CN117248146A - Strontium-containing nickel-based alloy and preparation method thereof - Google Patents
Strontium-containing nickel-based alloy and preparation method thereof Download PDFInfo
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- CN117248146A CN117248146A CN202311030545.2A CN202311030545A CN117248146A CN 117248146 A CN117248146 A CN 117248146A CN 202311030545 A CN202311030545 A CN 202311030545A CN 117248146 A CN117248146 A CN 117248146A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 95
- 239000000956 alloy Substances 0.000 title claims abstract description 95
- 229910052712 strontium Inorganic materials 0.000 title claims abstract description 77
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000010936 titanium Substances 0.000 claims abstract description 21
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 21
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 20
- 239000011651 chromium Substances 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000006698 induction Effects 0.000 claims abstract description 16
- 239000010955 niobium Substances 0.000 claims abstract description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 15
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 15
- 239000010941 cobalt Substances 0.000 claims abstract description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 15
- 239000011733 molybdenum Substances 0.000 claims abstract description 15
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 15
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 14
- 238000005266 casting Methods 0.000 claims abstract description 12
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 12
- 239000011572 manganese Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000003723 Smelting Methods 0.000 claims abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- 239000011777 magnesium Substances 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 5
- 238000010079 rubber tapping Methods 0.000 claims abstract description 5
- 238000011282 treatment Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 4
- 238000005303 weighing Methods 0.000 claims abstract description 4
- 238000005242 forging Methods 0.000 claims description 24
- 239000002893 slag Substances 0.000 claims description 19
- 238000002844 melting Methods 0.000 claims description 18
- 230000008018 melting Effects 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000010891 electric arc Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 238000010275 isothermal forging Methods 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims 1
- 238000005336 cracking Methods 0.000 abstract description 15
- 230000005496 eutectics Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229910000861 Mg alloy Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- ATTFYOXEMHAYAX-UHFFFAOYSA-N magnesium nickel Chemical compound [Mg].[Ni] ATTFYOXEMHAYAX-UHFFFAOYSA-N 0.000 description 3
- 238000005204 segregation Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PFZCZKYOFNEBAM-UHFFFAOYSA-N [Fe].[Sr] Chemical compound [Fe].[Sr] PFZCZKYOFNEBAM-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009851 ferrous metallurgy Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000010583 slow cooling Methods 0.000 description 2
- 229910000601 superalloy Inorganic materials 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 229910003668 SrAl Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001068 laves phase Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- 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
- 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
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
-
- 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)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a strontium-containing nickel-based alloy and a preparation method thereof, comprising the following components in percentage by mass: carbon: 0.01 to 0.06 percent; chromium: 14% -15%; cobalt: 26% -27%; niobium: 1.5 to 2.0 percent; molybdenum: 3% -4%; aluminum: 2.3 to 2.8 percent; titanium: 4.9 to 5.5 percent; manganese: 4.0 to 4.5 percent; strontium: 0.03 to 0.06 percent; magnesium: 2.0 to 3.5 percent; the balance being nickel and unavoidable impurity elements. The production process comprises the following steps: step 1) weighing metallurgical raw materials capable of obtaining carbon, chromium, cobalt, niobium, molybdenum, aluminum, titanium, manganese, strontium and magnesium according to an element proportioning principle of the strontium-containing alloy; step 2), adding the smelting raw materials in the step 1) into a vacuum induction furnace for treatment, and tapping and casting to form an alloy ingot; step 3) taking the alloy ingot in the step 2) as a base material to obtain a nickel-based alloy electroslag ingot through an electroslag remelting process; and 4) carrying out vacuum consumable operation post-treatment on the basis of the step 3) to obtain the strontium-containing nickel-based alloy product. The invention improves the hot workability of the nickel-based alloy and prevents the occurrence of cracking.
Description
Technical Field
The invention relates to the technical field of ferrous metallurgy, in particular to a strontium-containing nickel-based alloy and a preparation method thereof.
Background
The nickel-base alloy in ferrous metallurgy is widely used for hot end components of aeroengines and gas turbines due to the characteristic of higher strength under high-temperature corrosion conditions, and along with the continuous increase of engine thrust, higher working condition temperature is required, and the use temperature of the nickel-base alloy is generally 650 ℃, so that precipitated phases in the nickel-base alloy are coarsened due to the fact that the temperature is too high, and further performance is poor. The components of the precipitated phases can be stabilized by improving the content of aluminum and titanium in the nickel-based alloy, and the service temperature of the nickel-based alloy is improved, but the existence of the coarse eutectic precipitated phases in the solidification process (r+r') can cause cracks to occur between the eutectic phases and the matrix in the forging process of the nickel-based alloy when the content of aluminum and titanium is improved, so that the nickel-based alloy is scrapped. In addition, the large size of nickel-based alloys is also responsible for poor high temperature plasticity and forging cracking. There is thus an urgent need for improvements in the components produced by existing nickel-based alloys for this situation.
Disclosure of Invention
First, the technical problems to be solved
Aiming at the defects in the prior art, the invention provides the strontium-containing nickel-based alloy and the preparation method thereof, wherein proper amount of strontium element is added into the nickel-based alloy, so that the hot workability of the nickel-based alloy is improved, the high quality effect is achieved through process control, and the occurrence of cracking phenomenon is prevented.
(II) technical problem to be solved
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the strontium-containing nickel-based alloy comprises the following components in percentage by mass:
carbon: 0.01 to 0.06 percent;
chromium: 14% -15%;
cobalt: 26% -27%;
niobium: 1.5 to 2.0 percent;
molybdenum: 3% -4%;
aluminum: 2.3 to 2.8 percent;
titanium: 4.9 to 5.5 percent;
manganese: 4.0 to 4.5 percent;
strontium: 0.03 to 0.06 percent;
magnesium: 2.0 to 3.5 percent;
the balance being nickel and unavoidable impurity elements.
In addition, the invention also provides a preparation method of the strontium-containing nickel-base alloy, and the production process comprises the following steps:
step 1) weighing metallurgical raw materials capable of obtaining carbon, chromium (metal chromium), cobalt, niobium, molybdenum, aluminum, titanium, manganese, strontium and magnesium according to an element proportioning principle of the strontium-containing alloy;
step 2), adding the smelting raw materials in the step 1) into a vacuum induction furnace, and tapping and casting to form an alloy ingot after full melting and refining treatment in a vacuum condition through the vacuum induction furnace;
step 3) taking the alloy ingot in the step 2) as a base material, and obtaining a nickel-based alloy electroslag ingot through an electroslag remelting process;
step 4) forging, rolling and heat treatment are carried out after the vacuum consumable operation is carried out on the basis of the step 3) to obtain the strontium-containing nickel-based alloy product.
Preferably, the oxygen in the vacuum induction furnace in step 2) is less than 20ppm under vacuum conditions.
Preferably, the alloy ingot smelted in the step 2) comprises the following components: carbon: 0.01 to 0.06 percent of chromium: 14% -15%, cobalt: 26% -27%, niobium: 1.5 to 2.0 percent of molybdenum: 3% -4%; aluminum: 2.3 to 2.8 percent of titanium: 4.9 to 5.5 percent of manganese: 4.0 to 4.5 percent, strontium: 0.03 to 0.06 percent.
Preferably, in the step 3), the smelting slag system CaF in the electroslag remelting is carried out 2 -CaO-MgO-Al 2 O 3 -TiO 2 The SrO and the alloy ingot are matched for electroslag remelting to obtain a nickel-based alloy electroslag ingot, wherein the base slag system in the electroslag remelting comprises the following components in percentage by weight:
preferably, for nickel-based alloys containing 0.41% strontium and 3.52% aluminum, the composition of the slag is determined based on the composition characteristics of the consumable electrode: caF (CaF) 2 :Al 2 O 3 :CaO:MgO：T iO 2 :SrO＝53:17:13:3:3:10。
Preferably, the nickel-based alloy electroslag ingot in the step 4) is polished and then subjected to the first vacuum consumable long arc operation to obtain an ingot 1#, and the ingot 1# is polished again and then subjected to the second vacuum consumable short arc operation to obtain an ingot 2#.
Preferably, the first vacuum consumable requires controlling the arc to be long arc and high melting speed, the length of the arc is controlled to be 8-12mm, and the melting speed is controlled to be 3.5-3.7.KG/Mi; the electric arc is controlled to be short arc and low melting speed, the length of the electric arc is controlled to be 4-8mm, and the melting speed is controlled to be 3.0-3.3 KG/Mi.
Preferably, in the step 4), after the ingot casting 2# is kept at 1100 ℃ for 10 hours, the temperature is continuously raised to 1150 ℃ for 15 hours, the temperature is continuously raised to 1190 ℃ for 48 hours, then air cooling is carried out, isothermal forging is carried out on the ingot casting 2# after air cooling at 1000-1100 ℃, the forging ratio is larger than 5, finally, after the ingot casting 2# after forging is kept at 960 ℃ for 1 hour, the temperature is reduced to 780 ℃ at the cooling rate of 55-60 ℃ for 20 hours, and then air cooling is carried out, so as to obtain the strontium-containing nickel-based alloy product.
(III) technical effects to be achieved
Compared with the prior art, the invention has the beneficial effects that:
firstly, the strontium-containing nickel-base alloy disclosed by the invention is added with a proper amount of strontium element to improve high-temperature thermoplastic property, so that the problem of forging cracking of cast ingots is solved.
Secondly, the invention develops a slag system for electroslag remelting strontium-containing alloy, and determines the SrO content in the slag system from the thermodynamic equilibrium angle, thereby being beneficial to improving the forging cracking problem of cast ingots.
Thirdly, the strontium element is added into the nickel-based superalloy, so that the problem of coarse eutectic phase of r+r' is solved.
Fourthly, the invention provides a high-temperature diffusion annealing process of the nickel-based alloy cast ingot containing strontium, which can eliminate adverse factors of strontium, fully exert the beneficial effects of strontium and reduce the cracking phenomenon of the nickel-based alloy in the forging process.
Drawings
FIG. 1 is a diagram of a forging crack when strontium is not added to a prior art nickel-based alloy.
FIG. 2 is a schematic flow chart of a method for preparing a strontium-containing nickel-base alloy according to the present invention.
Detailed Description
Embodiment one: referring to fig. 1, a strontium-containing nickel-base alloy comprises the following components in mass percent:
carbon: 0.01 to 0.06 percent;
chromium: 14% -15%;
cobalt: 26% -27%;
niobium: 1.5 to 2.0 percent;
molybdenum: 3% -4%;
aluminum: 2.3 to 2.8 percent;
titanium: 4.9 to 5.5 percent;
manganese: 4.0 to 4.5 percent;
strontium: 0.03 to 0.06 percent;
magnesium: 2.0 to 3.5 percent;
the balance being nickel and unavoidable impurity elements.
As the strontium element is regarded as a cleaning element in some alloys, the strontium not only can play a role in deoxidizing, but also can denature clustered Al2O3 inclusions into SrAl 2O4 oxide particles with tiny dispersion distribution, can be used as nucleation particles of NbC, improves the size and distribution of NbC in the nickel-based alloy, and reduces the problem of NbC forging cracking. The strontium element in solid solution state can also strengthen the purification and strengthen the grain boundary, and improve the (r+r') eutectic problem. However, excessive amount is counterintuitive, and SrNi phase with low melting point appears, deteriorating hot workability of the alloy and increasing tendency of crack generation. Therefore, it is an optimal way to control the optimal composition range of the strontium element to improve the hot workability of the nickel-base alloy.
A preparation method of a strontium-containing nickel-based alloy comprises the following steps:
step 1) weighing smelting raw materials capable of obtaining carbon, chromium (metal chromium), cobalt, niobium, molybdenum, aluminum, titanium, manganese, strontium and magnesium according to an element proportioning principle of the strontium-containing alloy;
wherein, the composition comprises the following components in percentage by mass:
carbon: 0.01 to 0.06 percent;
chromium: 14% -15%;
cobalt: 26% -27%;
niobium: 1.5 to 2.0 percent;
molybdenum: 3% -4%;
aluminum: 2.3 to 2.8 percent;
titanium: 4.9 to 5.5 percent;
manganese: 4.0 to 4.5 percent;
strontium: 0.03 to 0.06 percent;
magnesium: 2.0 to 3.5 percent;
the balance being nickel and unavoidable impurity elements.
Step 2) adding the smelting raw materials in the step 1) into a vacuum induction furnace, and tapping and casting the vacuum induction furnace under vacuum conditions after full melting and refining treatment to form an alloy ingot, wherein the step is also called vacuum induction smelting;
wherein oxygen in the vacuum induction furnace is less than 20ppm under vacuum conditions.
Adding smelting raw materials (including industrial pure iron, metallic chromium, graphite, aluminum ingot, strontium iron, sponge titanium and nickel magnesium alloy) into a vacuum induction furnace, placing the industrial pure iron and the metallic chromium into a crucible of the vacuum induction furnace, placing the graphite, the aluminum ingot, the strontium iron and the sponge titanium into a feeding bin of the vacuum induction furnace, finally adding the nickel magnesium alloy, vacuumizing the vacuum induction furnace to below 15Pa, electrifying and heating to melt the smelting raw materials in the crucible; after the raw materials in the crucible are completely melted, sequentially adding graphite, aluminum ingot, strontium and titanium sponge into the crucible (sequentially adding the graphite according to the alloy content requirement in the steel grade), refining for half an hour at 1530-1590 ℃ after the alloy is completely melted, then charging argon into an induction furnace to slight positive pressure (50-200 pa higher than atmospheric pressure), adding nickel-magnesium alloy, keeping the temperature in the crucible at 1530-1590 ℃ for 10-15 minutes, and then tapping and casting to form the alloy ingot.
The alloy ingot smelted comprises the following components: carbon: 0.01 to 0.06 percent of chromium: 14% -15%, cobalt: 26% -27%, niobium: 1.5 to 2.0 percent of molybdenum: 3% -4%; aluminum: 2.3 to 2.8 percent of titanium: 4.9 to 5.5 percent of manganese: 4.0 to 4.5 percent, strontium: 0.03 to 0.06 percent.
Step 3) taking the alloy ingot in the step 2) as a base material, and smelting slag CaF in electroslag remelting 2 -CaO-MgO-A l 2 O 3 -T iO 2 The SrO and the alloy ingot are matched for electroslag remelting to obtain a nickel-based alloy electroslag ingot, wherein the base slag system in the electroslag remelting comprises the following components in percentage by weight:
aiming at nickel-based alloy containing 0.41 percent of strontium and 3.52 percent of aluminum, the method established by the invention is adopted to determine the components of the slag according to the component characteristics of the consumable electrode: caF (CaF) 2 :A l 2 O 3 :CaO:MgO：T iO 2 :SrO＝53:17:13:3:3:10。
The slag was charged in an electroslag furnace having a capacity of 100kg and an inner diameter of a mold of 36cm, with currents and voltages of 8000A and 67V, respectively, and an electrode diameter of 26cm, and a slag amount of 40kg. 20g of metal aluminum powder was added to the slag at the beginning of electroslag remelting. After remelting 2000kg of electroslag ingot, the electroslag remelting is finished. Demoulding the electroslag ingot, and then putting the electroslag ingot into a slow cooling pit for slow cooling. The composition of the electroslag ingot was measured, and the compositions of Al, T i, sr and S i in the axial direction of the electroslag ingot in a typical heat treatment are shown in the following table. The obtained alloy ingot has small axial Sr content deviation, the fluctuation range is 0.036-0.041 percent, and the contents of aluminum, strontium and titanium are in reasonable range although all the contents have fluctuation. Wherein the electroslag remelting reduces the oxygen content to within 5 ppm.
Content of aluminum, strontium, titanium elements in electroslag ingot along height of electroslag ingot
Step 4) carrying out primary vacuum consumable long arc operation after polishing the nickel-based alloy electroslag ingot in the step 3) to obtain an ingot 1#, wherein the primary vacuum consumable long arc is required to be controlled to be long arc and high melting speed, the purpose of removing impurities is achieved, the length of the arc is controlled to be 8-12mm, and the melting speed is controlled to be 3.5-3.7.KG/Mi, so that the purpose of removing the impurities is more facilitated; carrying out lighting on the cast ingot 1# again, and then carrying out short arc operation of secondary vacuum consumable supply again to obtain cast ingot 2# wherein the electric arc is controlled to be short arc and low melting speed, and the secondary vacuum consumable supply is carried out again to reduce the problems of solidification structure segregation and (r+r') coarse eutectic precipitated phases, wherein the electric arc length is controlled to be 4-8mm, and the melting speed is controlled to be 3.0-3.3KG/Mi n, so that the solidification structure segregation is reduced more favorably;
the method comprises the steps of polishing a nickel-based alloy electroslag ingot, performing a first vacuum consumable long-arc operation to obtain a vacuum consumable ingot 1#, polishing the vacuum consumable ingot 1#, performing a second vacuum consumable short-arc operation, wherein manganese is volatilized in the vacuum consumable operation, and finally the manganese content in the ingot is 1.2%. Wherein the vacuum consumable reduces the oxygen content to within 5 ppm.
Step 5) performing forging, rolling and heat treatment on the cast ingot 2# obtained in the step 4), wherein air cooling (a process of cooling in the atmosphere) is performed after a plurality of heating and heat preservation operations are required;
after the ingot casting 2# is kept at 1100 ℃ for 10 hours, the low-melting point SrNi precipitated phase can be fused back into the matrix, so that cracking defects in the forging process are avoided, after the temperature is continuously increased to 1150 ℃ and kept for 15 hours, the low-melting point Laves phase can be fused back into the matrix, so that cracking defects in the forging process are avoided, the temperature is continuously increased to 1190 ℃ and kept for 48 hours, and the Nb original segregation can be uniformly distributed in the matrix, and then air cooling is performed.
Step 6), carrying out isothermal forging on the cast ingot 2# subjected to air cooling in the step 5) at the temperature of 1000-1100 ℃, wherein the forging ratio is more than 5;
and 7) preserving heat for 1 hour at 960 ℃, cooling to 780 ℃ at a cooling rate of 55-60 ℃ and preserving heat for 20 hours, and then air-cooling to obtain the strontium-containing nickel-based alloy product, wherein the cracking problem does not occur in the forging process of the product.
Comparative example 1:
the present comparative example provides a nickel-based alloy comprising, in mass percent: carbon: 0.01 to 0.06 percent of chromium: 14% -15%, cobalt: 26-27, niobium: 1.5 to 2.0 percent of molybdenum: 3% -4%; aluminum: 2.3 to 2.8 percent of titanium: 4.9 to 5.5 percent of manganese: 1.0 to 1.5 percent and the balance of nickel. The remainder is the same as above, except for whether strontium is added. Cracking problems occur during forging as shown in fig. 1.
Comparative example 2:
the strontium-containing nickel-base alloy of this comparative example is the same as the application example except that ingot # 2 was not left to stand at 1100 ℃ for 10 hours. The ingot is directly heated to 1150 ℃ for 15 hours, then is continuously heated to 1190 for 48 hours, and is then air-cooled. The SrNi precipitated phase is molten by directly heating to 1150 ℃ in the heating process, so that the SrNi precipitated phase is molten into a liquid state, and the SrNi precipitated phase becomes a crack source during forging. Therefore, the ingot of comparative example 2 was cracked during forging.
Because the design of a remelting slag system in the electroslag remelting strontium-containing alloy in the prior art is not reasonable, unstable oxides in slag and continuous change of the reaction temperature of metal and slag can cause uneven distribution of strontium elements along the axial direction of an ingot, and the alloy exceeds the required range of the alloy and reduces the yield in serious cases. At present, the problem of controlling the uniformity of strontium element added with strontium in the nickel-based alloy along the axial direction of an electroslag ingot has become a bottleneck problem for producing high-quality strontium-containing alloy by electroslag remelting. In addition, the burning loss of manganese element can be caused by the vacuum high-temperature environment in the long-arc vacuum consumable and the short-arc vacuum consumable, so that the manganese element in the base metal is controlled, and the fact that the manganese element cannot be obtained in the control range in the prior art is realized after the vacuum consumable is carried out, so that the cracking phenomenon of the nickel-based alloy in the forging process can be reduced, and the use requirement can be met.
The nickel-based alloy provided by the invention is added with a proper amount of strontium element to improve high-temperature thermoplastic property, and is beneficial to improving the forging cracking problem of cast ingots. The invention develops a slag system for electroslag remelting strontium-containing alloy, and determines the SrO content in the slag system from the thermodynamic equilibrium angle; according to the invention, the strontium element is added into the nickel-based superalloy, so that the problem of coarse eutectic phase of r+r' is solved; the invention provides a high-temperature diffusion annealing process of a strontium-containing nickel-based alloy cast ingot, which can eliminate adverse factors of strontium, fully exert the beneficial effects of strontium and improve the problem of thermal processing cracking. The heat treatment and forging method of the strontium-containing nickel-base alloy can reduce the cracking phenomenon of the nickel-base alloy in the forging process.
It should be noted that, although the foregoing embodiments have been described herein, the scope of the present invention is not limited thereby. Therefore, based on the innovative concepts of the present invention, alterations and modifications to the embodiments described herein, or equivalent structures or equivalent flow transformations made by the present description and drawings, apply the above technical solutions directly or indirectly to other relevant technical fields, all of which are included in the scope of protection of the present patent.
Claims (10)
1. A strontium-containing nickel-base alloy characterized in that: the composite material comprises the following components in percentage by mass:
carbon: 0.01 to 0.06 percent;
chromium: 14% -15%;
cobalt: 26% -27%;
niobium: 1.5 to 2.0 percent;
molybdenum: 3% -4%;
aluminum: 2.3 to 2.8 percent;
titanium: 4.9 to 5.5 percent;
manganese: 4.0 to 4.5 percent;
strontium: 0.03 to 0.06 percent;
magnesium: 2.0 to 3.5 percent;
the balance being nickel and unavoidable impurity elements.
2. A preparation method of a strontium-containing nickel-based alloy comprises the following steps:
step 1) weighing metallurgical raw materials capable of obtaining carbon, chromium, cobalt, niobium, molybdenum, aluminum, titanium, manganese, strontium and magnesium according to an element proportioning principle of the strontium-containing alloy;
step 2), adding the smelting raw materials in the step 1) into a vacuum induction furnace, and tapping and casting to form an alloy ingot after full melting and refining treatment in a vacuum condition through the vacuum induction furnace;
step 3) taking the alloy ingot in the step 2) as a base material, and obtaining a nickel-based alloy electroslag ingot through an electroslag remelting process;
step 4) forging, rolling and heat treatment are carried out after the vacuum consumable operation is carried out on the basis of the step 3) to obtain the strontium-containing nickel-based alloy product.
3. The method of making a strontium containing nickel-base alloy as defined in claim 2, wherein: the metallurgical raw materials of carbon, chromium (metal chromium), cobalt, niobium, molybdenum, aluminum, titanium, manganese, strontium and magnesium in the step 1) comprise the following components in percentage by mass:
carbon: 0.01 to 0.06 percent;
chromium: 14% -15%;
cobalt: 26% -27%;
niobium: 1.5 to 2.0 percent;
molybdenum: 3% -4%;
aluminum: 2.3 to 2.8 percent;
titanium: 4.9 to 5.5 percent;
manganese: 4.0 to 4.5 percent;
strontium: 0.03 to 0.06 percent;
magnesium: 2.0 to 3.5 percent;
the balance being nickel and unavoidable impurity elements.
4. The method of making a strontium containing nickel-base alloy as defined in claim 2, wherein: and 2) oxygen is lower than 20ppm under the vacuum condition in the vacuum induction furnace in the step 2).
5. The method of making a strontium containing nickel-base alloy as defined in claim 2, wherein: the alloy ingot smelted in the step 2) comprises the following components: carbon: 0.01 to 0.06 percent of chromium: 14% -15%, cobalt: 26% -27%, niobium: 1.5 to 2.0 percent of molybdenum: 3% -4%; aluminum: 2.3 to 2.8 percent of titanium: 4.9 to 5.5 percent of manganese: 4.0 to 4.5 percent, strontium: 0.03 to 0.06 percent.
6. The method for preparing a strontium-containing nickel-base alloy as claimed in claim 2,the method is characterized in that: the step 3) is to remelt the smelting slag system CaF in the electroslag remelting 2 -CaO-MgO-Al 2 O 3 -TiO 2 The SrO and the alloy ingot are matched for electroslag remelting to obtain a nickel-based alloy electroslag ingot, wherein the base slag system in the electroslag remelting comprises the following components in percentage by weight:
7. the method of preparing a strontium-containing nickel-base alloy according to claim 6, wherein: for nickel-based alloys containing 0.41% strontium and 3.52% aluminum, the components of the slag are determined according to the component characteristics of the consumable electrode: caF (CaF) 2 :Al 2 O 3 :CaO:MgO：TiO 2 :SrO＝53:17:13:3:3:10。
8. The method of making a strontium containing nickel-base alloy as defined in claim 2, wherein: and 4) performing the first vacuum consumable long-arc operation after the nickel-based alloy electroslag ingot in the step 4) is polished to obtain an ingot 1#, performing the polishing on the ingot 1# again, and performing the second vacuum consumable short-arc operation again to obtain an ingot 2#.
9. The method of making a strontium containing nickel-base alloy according to claim 8, wherein: the first vacuum consumable requires to control the arc to be long arc and high melting speed, the length of the arc is controlled to be 8-12mm, and the melting speed is controlled to be 3.5-3.7.KG/Min; the electric arc is controlled to be short arc and low melting speed, the length of the electric arc is controlled to be 4-8mm, and the melting speed is controlled to be 3.0-3.3KG/Min.
10. The method of making a strontium containing nickel-base alloy according to claim 8 or 9, wherein: and 4) after the ingot casting 2# is kept at 1100 ℃ for 10 hours, continuously heating to 1150 ℃ for 15 hours, continuously heating to 1190 ℃ for 48 hours, then air-cooling, carrying out isothermal forging on the air-cooled ingot casting 2# at 1000-1100 ℃, wherein the forging ratio is more than 5, finally cooling to 780 ℃ at the cooling rate after the forged ingot casting 2# is kept at 960 ℃ for 1 hour, and carrying out air cooling to obtain the strontium-containing nickel-based alloy product.
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