CN116065056A - Large-specification nickel-based superalloy bar difficult to deform and preparation method thereof - Google Patents
Large-specification nickel-based superalloy bar difficult to deform and preparation method thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910000601 superalloy Inorganic materials 0.000 title claims abstract description 61
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 72
- 239000000956 alloy Substances 0.000 claims abstract description 72
- 238000005242 forging Methods 0.000 claims abstract description 31
- 238000011282 treatment Methods 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 230000006698 induction Effects 0.000 claims abstract description 12
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 10
- 238000000265 homogenisation Methods 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 8
- 230000008018 melting Effects 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 238000003723 Smelting Methods 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 34
- 230000008569 process Effects 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 21
- 229910000831 Steel Inorganic materials 0.000 claims description 16
- 239000010959 steel Substances 0.000 claims description 16
- 238000007670 refining Methods 0.000 claims description 13
- 238000005275 alloying Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 229910018505 Ni—Mg Inorganic materials 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 8
- 239000006104 solid solution Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 5
- 238000010079 rubber tapping Methods 0.000 claims description 5
- 238000003303 reheating Methods 0.000 claims description 3
- 238000010309 melting process Methods 0.000 claims description 2
- 239000000306 component Substances 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 238000005728 strengthening Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 101000912561 Bos taurus Fibrinogen gamma-B chain Proteins 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000004663 powder metallurgy Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000010313 vacuum arc remelting Methods 0.000 description 1
- 238000003466 welding Methods 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
- 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
- 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
- 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
-
- 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
- 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)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a difficult-to-deform large-specification nickel-based superalloy bar and a preparation method thereof, wherein the difficult-to-deform large-specification nickel-based superalloy bar comprises the following chemical components in percentage by weight: c:0.01 to 0.10 percent of Cr:10.0 to 20.0 percent of Co:9.0 to 14.0 percent of Al:1.0 to 3.0 percent of Ti:1.0 to 3.0 percent of Nb:1.0 to 3.0 percent of Mo:2.0 to 7.0 percent, W is less than or equal to 0.20 percent, B is less than or equal to 0.01 percent, N is less than or equal to 0.02 percent, O is less than or equal to 0.008 percent, and Fe:0.1 to 2.0 percent, and the balance of nickel and unavoidable impurities. According to the invention, the deformation high-temperature alloy with high performance and good tissue stability is obtained by optimizing alloy components and adopting vacuum induction melting, vacuum arc furnace remelting, homogenization treatment, forging and heat treatment, so that the engineering application feasibility of the alloy is ensured, and the application requirements of a ship gas turbine are met.
Description
Technical Field
The invention relates to the technical field of nickel-based alloy bars difficult to deform, in particular to a nickel-based superalloy bar difficult to deform and a preparation method thereof.
Background
The superalloy is one type of alloy which can bear certain stress at the temperature of above 600 ℃ and has oxidation resistance and corrosion resistance, and can be divided into iron base, nickel base and cobalt base according to a matrix, and three types are generally divided according to a forming process, namely, a deformed superalloy, a cast superalloy and a powder metallurgy superalloy; the nickel-based wrought superalloy benefits from excellent oxidation resistance and corrosion resistance and higher high-temperature strength, and is widely applied to the fields of aerospace engines, gas turbine engines, oil and gas fields, automobile industry and the like.
With the rapid development of naval vessels, the requirements on the core components of the naval vessels on the gas turbines are higher and higher, the existing 30 MW-level gas turbine is the only gas turbine for the medium-and-large-grade power vessels which can be applied at present in China, but the power of the gas turbine cannot meet the requirements of the development of the naval vessels of the next generation, and the 40 MW-level high-power gas turbine for the naval vessels is the main engine type adopted by the naval vessels within 10-15 years in the future; with the improvement of the power of the ship gas turbine, the working environment of the turbine disk is more severe, the use temperature is higher, and the corresponding high-temperature mechanical performance indexes such as high-temperature strength, heat intensity and the like are higher. Taking a common turbine disc material as an example, GH4169 alloy is the turbine disc material with the largest use amount of the aeroengine in China at present, but the use temperature is below 650 ℃, if the use temperature exceeds 650 ℃, the structure is unstable, and then the alloy fails; although powder metallurgy superalloy is a manufacturing scheme for future high performance turbine disk manufacturing, the powder metallurgy has complex and long procedures, and the manufacturing cost of the deformed superalloy is relatively low; according to the development of the high-temperature alloy for the turbine disc in recent years, the preparation of the high-performance high-temperature alloy by adopting a casting and forging deformation process with short flow and low cost is an important development direction and trend in the future.
In the prior art, publication No. CN 103498075A provides a refractory superalloy and a preparation method thereof, the composition control of which is shown in table 1, and the technology adopts vacuum induction and vacuum arc remelting for smelting and casting into steel ingots; but the remelted ingot has smaller diameter, only
Cannot be used for producing large-size disc parts, but can be used for producing cake parts and cake part rulerCun->
Publication No. CN 108441705A provides a high strength nickel-base superalloy, the composition of which is controlled in the following table 1, and the alloy designed by the technology has better high temperature and high temperature strength and durability compared with GH4169 and FGH 4097. However, the alloy has a higher Co content, which results in a corresponding increase in the cost of manufacturing the alloy.
TABLE 1 alloy composition of the prior art (wt%)
Therefore, it is necessary to develop a high-strength deformation superalloy with higher comprehensive performance than GH4169 and equivalent to powder metallurgy superalloy so as to meet the use requirement of the high-power ship gas turbine.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a nickel-based superalloy bar with difficult deformation and large specification and a preparation method thereof, and the alloy components are optimized, so that the Co and Cr contents in the alloy are reduced on the basis of ensuring the high strength of the alloy, al, ti and Nb elements are added in a compound manner, the volume fraction and the thermal stability of gamma' -phase are improved, and the upper limit temperature of the alloy is increased; the deformed high-temperature alloy with high performance and good tissue stability is obtained by adopting vacuum induction melting, vacuum arc furnace remelting, homogenization treatment, forging and heat treatment, so that the engineering application feasibility of the alloy is ensured, and the application requirement of a ship gas turbine is met.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a nickel-based superalloy bar with difficult deformation and large specification, which comprises the following chemical components in percentage by weight: c:0.01 to 0.10 percent of Cr:10.0 to 20.0 percent of Co:9.0 to 14.0 percent of Al:1.0 to 3.0 percent of Ti:1.0 to 3.0 percent of Nb:1.0 to 3.0 percent of Mo:2.0 to 7.0 percent, W is less than or equal to 0.20 percent, B is less than or equal to 0.010 percent, N is less than or equal to 0.020 percent, O is less than or equal to 0.008 percent, fe is 0.1 to 2.0 percent, and the balance is nickel and unavoidable impurities.
Preferably, C:0.020 to 0.080 percent, cr:13.0 to 15.0 percent of Co:9.0 to 11.0 percent of Al:2.0 to 3.0 percent of Ti:2.0 to 3.0 percent of Nb:2.0 to 3.0 percent of Mo:4.5 to 5.5 percent, N is less than or equal to 0.010 percent, O is less than or equal to 0.0050 percent, and Fe is less than or equal to 1.0 percent.
Preferably, at room temperature, the tensile strength sigma of the difficult-to-deform large-specification nickel-based superalloy bar b Not less than 1500MPa, yield strength sigma 0.2 Not less than 1150MPa, elongation delta 5 More than or equal to 21.5 percent, the area shrinkage psi is more than or equal to 31.5 percent;
the elongation delta of the difficult-to-deform large-specification nickel-based superalloy rod material under the conditions of the temperature of 650 ℃ and the pressure of 873MPa 5 The surface shrinkage ratio psi is more than or equal to 3.5 and is more than or equal to 8 percent.
The second aspect of the invention provides a preparation method of the nickel-based superalloy bar with difficult deformation and large specification, which comprises the following steps:
s1, smelting in a vacuum induction furnace, adding a main material component Ni, cr, co, mo, simultaneously adding C, vacuumizing to below 2.7Pa, carrying out power rising for material conversion, refining after material conversion is finished, adding alloying elements Ti, al, nb and B for alloying smelting, analyzing the components of molten steel, filling Ar after the target component requirement is met, adding Ni-Mg alloy, tapping and casting an electrode after smelting;
s2, performing vacuum consumable smelting, namely performing vacuum consumable smelting on the electrode after surface cleaning to obtain a consumable ingot;
s3, forging, namely homogenizing the consumable ingot, forging the consumable ingot by adopting a repeated upsetting process to obtain a large-size bar, and polishing the surface of the large-size bar;
s4, heat treatment, namely carrying out solution treatment and aging heat treatment on the large-specification bar, and finally obtaining the nickel-based superalloy bar difficult to deform.
Preferably, the step S1:
in the material melting process, the power is 300-1000 kw; and/or
In the refining process, the refining temperature is 1480-1530 ℃ and the refining time is 30-60 min; and/or
In the alloying smelting process, the power is 200-600 kw, and the temperature is 1490-1520 ℃; and/or
After Ar is filled, the pressure is 20-25 KPa; the addition amount of the Ni-Mg alloy in each ton of molten steel is 5-9 kg; and continuing smelting for 5-10 min after adding the Ni-Mg alloy.
Preferably, in the step S2, the melting speed is 3.5-5.5 kg/min in the vacuum consumable smelting process.
Preferably, in the step S3:
in the homogenization treatment process, the consumable ingot is heated to 1130-1180 ℃ and is preserved for more than 60 hours; and/or
In the forging process, the homogenized consumable ingot is heated to 1140-1160 ℃, upsetted to 1/2-2/3 of the original height of the consumable ingot, gradually cooled and drawn, and the reheating temperature is gradually reduced from 1160 ℃ to 1100 ℃, and the heat preservation time is more than or equal to 120min.
Preferably, in the step S3, during the forging process, the forging start temperature is equal to or higher than 1050 ℃, and the forging stop temperature is equal to or higher than 1000 ℃.
Preferably, in the step S4:
in the solid solution treatment process, the large-specification bar after being polished is heated to 1060-1100 ℃, and after heat preservation is carried out for 7-11 hours, the bar is discharged from a furnace for air cooling;
in the aging treatment process, the large-size bar after solution treatment is heated to 750-790 ℃, and is discharged from a furnace for air cooling after heat preservation for 14-19 hours.
The design principle of the chemical components of the difficult-to-deform large-specification nickel-based superalloy bar is as follows:
c: c is an important strengthening element between grain boundaries and dendrites in the high-temperature alloy and is an essential element for forming carbide; the content of C in the alloy is lower than 0.01 weight percent, so that the quantity of carbide in the alloy is less, and the refinement of crystal grains and the improvement of performance are not facilitated; too high a C content results in excessive carbide formation and increased segregation tendency, which makes the alloy grains nonuniform and deteriorates the alloy plasticity. Thus, the range of C is controlled to be 0.01 to 0.10wt%, preferably 0.02 to 0.08wt%.
Cr: the addition of Cr can improve the high-temperature oxidation resistance and corrosion resistance of the alloy and promote the formation of single-phase Orient solid solution; when the Cr content in the alloy is not less than 10%, the oxidation resistance and corrosion resistance of Cr are fully exerted, but too high a Cr content in the alloy results in the formation of sigma phase, thereby deteriorating the usability of the alloy. In order to ensure the comprehensive performance of the alloy and inhibit harmful phases, the range of Cr is controlled to be 10.0-20.0 wt percent, and the range is controlled to be 13.0-15.0 wt percent preferentially.
Co: co can form a substitutional solid solution with Ni, and can play a solid solution strengthening effect; the addition of Co element in the alloy can reduce the stacking fault energy of the matrix, thereby improving the durability and creep resistance of the alloy; however, too much Co element is disadvantageous in that it causes precipitation of a harmful phase, and Co is a strategic resource, and too much Co element is added to the alloy, which increases the cost. Therefore, the Co is controlled in the range of 9.0 to 14.0wt%, and preferably in the range of 9.0 to 11.0wt%.
Al: al is an essential element for forming gamma' phase in the nickel-based alloy, the higher the Al content is, the larger the precipitation amount is, the better the precipitation strengthening effect is, and the corresponding strength of the alloy is also improved; however, too high an Al content increases the difficulty of hot working and tends to cause cracking. Therefore, the Al is controlled in the range of 1.0 to 3.0wt%, and preferably in the range of 2.0 to 3.0wt%.
Ti: the Ti element is also an essential forming element of the gamma 'phase, and is dissolved in the gamma' phase and can replace two thirds of Al atoms; after Ti enters gamma ', the precipitation of gamma' is slowed down, and the overaging is effectively prevented, so that the alloy has long-term service in a high-temperature environment; however, when Ti is excessively added, coarse flaky eta-Ni 3Ti phases appear, so that the alloy is embrittled, and the strength and the plasticity are reduced. Therefore, the Ti is controlled in the range of 1.0 to 3.0wt%, and preferably in the range of 2.0 to 3.0wt%.
Nb: nb has stronger affinity with C, and the addition of Nb can promote carbide precipitation, thereby refining grains and playing a role in strengthening grain boundaries. Besides being combined with C, most Nb element enters into gamma 'phase, so that the dissolution of Al and Ti in a matrix is reduced, the precipitation of gamma' phase is promoted, the aggregation growth of gamma 'phase is delayed, the strength and the dissolution temperature of gamma' phase are improved, and the use temperature of the alloy can be improved by comprehensively combining the Nb element. However, excessive addition of Nb element leads to easy formation of segregation during smelting, and metallurgical defects such as black specks. Accordingly, the range of Nb is controlled to be 1.0 to 3.0wt%, and preferably 2.0 to 3.0wt%.
Mo: mo element is mainly dissolved in the g phase of the matrix, the atomic radius of Mo is far larger than that of Ni, the solid solution strengthening effect is achieved, and the corrosion resistance and the high-temperature stability of the alloy are improved. However, excessive Mo can lead to precipitation of TCP phase, and deteriorate mechanical properties of the alloy. The Mo content is controlled to be 2.0-7.0 wt% by comprehensive consideration, and the control range is preferably 4.5-5.5 wt%.
B: b is a grain boundary strengthening element which is mainly distributed between a grain boundary and a column crystal in the form of boride and plays a role in strengthening; the addition of B element can obviously improve the high-temperature durability and creep life of the alloy, but excessive B can obviously deteriorate the hot workability of the alloy and also deteriorate the welding process performance of the alloy. The B content is controlled within 0.010wt% by comprehensive consideration.
N, O: n, O in the alloy is controlled to provide a bright spot for the composition of the invention. By controlling the interstitial element, in particular N, O, the effect on improving the fatigue performance of the alloy is obvious. Therefore, the invention selects to control according to N less than or equal to 0.020wt percent, O less than or equal to 0.0080wt percent, preferably controls the range of N less than or equal to 0.010wt percent, and preferably controls O less than or equal to 0.0050wt percent.
Fe: the addition of Fe is mainly used for utilizing the high-temperature alloy return material containing Fe, so that the vacuum induction smelting cost is reduced; however, excessive addition of the return material leads to exceeding of the Fe content in the alloy, so that the Fe content is considered to be less than or equal to 1.0wt% comprehensively, and the Fe content is controlled to be 0.1-2.0 wt% preferentially.
The invention has the following beneficial effects:
1. according to the difficult-to-deform large-specification nickel-based superalloy bar and the preparation method thereof, the Co and Cr contents in the alloy are reduced on the basis of ensuring the high strength of the alloy by optimizing the alloy components, and Al, ti and Nb elements are added in a compound manner, so that the volume fraction and the thermal stability of gamma' -phase are improved, and the upper limit temperature of the alloy is increased;
2. according to the preparation method of the difficult-to-deform large-specification nickel-base superalloy bar, the preparation process of vacuum induction melting, vacuum arc furnace remelting, consumable ingot homogenization treatment, forging and heat treatment is adopted to obtain the difficult-to-deform large-specification nickel-base superalloy bar with high performance and good tissue stability, so that the use requirement of a large-scale ship gas turbine on the high-performance nickel-base superalloy can be met, and a solid foundation is laid for application research of the difficult-to-deform nickel-base superalloy in China in the future.
Detailed Description
In order to better understand the above technical solution of the present invention, the technical solution of the present invention is further described below with reference to examples.
The invention relates to a nickel-based superalloy bar with difficult deformation and large specification and a preparation method thereof, wherein the nickel-based superalloy bar comprises the following chemical components in percentage by weight: c:0.01 to 0.10 percent of Cr:10.0 to 20.0 percent of Co:9.0 to 14.0 percent of Al:1.0 to 3.0 percent of Ti:1.0 to 3.0 percent of Nb:1.0 to 3.0 percent of Mo:2.0 to 7.0 percent, W is less than or equal to 0.20 percent, B is less than or equal to 0.010 percent, N is less than or equal to 0.020 percent, O is less than or equal to 0.008 percent, fe is 0.1 to 2.0 percent, and the balance is nickel and unavoidable impurities. In a preferred embodiment, C:0.020 to 0.080 percent, cr:13.0 to 15.0 percent of Co:9.0 to 11.0 percent of Al:2.0 to 3.0 percent of Ti:2.0 to 3.0 percent of Nb:2.0 to 3.0 percent of Mo:4.5 to 5.5 percent, N is less than or equal to 0.010 percent, O is less than or equal to 0.0050 percent, and Fe is 0.1 to 1.0 percent.
The high-specification nickel-based superalloy bar difficult to deform has tensile strength sigma at room temperature b Not less than 1500MPa, yield strength sigma 0.2 Not less than 1150MPa, elongation delta 5 More than or equal to 21.5 percent, the area shrinkage psi is more than or equal to 31.5 percent; under the conditions that the temperature is 650 ℃ and the pressure is 873MPa, the elongation delta 5 of the difficult-to-deform large-specification nickel-based superalloy bar is more than or equal to 3.5, and the surface shrinkage psi is more than or equal to 8%.
The preparation method of the nickel-based superalloy bar with difficult deformation and large specification comprises the following steps:
s1, smelting in a vacuum induction furnace, adding a main material component Ni, cr, co, mo, simultaneously adding C, vacuumizing to below 2.7Pa, carrying out material conversion by power increase, refining after material conversion is finished, adding alloying elements Ti, al, nb and B for alloying smelting, analyzing the components of molten steel, filling Ar after the target component requirement is met, adding Ni-Mg alloy, tapping and casting an electrode after smelting;
the specific process is as follows: proportioning according to chemical components of a large-size nickel-based superalloy bar difficult to deform, adding a main material element Ni, cr, co, mo, and simultaneously adding C, carrying out high-vacuum and high-power smelting, ensuring that the vacuum degree in a vacuum induction furnace is lower than 2.7Pa in the smelting process, increasing the power to 300-1000 kw, and ensuring that the O, N content in molten steel is reduced to the control requirement, wherein the C content is added according to the middle limit and the lower limit; after the melting is finished, the temperature is increased to 1480-1530 ℃ for refining, and the refining time is about 30-60 min; then reducing the power to 200-600 kw, reducing the temperature of the molten steel to 1490-1520 ℃, focusing on the condition of scum on the surface of the molten steel, and adding alloying elements Ti, al, nb and B for alloying smelting; then sampling and analyzing the molten steel components, filling Ar when the content of Ni, co, cr, mo, al, ti, nb, B and trace elements in the sample reaches the target component requirement, filling the Ar under the pressure of 20-25 KPa, adding Ni-Mg alloy, wherein the adding amount of the Ni-Mg alloy in each ton of molten steel is 5-9 kg, tapping and pouring electrodes after smelting for 5-10 min;
s2, performing vacuum consumable smelting, namely performing vacuum consumable smelting on the electrode after surface cleaning to obtain a consumable ingot;
the specific process is as follows: cleaning the surface of the electrode cast in the step S1, grinding cleanly, not allowing stains, oxide skin, water stains and the like to exist, then carrying out vacuum consumable smelting on the shrinkage cavity of the electrode head upwards, setting the smelting speed to be 3.5-5.5 kg/min, and finally obtaining a consumable ingot; wherein the electrode anneal may be performed prior to electrode surface cleaning.
S3, forging, namely homogenizing the consumable ingot, forging the consumable ingot by adopting a repeated upsetting process to obtain a large-size bar, and polishing the surface of the large-size bar;
the specific process is as follows: heating the consumable ingot in a heating furnace for 22-28 h, slowly raising the heating temperature from 480-530 ℃ to 1130-1160 ℃, preserving heat for more than 60h, homogenizing and diffusing, and peeling and finishing after discharging the consumable ingot. Then heating the finished consumable ingot to 1140-1160 ℃ and preserving heat for 7-11 h, discharging and forging, forging by adopting a multiple upsetting process, upsetting to 1/2-2/3 of the original height of the consumable ingot, gradually cooling and drawing, returning to the furnace, gradually reducing the reheating temperature from 1160 ℃ to 1100 ℃, preserving heat for more than or equal to 120min, finally forging a large-size bar, and polishing the surface of the large-size bar; in the forging process, the forging temperature is equal to or higher than 1050 ℃, and the forging stopping temperature is equal to or higher than 1000 ℃.
S4, heat treatment, namely carrying out solution treatment and aging heat treatment on the large-specification bar, and finally obtaining the nickel-based superalloy bar difficult to deform.
The specific process is as follows: carrying out solution treatment and aging heat treatment on the large-size bar to finally obtain a large-size nickel-based superalloy bar difficult to deform, wherein in the solution treatment process, the large-size bar subjected to polishing is heated to 1060-1100 ℃, and after heat preservation for 7-11 h, the bar is discharged from a furnace for air cooling; in the aging treatment process, the large-size bar after solution treatment is heated to 750-790 ℃, and is discharged from the furnace for air cooling after heat preservation for 14-19 hours. And then carrying out flaw detection and physicochemical property detection on the prepared nickel-based superalloy bar with difficult deformation and large specification, and warehousing and storing after reaching standards.
The invention relates to a nickel-based superalloy bar with difficult deformation and large specification and a preparation method thereof.
Examples
According to the preparation method of the difficult-to-deform large-specification nickel-based superalloy bar, 3-furnace alloy is produced, wherein in the specific preparation process, smelting is carried out by using a 12-ton vacuum induction furnace and a 10-ton vacuum consumable furnace, and then a consumable ingot is subjected to homogenization treatment, forging and 'solid solution and aging' heat treatment to obtain the difficult-to-deform large-specification nickel-based superalloy bar, and the specific process is as follows:
1) Smelting in 12 ton vacuum induction furnace
Selecting high-purity metal Ni, cr, co and W raw materials, and derusting and cleaning the surfaces of raw material lump materials without greasy dirt. The main material element Ni, cr, co, W is distributed according to the target composition, particularly attention is paid to substitution of Si, mn and Cu, and C is distributed according to the lower limit; vacuumizing to below 2.6Pa, starting to raise the power to be converted into materials, and controlling the power to be 300-1000 kw. Refining is carried out by raising the temperature to 1480-1530 ℃ for about 30-60 min. Then the power value is reduced to 200-600 kw, the temperature of the molten steel is reduced to 1490-1520 ℃, and the condition of scum on the surface of the molten steel is concerned; adding Ti, al, nb and B elements to carry out alloying smelting. Sampling for component analysis, and filling 20-25 kPa Ar when the content of alloy elements in the cup sample meets the technical protocol requirement, wherein the adding amount of Ni-Mg alloy in each ton of molten steel is 5-9 kg, smelting for 5-10 min at 400-1000 kw power, and tapping and pouring an electrode.
2) 10 ton vacuum consumable remelting
Grinding the surface of the electrode, not allowing stains, oxide skin, water stains and the like to exist, smelting the shrinkage cavity of the head of the electrode upwards to obtain a consumable ingot, and selecting
The melting speed of the self-consuming crystallizer is set to be 3.5-5.5 Kg/min.
3) Forging
Heating and preserving the temperature of the consumable ingot at 1130-1180 ℃ for more than 60 hours to perform homogenization diffusion, and then peeling and finishing. Then heating the consumable ingot to 1140-1160 ℃ and preserving heat for 7-11 h, discharging and forging, upsetting the consumable ingot for multiple times, upsetting to 1/2-2/3 of the original height of the consumable ingot, wherein the diameter of the steel ingot is about 650-750 mm, and increasing the forging ratio to break the internal structure of the steel ingot as much as possible; gradually cooling and drawing, returning to furnace, and gradually cooling from 1160 deg.C to 1100 deg.C, maintaining for 120min or more, and finally forging
Large-size bar, turning to +.>
Wherein the forging temperature is equal to or higher than 1050 ℃, and the forging stopping temperature is equal to or higher than 1000 ℃.
4) Heat treatment of
The forged large-size bar is subjected to heat treatment according to the following process:
solution treatment: preserving the temperature of the sample for 7-11 h within the temperature range of 1060-1100 ℃, discharging and air cooling;
aging treatment: preserving heat for 14-19 h at 750-790 ℃, discharging and air cooling; finally, the nickel-based superalloy bar with difficult deformation and large specification is obtained.
Specific chemical compositions of the 3-furnace alloy produced by the preparation method of the nickel-based superalloy bar with difficult deformation are shown in table 2, the 3-furnace alloy is sampled, and high-temperature durability tests are respectively carried out at room temperature and under the conditions of 650 ℃ and 873MPa of pressure, and specific results are shown in tables 3 and 4;
TABLE 2 chemical composition (wt%) of difficult-to-deform large-sized nickel-based superalloy rod
TABLE 3 mechanical Properties of alloys at room temperature
| Sequence number | σ b /MPa | σ 0.2 /MPa | δ 5 /％ | ψ/％ |
| Example 1 | 1580 | 1240 | 21.5 | 32 |
| Example 2 | 1580 | 1230 | 21.5 | 31.5 |
| Example 3 | 1500 | 1160 | 23.5 | 32.5 |
| GH4169 | 1400 | 1240 | 13 | 22 |
| GH738 | 1310 | 980 | 25 | 32 |
TABLE 4 high temperature durability at 650℃and 873MPa
The high-temperature alloy bar with the difficult-to-deform and large specification prepared in the embodiment has the comprehensive performance superior to that of GH4169 and GH738 alloy and excellent high-temperature mechanical property at the temperature of more than 650 ℃, is expected to become a high-temperature alloy alternative material for a turbine disc of a gas turbine for a next generation of ships, and lays a solid foundation for application research of the difficult-to-deform nickel-based superalloy in China in the future.
In summary, according to the difficult-to-deform large-specification nickel-based superalloy bar and the preparation method thereof, the alloy components are optimized, the Co and Cr contents in the alloy are reduced on the basis of ensuring the high strength of the alloy, and Al, ti and Nb elements are added in a composite manner, so that the volume fraction and the thermal stability of gamma' -phase are improved, and the upper limit temperature of the alloy is increased; the preparation method of the difficult-to-deform large-specification nickel-base superalloy bar adopts the preparation processes of vacuum induction melting, vacuum arc furnace remelting, self-consumption ingot homogenization treatment, forging and heat treatment to obtain the difficult-to-deform large-specification nickel-base superalloy bar with high performance and good tissue stability, so that the use requirement of a large-scale ship gas turbine on the high-performance nickel-base superalloy can be met, and a solid foundation is laid for application research of the difficult-to-deform nickel-base superalloy in China in the future.
It will be appreciated by persons skilled in the art that the above embodiments are provided for illustration only and not as limitations of the present invention, and that variations and modifications of the above described embodiments will fall within the scope of the claims of the present invention as long as they fall within the true spirit of the present invention.
Claims (9)
1. The nickel-based superalloy bar is characterized by comprising the following chemical components in percentage by weight: c:0.01 to 0.10 percent of Cr:10.0 to 20.0 percent of Co:9.0 to 14.0 percent of Al:1.0 to 3.0 percent of Ti:1.0 to 3.0 percent of Nb:1.0 to 3.0 percent of Mo:2.0 to 7.0 percent, W is less than or equal to 0.20 percent, B is less than or equal to 0.010 percent, N is less than or equal to 0.020 percent, O is less than or equal to 0.008 percent, and Fe:0.1 to 2.0 percent, and the balance of nickel and unavoidable impurities.
2. The difficult-to-deform large-gauge nickel-base superalloy rod of claim 1, wherein C:0.020 to 0.080 percent, cr:13.0 to 15.0 percent of Co:9.0 to 11.0 percent of Al:2.0 to 3.0 percent of Ti:2.0 to 3.0 percent of Nb:2.0 to 3.0 percent of Mo:4.5 to 5.5 percent, N is less than or equal to 0.010 percent, O is less than or equal to 0.0050 percent, fe:0.1 to 1.0 percent.
3. The difficult-to-deform large-gauge nickel-base superalloy rod of claim 1, wherein the difficult-to-deform large-gauge nickel-base superalloy rod has a tensile strength σ at room temperature b Not less than 1500MPa, yield strength sigma 0.2 Not less than 1150MPa, elongation delta 5 More than or equal to 21.5 percent, the area shrinkage psi is more than or equal to 31.5 percent;
the elongation delta of the nickel-based superalloy bar with difficult deformation and large specification is realized under the conditions that the temperature is 650 ℃ and the pressure is 873MPa 5 The surface shrinkage ratio psi is more than or equal to 3.5 and is more than or equal to 8 percent.
4. A method for producing a nickel-base superalloy rod of large specification which is difficult to deform as claimed in any of claims 1 to 3, comprising the steps of:
s1, smelting in a vacuum induction furnace, adding a main material component Ni, cr, co, mo, simultaneously adding C, vacuumizing to below 2.7Pa, carrying out material conversion by power increase, refining after material conversion is finished, adding alloying elements Ti, al, nb and B for alloying smelting, analyzing the components of molten steel, filling Ar after the target component requirement is met, adding Ni-Mg alloy, tapping and casting an electrode after smelting;
s2, performing vacuum consumable smelting, namely performing vacuum consumable smelting on the electrode after surface cleaning to obtain a consumable ingot;
s3, forging, namely homogenizing the consumable ingot, forging the consumable ingot by adopting a repeated upsetting process to obtain a large-size bar, and polishing the surface of the large-size bar;
s4, heat treatment, namely carrying out solution treatment and aging heat treatment on the large-specification bar, and finally obtaining the nickel-based superalloy bar difficult to deform.
5. The method for preparing a nickel-base superalloy rod with difficult deformation according to claim 4, wherein the step S1:
in the material melting process, the power is 300-1000 kw; and/or
In the refining process, the refining temperature is 1480-1530 ℃ and the refining time is 30-60 min; and/or
In the alloying smelting process, the power is 200-600 kw, and the temperature is 1490-1520 ℃; and/or
After Ar is filled, the pressure is 20-25 KPa; the addition amount of the Ni-Mg alloy in each ton of molten steel is 5-9 kg; and continuing smelting for 5-10 min after adding the Ni-Mg alloy.
6. The method for producing a nickel-base superalloy rod with high deformation resistance according to claim 4, wherein in the step S2, the melting speed is 3.5-5.5 kg/min in the vacuum consumable smelting process.
7. The method for producing a difficult-to-deform large-sized nickel-base superalloy rod according to claim 4, wherein in step S3:
in the homogenization treatment process, the consumable ingot is heated to 1130-1180 ℃ and is preserved for more than 60 hours; and/or
In the forging process, the homogenized consumable ingot is heated to 1140-1160 ℃, upsetted to 1/2-2/3 of the original height of the consumable ingot, gradually cooled and drawn, returned to the furnace, and the reheating temperature is gradually reduced from 1160 ℃ to 1100 ℃, and the heat preservation time is more than or equal to 120min.
8. The method for producing a nickel-base superalloy rod with high formability according to claim 4, wherein in the step S3, the forging temperature is equal to or higher than 1050 ℃ and the forging stopping temperature is equal to or higher than 1000 ℃.
9. The method for producing a difficult-to-deform large-sized nickel-base superalloy rod according to claim 4, wherein in step S4:
in the solid solution treatment process, the large-specification bar after being polished is heated to 1060-1100 ℃, and after heat preservation is carried out for 7-11 hours, the bar is discharged from a furnace for air cooling;
in the aging treatment process, the large-size bar after solution treatment is heated to 750-790 ℃, and is discharged from a furnace for air cooling after heat preservation for 14-19 hours.
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| JP2004256840A (en) * | 2003-02-24 | 2004-09-16 | Japan Steel Works Ltd:The | COMPOSITE REINFORCED TYPE Ni BASED SUPERALLOY, AND PRODUCTION METHOD THEREFOR |
| CN108315599A (en) * | 2018-05-14 | 2018-07-24 | 钢铁研究总院 | A kind of high cobalt nickel base superalloy and preparation method thereof |
| CN108441705A (en) * | 2018-03-16 | 2018-08-24 | 中国航发北京航空材料研究院 | A kind of high intensity ni-base wrought superalloy and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004256840A (en) * | 2003-02-24 | 2004-09-16 | Japan Steel Works Ltd:The | COMPOSITE REINFORCED TYPE Ni BASED SUPERALLOY, AND PRODUCTION METHOD THEREFOR |
| CN108441705A (en) * | 2018-03-16 | 2018-08-24 | 中国航发北京航空材料研究院 | A kind of high intensity ni-base wrought superalloy and preparation method thereof |
| CN108315599A (en) * | 2018-05-14 | 2018-07-24 | 钢铁研究总院 | A kind of high cobalt nickel base superalloy and preparation method thereof |
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