CN117987690A - Antioxidant corrosion-resistant nickel-based superalloy, and preparation method and application thereof - Google Patents
Antioxidant corrosion-resistant nickel-based superalloy, and preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 230000007797 corrosion Effects 0.000 title claims abstract description 89
- 238000005260 corrosion Methods 0.000 title claims abstract description 89
- 229910000601 superalloy Inorganic materials 0.000 title claims abstract description 76
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003963 antioxidant agent Substances 0.000 title description 7
- 230000003078 antioxidant effect Effects 0.000 title description 7
- 230000003647 oxidation Effects 0.000 claims abstract description 78
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 78
- 239000000126 substance Substances 0.000 claims abstract description 16
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 14
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 12
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 9
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 9
- 229910052796 boron Inorganic materials 0.000 claims abstract description 8
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- 239000000956 alloy Substances 0.000 claims description 94
- 229910045601 alloy Inorganic materials 0.000 claims description 93
- 238000010438 heat treatment Methods 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 24
- 238000005495 investment casting Methods 0.000 claims description 20
- 239000011651 chromium Substances 0.000 claims description 19
- 238000003723 Smelting Methods 0.000 claims description 17
- 238000007670 refining Methods 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 13
- 238000005266 casting Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 230000000630 rising effect Effects 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000000306 component Substances 0.000 description 18
- 229910052799 carbon Inorganic materials 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 238000005728 strengthening Methods 0.000 description 12
- 101000912561 Bos taurus Fibrinogen gamma-B chain Proteins 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000006104 solid solution Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 230000003064 anti-oxidating effect Effects 0.000 description 6
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- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
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- 239000000243 solution Substances 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
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- 238000010998 test method Methods 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 241001417490 Sillaginidae Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides an oxidation-resistant corrosion-resistant nickel-based superalloy, and a preparation method and application thereof, and belongs to the technical field of nickel-based superalloy. The invention provides an oxidation-resistant corrosion-resistant nickel-based superalloy, which comprises the following chemical components ：C：0.05~0.15%,Cr：16~18%,Co：9~11%,W：2.5~3%,Mo：1~2%,Al：3.5~4%,Ti：3.5~4%,Nb：0.8~1.5%,Ta：1~3%,B：0.002~0.015%,Zr：0.002~0.04% and the balance of Ni in percentage by mass. The results of the examples show that the oxidation rate of the oxidation-resistant corrosion-resistant nickel-based superalloy provided by the invention is less than or equal to 0.012g/m 2.h at 850 ℃ and less than or equal to 0.06g/m 2.h at 900 ℃.
Description
Technical Field
The invention relates to the technical field of nickel-based superalloy, in particular to an oxidation-resistant corrosion-resistant nickel-based superalloy, and a preparation method and application thereof.
Background
With the development of ship technology, the development of ship power is in great demand. Currently gas turbines are the primary choice for ship power. The thermodynamic cycle characteristics of a conventional gas turbine are fixed and the engine can only operate in one mode. The characteristics of ship power require that the engine be in different working states under different conditions, so for the core components of the gas turbine, the turbine rotor is often in complex environments such as cold-hot alternation, stress alternation and the like, which is a great challenge for the materials of the turbine blades. The working environment of the ship power is a marine environment, and long-term corrosion of acid ions generated by the marine environment and heavy oil combustion needs to be resisted simultaneously, so that the material is required to have good corrosion resistance. The output power requirements of gas turbines are continuously increased, the inlet temperature of the gas turbines is higher, and the guide vanes of the gas turbines are subjected to more severe temperature conditions at first, so that the guide vane materials are required to have higher high-temperature resistance and oxidation resistance.
Therefore, providing a nickel-based superalloy that still has excellent oxidation resistance and corrosion resistance at a high temperature of 900 ℃ is a technical problem to be solved in the art.
Disclosure of Invention
The invention aims to provide an oxidation-resistant corrosion-resistant nickel-based superalloy, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
The invention provides an oxidation-resistant corrosion-resistant nickel-based superalloy, which comprises the following chemical components ：C：0.05~0.15%,Cr：16~18%,Co：9~11%,W：2.5~3%,Mo：1~2%,Al：3.5~4%,Ti：3.5~4%,Nb：0.8~1.5%,Ta：1~3%,B：0.002~0.015%,Zr：0.002~0.04% and the balance of Ni in percentage by mass.
Preferably, the oxidation-resistant corrosion-resistant nickel-based superalloy comprises the following chemical components ：C：0.06~0.12%,Cr：16~17%,Co：9~11%,W：2.6~3%,Mo：1.5~2%,Al：3.5~3.8%,Ti：3.5~3.8%,Nb：0.8~1.2%,Ta：1.75~3%,B：0.004~0.01%,Zr：0.005~0.03% and the balance of Ni in mass percent.
Preferably, the chemical components of the oxidation-resistant corrosion-resistant nickel-based superalloy further comprise, in mass percent: y is less than or equal to 0.2 percent.
The invention provides a preparation method of the antioxidation corrosion-resistant nickel-based superalloy, which comprises the following steps:
(1) Smelting alloy raw materials to obtain alloy melt;
(2) Sequentially carrying out gradient refining and pouring on the alloy melt obtained in the step (1) to obtain an alloy cast ingot;
(3) And (3) sequentially performing precision casting and heat treatment on the alloy cast ingot obtained in the step (2) to obtain the oxidation-resistant corrosion-resistant nickel-based superalloy.
Preferably, the alloy raw material in the step (1) comprises electrolytic nickel, metallic chromium, metallic cobalt, metallic tungsten, molybdenum bar, tantalum bar, graphite electrode, nickel-boron master alloy, metallic yttrium, manganese and silicon.
Preferably, the gradient refining in the step (2) is as follows: heating the alloy melt to 1550 ℃ and preserving heat for 15min, and then heating to 1600 ℃ and preserving heat for 30min; the temperature rising mechanism for rising the temperature to 1600 ℃ is to keep the temperature for 10min at 10 ℃ per rise.
Preferably, the casting temperature of the precision casting in the step (3) is 1500-1550 ℃, the shell temperature during the precision casting is 900-950 ℃, and the cooling time of the precision casting is 15-25 min.
Preferably, the heat treatment in the step (3) includes a high-temperature heat treatment and a low-temperature heat treatment which are sequentially performed.
Preferably, the temperature of the high-temperature heat treatment is 1120-1130 ℃, the heat preservation time of the high-temperature heat treatment is 2-2.5 h, the temperature of the low-temperature heat treatment is 840-870 ℃, and the heat preservation time of the low-temperature heat treatment is 20-24 h.
The invention provides an application of the antioxidation corrosion-resistant nickel-based superalloy prepared by the technical scheme or the preparation method in the gas turbine guide vane.
The invention provides an oxidation-resistant corrosion-resistant nickel-based superalloy, which comprises the following chemical components ：C：0.05~0.15%,Cr：16~18%,Co：9~11%,W：2.5~3%,Mo：1~2%,Al：3.5~4%,Ti：3.5~4%,Nb：0.8~1.5%,Ta：1~3%,B：0.002~0.015%,Zr：0.002~0.04% and the balance of Ni in percentage by mass. The Cr element added in the invention exists in the matrix in a solid solution state, and a small amount of Cr element generates carbide, so that the mechanical property of the high-temperature alloy is improved; the combination of Cr element and other environment resistance elements (such as W, mo, nb, ti, al, ta and the like) can be promoted by controlling the dosage of Cr element, so that the stability of a structure is improved, and the comprehensive performance of the alloy is further improved; the addition of a large amount of Co elements can not only improve the hot corrosion resistance of the nickel-based superalloy, but also improve the tissue stability and the high-temperature strength; the W element is a matrix solid solution strengthening element in the high-temperature alloy, so that the strength of the alloy can be improved; the addition of a small amount of Mo element is beneficial to improving the degree of mismatching, achieving the effect of interface reinforcement, and meanwhile, TCP is not formed to damage the structural stability, and the Mo element can reduce the hot corrosion resistance of the alloy, and the hot corrosion resistance is not damaged by the addition of a small amount of Mo element; al, ti and Nb are gamma' -phase forming elements, the Al element can form a protective oxide film at high temperature, the oxidation resistance of the alloy is improved, the Ti element can improve the hot corrosion resistance of the alloy, the problem of tissue instability of the alloy in the long-term use process caused by the increase of the electron space number of the alloy due to the excessively high content of Al and Ti can be avoided by controlling the dosage of the Al element and the Ti element, and the strength and the plasticity of the alloy are further improved; ta is not only a gamma ' -phase forming element, but also a gamma-phase strengthening element, and by controlling the dosage of the Ta, the order degree of the gamma ' -phase can be increased, the solid solution strengthening capability of the gamma ' -phase is improved, and meanwhile, the cost is not increased too much. The results of the examples show that the content of O in the oxidation-resistant corrosion-resistant nickel-based superalloy provided by the invention is less than or equal to 6ppm, the content of N is less than or equal to 6ppm, the oxidation rate of the nickel-based superalloy at 850 ℃ is less than or equal to 0.012g/m 2.h, the oxidation rate of the nickel-based superalloy at 900 ℃ is less than or equal to 0.06g/m 2.h, the hot corrosion rate at 900 ℃ is less than or equal to 0.18 g/(m 2.h), δb is more than 1000MPa at 800 ℃, δp 0.2 is more than 850MPa, δb is more than or equal to 450MPa, τ is more than or equal to 120MPa, δb is more than 830MPa at 900 ℃, δp 0.2 is more than 580MPa, δis more than or equal to 250MPa, δmax is more than or equal to 300MPa, and nf is more than 1×10 7 at 850 ℃.
Detailed Description
The invention provides an oxidation-resistant corrosion-resistant nickel-based superalloy, which comprises the following chemical components ：C：0.05~0.15%,Cr：16~18%,Co：9~11%,W：2.5~3%,Mo：1~2%,Al：3.5~4%,Ti：3.5~4%,Nb：0.8~1.5%,Ta：1~3%,B：0.002~0.015%,Zr：0.002~0.04% and the balance of Ni in percentage by mass.
The oxidation-resistant corrosion-resistant nickel-based superalloy provided by the invention comprises the following components in percentage by mass: 0.05 to 0.15%, preferably 0.06 to 0.12%, more preferably 0.08 to 0.11%. The invention can reduce the oxygen content in the alloy by adding a certain amount of C element.
The oxidation-resistant corrosion-resistant nickel-based superalloy provided by the invention comprises the following components in percentage by mass: 16 to 18%, preferably 16 to 17%, more preferably 16 to 16.5%. According to the invention, cr element is added and exists in a matrix in a solid solution state, and a small amount of carbide is generated, so that the mechanical property of the high-temperature alloy is improved; the combination of Cr element and other environment resistance elements can be promoted by controlling the dosage of Cr element, so that the stability of the structure is improved, and the comprehensive performance of the alloy is further improved.
The oxidation-resistant corrosion-resistant nickel-based superalloy provided by the invention comprises the following components in percentage by mass: 9 to 11%, preferably 9.5 to 11%, more preferably 10 to 10.5%. The invention can not only improve the hot corrosion resistance of the nickel-based superalloy, but also improve the structural stability and the high-temperature strength by adding a large amount of Co elements.
The oxidation-resistant corrosion-resistant nickel-based superalloy provided by the invention comprises the following components in percentage by mass: 2.5 to 3%, preferably 2.6 to 3%. In the invention, the W element is a matrix solid solution strengthening element in the high-temperature alloy, the strength of the alloy can be improved by adding the W element, and meanwhile, excessive W element can promote the formation of TCP, so that the stability of the alloy structure is very unfavorable, and the dosage of the W element is strictly controlled.
The oxidation-resistant corrosion-resistant nickel-based superalloy provided by the invention comprises the following components in percentage by mass: 1 to 2%, preferably 1.5 to 2%, more preferably 1.5 to 1.75%. In the invention, a small amount of Mo element is beneficial to improving the mismatching degree, achieving the effect of interface strengthening, simultaneously, TCP is not formed to damage the tissue stability, and the Mo element can reduce the hot corrosion resistance of the alloy, and a small amount of Mo element can not damage the hot corrosion resistance.
The oxidation-resistant corrosion-resistant nickel-based superalloy provided by the invention comprises the following components in percentage by mass: 3.5 to 4%, preferably 3.5 to 3.8%. In the invention, al element is the most main gamma' phase forming element, and can form a protective oxide film at high temperature, thereby improving the oxidation resistance of the alloy; the excessive content of Al element and Ti element can increase the electron space number of the alloy, so that the alloy is unstable in structure in the long-term use process, and the strength and plasticity of the alloy are damaged by precipitation of harmful phases, so that the dosage of the alloy needs to be strictly controlled.
The oxidation-resistant corrosion-resistant nickel-based superalloy provided by the invention comprises the following components in percentage by mass: 3.5 to 4%, preferably 3.5 to 3.8%. In the invention, ti element is gamma' phase forming element, and simultaneously, the heat corrosion resistance of the alloy can be improved, and the difficulty of solution treatment is increased by controlling the dosage of Ti element and avoiding the eutectic from being difficult to dissolve due to excessive Ti.
The oxidation-resistant corrosion-resistant nickel-based superalloy provided by the invention comprises the following components in percentage by mass: 0.8 to 1.5%, preferably 0.8 to 1.2%. In the present invention, nb element is a γ' phase forming element, and by controlling the amount thereof, the deterioration of the stability of the alloy structure can be avoided.
The oxidation-resistant corrosion-resistant nickel-based superalloy provided by the invention comprises the following components in percentage by mass: 1 to 3%, preferably 1.75 to 3%. In the invention, ta is not only a gamma ' -phase forming element, but also a gamma-phase strengthening element, and by controlling the dosage of the Ta, the ordering degree of the gamma ' -phase can be increased, the solid solution strengthening capability of the gamma ' -phase is improved, and meanwhile, the cost is not increased too much.
The oxidation-resistant corrosion-resistant nickel-based superalloy provided by the invention comprises the following components in percentage by mass: 0.002 to 0.015%, preferably B: 0.004-0.01%. In the present invention, B is a strengthening element between grain boundaries and dendrites in a high temperature alloy, and B, which is biased between grain boundaries and dendrites, can fill gaps in these regions as a gap element, slow diffusion to reduce the tendency of cracking between grain boundaries and dendrites, and also form boride to strengthen grain boundaries and dendrites, and by controlling the content of boron element within the above-mentioned range, the strength of the alloy can be improved.
The oxidation-resistant corrosion-resistant nickel-based superalloy provided by the invention comprises the following components in percentage by mass: 0.002 to 0.04%, preferably 0.005 to 0.03%. In the invention, zr atoms are biased to grain boundaries, so that the grain boundary strength can be improved, and the appearance and distribution result of carbide are improved.
The oxidation-resistant corrosion-resistant nickel-based superalloy provided by the invention preferably further comprises less than or equal to 0.2% of Y, and more preferably 0.005-0.15% of Y. In the invention, the Y element can promote the selective oxidation of Al and Cr elements, reduce the oxidation rate of the alloy, and simultaneously, the Y element is in a composite addition form, so that the alloy has complete oxidation resistance at 1100 ℃, and the oxidation resistance of the alloy can be improved by controlling the content of the Y element in the range.
The oxidation-resistant corrosion-resistant nickel-based superalloy provided by the invention comprises the balance of Ni in percentage by mass. In the present invention, ni element is a matrix element of the alloy.
In the invention, cr element exists in a matrix in a solid solution state, and a small amount of Cr element generates carbide, so that the mechanical property of the high-temperature alloy is improved; the combination of Cr element and other environment resistance elements (such as W, mo, nb, ti, al, ta and the like) can be promoted by controlling the dosage of Cr element, so that the stability of a structure is improved, and the comprehensive performance of the alloy is further improved; the addition of a large amount of Co elements can not only improve the hot corrosion resistance of the nickel-based superalloy, but also improve the tissue stability and the high-temperature strength; the W element is a matrix solid solution strengthening element in the high-temperature alloy, so that the strength of the alloy can be improved; the addition of a small amount of Mo element is beneficial to improving the degree of mismatching, achieving the effect of interface reinforcement, and meanwhile, TCP is not formed to damage the structural stability, and the Mo element can reduce the hot corrosion resistance of the alloy, and the hot corrosion resistance is not damaged by the addition of a small amount of Mo element; al, ti and Nb are gamma' -phase forming elements, the Al element can form a protective oxide film at high temperature, the oxidation resistance of the alloy is improved, the Ti element can improve the hot corrosion resistance of the alloy, the problem of tissue instability of the alloy in the long-term use process caused by the increase of the electron space number of the alloy due to the excessively high content of Al and Ti can be avoided by controlling the dosage of the Al element and the Ti element, and the strength and the plasticity of the alloy are further improved; ta is not only a gamma ' -phase forming element, but also a gamma-phase strengthening element, and by controlling the dosage of the Ta, the order degree of the gamma ' -phase can be increased, the solid solution strengthening capability of the gamma ' -phase is improved, and meanwhile, the cost is not increased too much.
The invention provides a preparation method of the antioxidation corrosion-resistant nickel-based superalloy, which comprises the following steps:
(1) Smelting alloy raw materials to obtain alloy melt;
(2) Sequentially carrying out gradient refining and pouring on the alloy melt obtained in the step (1) to obtain an alloy cast ingot;
(3) And (3) sequentially performing precision casting and heat treatment on the alloy cast ingot obtained in the step (2) to obtain the oxidation-resistant corrosion-resistant nickel-based superalloy.
The invention smelts alloy raw materials to obtain alloy melt.
In the present invention, the alloy raw material preferably includes electrolytic nickel, metallic chromium, metallic aluminum, metallic zirconium, metallic cobalt, metallic tungsten, molybdenum bar, tantalum bar, carbon, nickel-boron master alloy, metallic yttrium, manganese and silicon; the electrolytic nickel is preferably Ni9996; the metallic chromium is preferably GCCr-1; the metallic cobalt is preferably Co9995; the metallic tungsten is preferably TW-1; the molybdenum strip is preferably Mo-1; the tantalum strip is preferably TD-T; the carbon is preferably a spectrographite electrode (TSG); the nickel boron master alloy is preferably a Ni- (18 wt%) B master alloy; the yttrium metal is preferably Y99.99; the manganese is preferably DJMnG; the silicon is preferably Si-1; the aluminum metal is preferably Al99.995; the zirconium metal is preferably HZr-01. The specific dosage of the alloy raw materials is not particularly limited, and the chemical components of the finally obtained oxidation-resistant corrosion-resistant nickel-based superalloy can meet the requirements. The source of the alloy raw material is not particularly limited, and commercially available products known to those skilled in the art may be used.
In the present invention, the smelting is preferably performed in a smelting furnace. The specific type of the smelting furnace is not particularly limited, and commercially available products known to those skilled in the art may be used.
In the invention, the charging sequence in smelting is preferably as follows: adding part of carbon into a crucible, then adding electrolytic nickel, metallic chromium, metallic cobalt, metallic tungsten, molybdenum strips, tantalum strips, nickel-boron intermediate alloy, manganese and silicon, and finally adding the rest of carbon. In the present invention, when Y is contained in the oxidation-resistant corrosion-resistant nickel-based superalloy, the yttrium metal is preferably added together with manganese. In the present invention, the mass of the partial carbon is preferably 1/2 of the total mass of carbon. According to the invention, through the feeding mode, carbon can be contacted with the smelting furnace, the crucible and the raw materials, so that oxygen elements adsorbed by the raw materials, the inner wall of the furnace body and the inner wall of the crucible in the refining process are removed, and the oxygen content in the alloy is further reduced.
In the present invention, the crucible is preferably coated with a yttria coating on the surface thereof before use. According to the invention, the yttrium oxide coating is coated on the surface of the crucible, so that the heat resistance of the crucible can be enhanced, the reaction between the molten superalloy and the crucible in the refining process can be reduced, and the release of O, N and other elements into the crucible can be reduced.
In the present invention, the atmosphere for smelting is preferably a vacuum atmosphere. The vacuum degree of the vacuum atmosphere is not particularly limited, and may be determined according to the technical common knowledge of a person skilled in the art. The invention can reduce the oxygen content in smelting and avoid oxidation in the smelting process by controlling the smelting atmosphere.
The temperature and time of the smelting are not particularly limited, and the raw materials can be completely melted according to the technical common knowledge of the person skilled in the art.
After the alloy melt is obtained, the alloy melt is subjected to gradient refining and pouring in sequence to obtain an alloy cast ingot.
In the present invention, the gradient refining method is preferably as follows: heating the alloy melt to 1550 ℃ and preserving heat for 15min, and then heating to 1600 ℃ and preserving heat for 30min; the temperature rising mechanism for rising the temperature to 1600 ℃ is to keep the temperature for 10min at 10 ℃ per rise. According to the invention, the gradient heating process is adopted for refining, so that the crucible can be prevented from discharging oxygen due to rapid heating, and the slow heating process is beneficial to increasing the gas removal effect of Sievert's law.
In the invention, the chute preferably uses double filter screens during pouring; the pore diameter of the first filter screen in the double filter screens is preferably 10ppi; the pore diameter of the second filter screen in the double filter screen is preferably 15ppi. The filter screen can remove impurities.
After the casting is finished, the invention preferably carries out excircle grinding and cutting on the cast product into sections. The specific operations of polishing and cutting the outer circle into segments are not particularly limited, and can be determined according to the technical common knowledge of a person skilled in the art.
After the alloy ingot is obtained, the alloy ingot is subjected to precision casting, pouring and heat treatment in sequence, so that the oxidation-resistant corrosion-resistant nickel-based superalloy is obtained.
In the present invention, the precision casting is preferably performed in an equiaxed crystal furnace. The specific model of the isometric crystal furnace is not particularly limited, and commercial products known to those skilled in the art can be adopted.
In the invention, the casting temperature of the precision casting is preferably 1500-1550 ℃; the shell temperature during precision casting and pouring is preferably 900-950 ℃; the cooling time of the precision casting pouring is preferably 15-25 min, more preferably 20min. In the invention, the low casting temperature can seriously affect the fluidity of the alloy, so that the alloy has poor filling property and has the defects of shrinkage cavity, shrinkage porosity and the like; the casting temperature is too high, the crystal grain size is too large, the strength of the alloy can be seriously affected, and the mechanical property of the alloy can be further improved by controlling the temperature during precision casting and casting.
In the present invention, the heat treatment preferably includes a high-temperature heat treatment and a low-temperature heat treatment performed in this order; the temperature of the high-temperature heat treatment is preferably 1120-1130 ℃; the heat preservation time of the high-temperature heat treatment is preferably 2-2.5 h; the temperature of the low-temperature heat treatment is preferably 840-870 ℃; the heat preservation time of the low-temperature heat treatment is preferably 20-24 hours. By adopting the mode to heat treat the alloy cast ingot, the invention can eliminate the component segregation of the alloy, improve the cube degree of the strengthening phase and improve the strength of the alloy.
According to the invention, C with the total mass of 1/2 of that of carbon is added during the feeding process, so that oxygen elements adsorbed by raw materials, the inner wall of a furnace body and the inner wall of a crucible in the refining process are removed, then the gradient heating refining process can avoid oxygen discharge of the crucible caused by rapid heating, and the slow heating process is beneficial to increasing the gas removal effect of Sievert's law; in the alloy smelting process, the raw materials are carried out in a crucible coated with a yttrium oxide coating, the yttrium oxide coating can enhance the heat resistance of the crucible, reduce the reaction between molten high-temperature alloy and the crucible in the refining process, and reduce the release of O, N and other elements into the crucible; by controlling parameters in the precision casting process, the defects of poor alloy filling property, shrinkage cavity, shrinkage porosity and the like caused by too low casting temperature, too high casting temperature, too large grain size and serious influence on alloy strength are avoided.
The preparation method provided by the invention is simple, can be carried out by the existing equipment, has low production cost, and is suitable for industrial mass production.
The invention provides an application of the antioxidation corrosion-resistant nickel-based superalloy prepared by the technical scheme or the preparation method in the gas turbine guide vane.
The specific mode of the application of the present invention is not particularly limited, and modes well known to those skilled in the art can be adopted.
The oxidation-resistant corrosion-resistant nickel-based superalloy provided by the invention has the characteristics of oxidation resistance, corrosion resistance and long service life, and the prepared gas turbine guide vane can still have good mechanical properties at 900 ℃.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the oxidation-resistant corrosion-resistant nickel-based superalloy comprises the following steps:
(1) Coating a layer of yttrium oxide coating on the surface of a crucible in a smelting furnace, firstly adding 1/2 of carbon by the total mass of carbon into the crucible, then adding Ni9996, GCCr-1, co9995, TW-1, mo-1, TD-T, nickel boron intermediate alloy, Y99.99, DJMnG and Si-1, finally adding the rest carbon, and smelting to obtain alloy melt; the smelting atmosphere is vacuum atmosphere; the carbon is a spectrographite electrode (TSG);
(2) Sequentially carrying out gradient refining and pouring on the alloy melt obtained in the step (1), and sequentially carrying out excircle polishing and cutting into sections on a poured product after pouring to obtain an alloy cast ingot; the gradient refining mode is as follows: heating the alloy melt to 1550 ℃ and preserving heat for 15min, and then heating to 1600 ℃ and preserving heat for 30min; the temperature rising mechanism for rising the temperature to 1600 ℃ is to keep the temperature for 10min at 10 ℃ per rise; during pouring, the chute uses double filter screens, wherein the aperture of a first filter screen in the double filter screens is 10ppi, and the aperture of a second filter screen in the double filter screens is 15ppi;
(3) Sequentially performing precision casting and pouring on the alloy cast ingot obtained in the step (2) in an isometric crystal furnace, and then performing high-temperature heat treatment and low-temperature heat treatment to obtain an oxidation-resistant corrosion-resistant nickel-based superalloy; the casting temperature of the precision casting is 1550 ℃, the shell temperature during the precision casting is 950 ℃, and the cooling time of the precision casting is 20min; the temperature of the high-temperature heat treatment is 1120 ℃, and the heat preservation time of the high-temperature heat treatment is 2h; the temperature of the low-temperature heat treatment is 850 ℃, and the heat preservation time of the low-temperature heat treatment is 24 hours.
The chemical compositions of the oxidation-resistant corrosion-resistant nickel-based superalloy prepared in example 1 are shown in table 1:
TABLE 1 chemical composition of antioxidant corrosion resistant Nickel-based superalloy prepared in example 1
| Chemical composition | wt.% |
| C | 0.11 |
| Cr | 16.5 |
| Co | 9 |
| W | 2.6 |
| Mo | 1.75 |
| Al | 3.6 |
| Ti | 3.5 |
| Nb | 0.8 |
| Ta | 1.75 |
| B | 0.01 |
| Zr | 0.03 |
| Y | 0 |
| Ni | Allowance of |
| O | 4ppm |
| N | 4ppm |
Example 2
The preparation method is the same as in example 1.
The chemical compositions of the oxidation-resistant corrosion-resistant nickel-based superalloy prepared in example 2 are shown in table 2:
TABLE 2 chemical compositions of the oxidation-resistant corrosion-resistant nickel-based superalloy prepared in EXAMPLE 2
| Chemical composition | wt.% |
| C | 0.013 |
| Cr | 16 |
| Co | 11 |
| W | 3 |
| Mo | 2 |
| Al | 3.5 |
| Ti | 3.5 |
| Nb | 1.2 |
| Ta | 3 |
| B | 0.004 |
| Zr | 0.03 |
| Y | 0.005 |
| Ni | Allowance of |
| O | 5ppm |
| N | 5ppm |
The oxidation resistance and corrosion resistance of the oxidation-resistant corrosion-resistant nickel-based superalloy prepared in example 1 and example 2 at high temperature were tested with the following test criteria: HB5258 test method for measuring oxidation resistance of Steel and superalloy and HB7740 test method for gas Hot Corrosion, the results are shown in Table 3:
TABLE 3 high temperature Oxidation resistance and Corrosion resistance of the antioxidant corrosion resistant Nickel-based superalloy prepared in examples 1-2
| Example 1 | Example 2 | |
| Oxidation rate at 850 ℃ | 0.012g/m2·h | 0.009g/m2·h |
| Oxidation rate at 900 °c | 0.06g/m2·h | 0.04g/m2·h |
| Oxidation rate at 1000 DEG C | 0.3g/m2·h | 0.1g/m2·h |
| Oxidation rate at 1100 °c | 0.3g/m2·h | 0.1g/m2·h |
| Hot corrosion rate at 900 DEG C | 0.18g/（m2·h） | 0.14g/（m2·h） |
As can be seen from Table 3, the oxidation-resistant corrosion-resistant nickel-based superalloy prepared by the method has excellent oxidation resistance and corrosion resistance at the temperature of less than or equal to 900 ℃, and has better oxidation resistance at the moment although the oxidation rate is increased when the temperature reaches more than 1000 ℃.
The tensile properties of the oxidation-resistant corrosion-resistant nickel-based superalloy prepared in example 1 and example 2at high temperature were tested respectively, with the test criteria: HB5195 "Metal high temperature tensile test method", the results are shown in tables 4 and 5, respectively:
TABLE 4 high temperature tensile Properties of the antioxidant corrosion resistant Nickel-based superalloy prepared in example 1
| Temperature (temperature) | δb/MPa | δp0.2/MPa |
| 20℃ | 1030 | 880 |
| 700℃ | 1065 | 835 |
| 800℃ | 1020 | 855 |
| 900℃ | 835 | 585 |
| 1000℃ | 485 | 375 |
TABLE 5 high temperature tensile Properties of the antioxidant corrosion resistant Nickel-based superalloy prepared in example 2
| Temperature (temperature) | δb/MPa | δp0.2/MPa |
| 20℃ | 1056 | 890 |
| 700℃ | 1070 | 860 |
| 800℃ | 1065 | 870 |
| 900℃ | 900 | 612 |
| 1000℃ | 500 | 401 |
In tables 4 and 5, δb is the breaking strength, δp 0.2 is the stress at which 0.2% plastic strain is generated. As can be seen from tables 4 and 5, the oxidation-resistant corrosion-resistant nickel-based superalloy prepared by the invention has excellent high-temperature tensile properties at a temperature of less than or equal to 900 ℃, and the high-temperature tensile properties are greatly reduced when the temperature reaches more than 1000 ℃.
The oxidation-resistant corrosion-resistant nickel-based superalloy prepared in example 1 and example 2 were tested for durability at high temperature, respectively, with the test criteria: HB5150 "method for high temperature endurance test of metals", the results of which are shown in Table 6 and Table 7, respectively:
TABLE 6 high temperature durability of the oxidation resistant corrosion resistant nickel-based superalloy prepared in EXAMPLE 1
| Temperature (temperature) | δ/MPa | τ/MPa |
| 700℃ | 650 | 251 |
| 800℃ | 450 | 120 |
| 900℃ | 250 | 136 |
TABLE 7 high temperature durability of the oxidation resistant corrosion resistant nickel-based superalloy prepared in EXAMPLE 2
| Temperature (temperature) | δ/MPa | τ/MPa |
| 700℃ | 650 | 268 |
| 800℃ | 450 | 135 |
| 900℃ | 250 | 152 |
In tables 6 and 7, δ is the loading stress at the time of the endurance test; τ is the permanent break time. As can be seen from tables 6 and 7, the high-temperature durability of the anti-oxidation corrosion-resistant nickel-based superalloy prepared by the invention is continuously reduced along with the increase of temperature, but the high-temperature durability is excellent at 900 ℃, which indicates that the anti-oxidation corrosion-resistant nickel-based superalloy prepared by the invention can work for a long time at the high temperature of 900 ℃.
The oxidation-resistant corrosion-resistant nickel-based superalloy prepared in example 1 and example 2 was tested for high cycle fatigue performance at high temperature, respectively, with the test criteria: HB 20449-2018, method for high-temperature axial high-cycle fatigue test of metallic Material, wherein R=0.1; f= (15 to 30) HZ, and the results are shown in table 8 and table 9, respectively:
TABLE 8 high cycle fatigue Properties of the antioxidant corrosion resistant Nickel-based superalloy prepared in example 1
| Temperature (temperature) | δmax/MPa | Nf |
| 850℃ | 300 | ＞1×107 |
Table 9 high cycle fatigue properties of the oxidation-resistant corrosion-resistant nickel-based superalloy prepared in example 2
| Temperature (temperature) | δmax//MPa | Nf |
| 850℃ | 300 | ＞1×107 |
In tables 8 and 9, δmax is the maximum value of cyclic stress, and Nf is the number of cycles. As can be seen from tables 8 and 9, the oxidation-resistant corrosion-resistant cobalt-based superalloy prepared by the method has good fatigue resistance while ensuring certain durability and good oxidation-resistant corrosion resistance.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. An oxidation-resistant corrosion-resistant nickel-based superalloy comprises the following chemical components ：C：0.05~0.15%,Cr：16~18%,Co：9~11%,W：2.5~3%,Mo：1~2%,Al：3.5~4%,Ti：3.5~4%,Nb：0.8~1.5%,Ta：1~3%,B：0.002~0.015%,Zr：0.002~0.04% and the balance of Ni in percentage by mass.
2. The oxidation-resistant corrosion-resistant nickel-base superalloy of claim 1, comprising, in mass percent, the following chemical composition ：C：0.06~0.12%,Cr：16~17%,Co：9~11%,W：2.6~3%,Mo：1.5~2%,Al：3.5~3.8%,Ti：3.5~3.8%,Nb：0.8~1.2%,Ta：1.75~3%,B：0.004~0.01%,Zr：0.005~0.03% and the balance Ni.
3. The oxidation-resistant corrosion-resistant nickel-base superalloy according to claim 1 or 2, wherein the chemical composition of the oxidation-resistant corrosion-resistant nickel-base superalloy further comprises, in mass percent: y is less than or equal to 0.2 percent.
4. The method for preparing the oxidation-resistant corrosion-resistant nickel-based superalloy according to any one of claims 1 to 3, comprising the following steps:
(1) Smelting alloy raw materials to obtain alloy melt;
(2) Sequentially carrying out gradient refining and pouring on the alloy melt obtained in the step (1) to obtain an alloy cast ingot;
(3) And (3) sequentially performing precision casting and heat treatment on the alloy cast ingot obtained in the step (2) to obtain the oxidation-resistant corrosion-resistant nickel-based superalloy.
5. The method according to claim 4, wherein the alloy material in the step (1) comprises electrolytic nickel, metallic chromium, metallic cobalt, metallic tungsten, molybdenum strip, tantalum strip, graphite electrode, nickel boron master alloy, metallic yttrium, manganese and silicon.
6. The method according to claim 4, wherein the gradient refining in the step (2) is performed by: heating the alloy melt to 1550 ℃ and preserving heat for 15min, and then heating to 1600 ℃ and preserving heat for 30min; the temperature rising mechanism for rising the temperature to 1600 ℃ is to keep the temperature for 10min at 10 ℃ per rise.
7. The method according to claim 4, wherein the casting temperature of the precision casting in the step (3) is 1500-1550 ℃, the shell temperature of the precision casting is 900-950 ℃, and the cooling time of the precision casting is 15-25 min.
8. The method according to claim 4, wherein the heat treatment in the step (3) comprises a high-temperature heat treatment and a low-temperature heat treatment which are sequentially performed.
9. The method according to claim 8, wherein the high-temperature heat treatment is performed at 1120-1130 ℃, the heat preservation time of the high-temperature heat treatment is 2-2.5 h, the temperature of the low-temperature heat treatment is 840-870 ℃, and the heat preservation time of the low-temperature heat treatment is 20-24 h.
10. Use of the oxidation-resistant corrosion-resistant nickel-base superalloy according to any of claims 1 to 3 or the oxidation-resistant corrosion-resistant nickel-base superalloy prepared by the preparation method according to any of claims 4 to 9 in a gas turbine guide vane.
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