apparent dimension of the titanium alloy is measured, so that the accuracy of the dimension of the forging is ensured, the yield of the forging is improved, and meanwhile, the production cost of the titanium alloy forging is reduced. Further, the results of the performance test of the cobalt-containing nickel-chromium-based superalloy molds of different cobalt contents prepared in examples 1, 2 and comparative example 4 revealed that the strength and elongation increased with the increase of the cobalt content. When the cobalt content is 1.2%, the highest value is reached, and after the cobalt content exceeds 1.2%, the alloy performance is not obviously improved and has a descending trend.
The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.
Claims (9)
1. A cobalt-containing nickel-chromium-based superalloy, comprising, in weight percent: 0.03% -0.08% of C, 0% -0.65% of Si, 0% -0.35% of Mn, 0% -0.001% of S, 0% -0.001% of P, 19.0% -22.0% of Cr, 0% -4% of Fe, 0.6% -1.0% of Al, 2.4% -2.8% of Ti, 0% -0.01% of B, 0.9% -1.2% of Co and the balance of Ni and unavoidable impurity elements.
2. A method for preparing the cobalt-containing nickel-chromium-based superalloy according to claim 1, comprising the steps of:
S1: the ingredients were dosed according to the following elemental ratios: 0.03% -0.08% of C, 0% -0.65% of Si, 0% -0.35% of Mn, 0% -0.001% of S, 0% -0.001% of P, 19.0% -22.0% of Cr, 0% -4% of Fe, 0.6% -1.1% of Al, 2.4% -2.85% of Ti, 0% -0.01% of B, 0.75% -1.3% of Co and the balance of nickel;
S2: smelting the ingredients by adopting vacuum induction smelting, casting to obtain an electrode ingot after alloying uniformly, and then carrying out secondary electroslag remelting to prepare an electroslag ingot;
S3: homogenizing the electroslag ingot prepared by the method to obtain an alloy ingot;
S4: carrying out two-pier two-drawing re-forging treatment on the alloy cast ingot, wherein the deformation of each pass is controlled within the range of 10-20%;
S5: and sequentially carrying out solution heat treatment and aging heat treatment on the cast ingot after forging to obtain the cobalt-containing nickel-chromium-based superalloy.
3. The method for preparing the cobalt-containing nickel-chromium-based superalloy according to claim 2, wherein in S2, during vacuum induction melting, the vacuum degree is less than or equal to 1.0 x 10 -4 MPa, and during charging, firstly a Fe source and a Ni source are added, and then a Cr source is added for refining; heating to 1480-1500 ℃ after refining sampling and measuring main elements, and adding Si source, mn source and Co source after preserving heat for 15-20 minutes; after preserving heat for 15-20 minutes, adding an Al source, a Ti source and a B source, homogenizing the temperature for 12-15 minutes after all raw materials are cleared, and heating to a casting temperature of 1520-1550 ℃ for casting; the secondary electroslag remelting is carried out in an argon atmosphere, 4Ti slag system accounting for 5% -6% of the weight of the electrode ingot is adopted, and the melting speed is 5.9-6.3 Kg/min.
4. The method for preparing the cobalt-containing nickel-chromium-based superalloy according to claim 3, wherein before the vacuum induction melting starts to feed, magnesia is used for furnace charging, and a pure nickel plate is used for cleaning after the furnace charging is completed.
5. The method for preparing a cobalt-containing nickel-chromium-based superalloy according to claim 2, wherein in S3, the homogenization treatment is specifically: heating the cast ingot to 1045-1055 ℃, preserving heat for 1-2 hours, continuously heating to 1120-1150 ℃, and preserving heat for 22-24 hours; and the temperature is raised to 1045-1055 ℃ from the furnace temperature, the heating rate is not higher than 10 ℃/min, the temperature is continuously raised to 1120-1150 ℃, and the heating rate is not higher than 5 ℃/min.
6. The method for preparing a cobalt-containing nickel-chromium-based superalloy according to claim 2, wherein in S4, the forging process is performed at a temperature of: charging Wen Zhuding at the temperature below 700 ℃ into a furnace, heating to 995-1005 ℃ for 4 hours, homogenizing for 2 hours, heating to 1145-1155 ℃ for 3 hours, and preserving heat for 3-4 hours, wherein the final forging temperature is 950-960 ℃; the forging ratio is more than 3.
7. The method for preparing a cobalt-containing nickel-chromium-based superalloy according to claim 2, wherein in S5, the solution heat treatment temperature system is: the solid solution temperature is 1020-1030 ℃, the heat preservation time is 8-9 hours, and the cooling mode is air cooling; the temperature system of the aging heat treatment is as follows: the aging temperature is 750-755 ℃, the heat preservation time is 8-9 hours, the furnace cooling is carried out at 50 ℃/h to 620-625 ℃, the heat preservation time is 8-9 hours, and the cooling mode is air cooling.
8. A die, wherein the die is machined from the cobalt-containing nickel-chromium-based superalloy of claim 1.
9. Use of a die according to claim 8 in forging of titanium alloys.
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