CN118028660A - Antioxidant corrosion-resistant cobalt-based superalloy, and preparation method and application thereof - Google Patents
Antioxidant corrosion-resistant cobalt-based superalloy, and preparation method and application thereof Download PDFInfo
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 93
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- 230000007797 corrosion Effects 0.000 title claims abstract description 93
- 238000005260 corrosion Methods 0.000 title claims abstract description 93
- 229910000601 superalloy Inorganic materials 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003963 antioxidant agent Substances 0.000 title description 11
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- 238000007254 oxidation reaction Methods 0.000 claims abstract description 79
- 239000000126 substance Substances 0.000 claims abstract description 20
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 19
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- 238000003723 Smelting Methods 0.000 claims description 59
- 238000007670 refining Methods 0.000 claims description 31
- 239000011572 manganese Substances 0.000 claims description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- 238000005266 casting Methods 0.000 claims description 22
- 239000011651 chromium Substances 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 238000005495 investment casting Methods 0.000 claims description 19
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- 229910052748 manganese Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 10
- 239000010937 tungsten Substances 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 229910052715 tantalum Inorganic materials 0.000 claims description 9
- 229910052727 yttrium Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
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- Turbine Rotor Nozzle Sealing (AREA)
Abstract
The invention provides an oxidation-resistant corrosion-resistant cobalt-based superalloy, and a preparation method and application thereof, and belongs to the technical field of cobalt-based superalloys. The invention provides an oxidation-resistant corrosion-resistant cobalt-based superalloy, which comprises the following chemical components in percentage by mass: c: 0.3-0.6%, cr: 26-30%, ni: 8.5-10.5%, W: 7-10%, B: 0.003-0.006%, mn less than or equal to 1.5%, si less than or equal to 1.5% and the balance Co. The results of the examples show that the oxidation rate of the cobalt-based superalloy provided by the invention is less than or equal to 0.05 g/(m 2.h) at 900 ℃, the oxidation rate of the cobalt-based superalloy at 1000 ℃ is less than or equal to 0.09 g/(m 2.h), and the hot corrosion rate of the cobalt-based superalloy at 900 ℃ is less than or equal to 0.18 g/(m 2.h).
Description
Technical Field
The invention relates to the technical field of cobalt-based superalloy, in particular to an oxidation-resistant corrosion-resistant cobalt-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 cobalt-based superalloy with excellent oxidation resistance and corrosion resistance at 1000 ℃ is a technical problem to be solved in the art.
Disclosure of Invention
The invention aims to provide an oxidation-resistant corrosion-resistant cobalt-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 cobalt-based superalloy, which comprises the following chemical components in percentage by mass: c: 0.3-0.6%, cr: 26-30%, ni: 8.5-10.5%, W: 7-10%, B: 0.003-0.006%, mn less than or equal to 1.5%, si less than or equal to 1.5% and the balance Co.
Preferably, the composition comprises the following chemical components in percentage by mass: c: 0.3-0.5%, cr: 26-28%, ni: 9-10.5%, W: 7.5-9%, B: 0.003-0.006%, mn: 0.5-0.8%, si: 0.5-0.8% and the balance of Co.
Preferably, the chemical components of the oxidation-resistant corrosion-resistant cobalt-based superalloy further comprise, in mass percent: ta is less than or equal to 2%, mo is less than or equal to 1% and Y is less than or equal to 0.2%.
The invention provides a preparation method of the antioxidation corrosion-resistant cobalt-based superalloy, which comprises the following steps:
(1) Mixing a nickel source, a chromium source, a cobalt source, a tungsten source and a part of carbon source, and then sequentially carrying out low-temperature smelting, high-temperature smelting and high-temperature refining to obtain a first alloy melt;
(2) Adding a residual carbon source, a silicon source and a boron source into the first alloy melt obtained in the step (1) to perform secondary smelting to obtain a second alloy melt;
(3) Adding a manganese source into the second alloy melt obtained in the step (2), and then refining and pouring in sequence to obtain an alloy cast ingot;
(4) Performing precision casting on the alloy cast ingot obtained in the step (3) to obtain an oxidation-resistant corrosion-resistant cobalt-based superalloy;
When Ta and Mo are included in the prepared oxidation-resistant corrosion-resistant cobalt-based superalloy, the tantalum source and the molybdenum source are mixed with a nickel source, a chromium source, a cobalt source, a tungsten source and a part of carbon source;
when Y is included in the prepared oxidation-resistant corrosion-resistant cobalt-based superalloy, the yttrium source and the manganese source are added into the second alloy melt together.
Preferably, the power of low-temperature smelting in the step (1) is 80-85 kW, and the time of low-temperature smelting is 50-60 min.
Preferably, the power of high-temperature smelting in the step (1) is 140-160 kW, and the time of high-temperature smelting is 60-80 min.
Preferably, the temperature of the high-temperature refining in the step (1) is 1620-1650 ℃, and the time of the high-temperature refining is 60min.
Preferably, the power of the second smelting in the step (2) is 140-160 kw, and the time of the second smelting is 10min.
Preferably, the casting temperature of the precision casting in the step (4) is 1500-1550 ℃, the shell temperature during the precision casting is 1000-1050 ℃, and the cooling time of the precision casting is 15-25 min.
The invention provides an application of the antioxidation corrosion-resistant cobalt-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 cobalt-based superalloy, which comprises the following chemical components in percentage by mass: c: 0.3-0.6%, cr: 26-30%, ni: 8.5-10.5%, W: 7-10%, B: 0.003-0.006%, mn less than or equal to 1.5%, si less than or equal to 1.5% and the balance Co. The Co element is used as a matrix element of the alloy, so that the alloy has good hot corrosion resistance, and meanwhile, the structure stability and the high-temperature strength can be improved; 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, 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 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 Mn element can promote the fluidity of the alloy in the casting process, improve the welding performance and inhibit the hot cracking tendency of the alloy in a high-temperature environment; the Si element can promote the fluidity of the alloy in the casting process, improve the welding performance and inhibit the hot cracking tendency of the alloy in a high-temperature environment; the problem that the alloy strength is reduced due to the formation of harmful inclusions in the casting process caused by excessive content of Mn and Si elements is avoided by controlling the content of Mn and Si elements, and the grain boundary is gradually embrittled in the long-term use process is avoided; ta is not only a gamma ' -phase forming element, but also a gamma-phase strengthening element, 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 addition of a small amount of Mo is beneficial to improving the degree of mismatching and achieving the effect of interface reinforcement, meanwhile, TCP is not formed to damage the tissue stability, and meanwhile, the addition of a small amount of Mo element does not damage the hot corrosion resistance of the high-temperature alloy; the Y element can promote the selective oxidation of Cr element, and reduce the oxidation rate of the alloy; meanwhile, the Y element can inhibit the sulfur effect and the like by reducing holes at the interface of the oxide film and the alloy, so that the anti-stripping capability of the oxide film on the surface of the alloy is improved; by controlling the dosage of the Y element and the compound addition form of the trace elements, the alloy achieves the complete oxidation resistance at 1000 ℃, and the problems that the oxidation condition of the alloy is not obviously improved due to too little element and the oxidation resistance of the alloy is deteriorated due to too much content are avoided. The results of the examples show that the oxidation rate of the oxidation-resistant corrosion-resistant cobalt-based superalloy provided by the invention is less than or equal to 0.05 g/(m 2.h) at 900 ℃, the oxidation rate at 1000 ℃ is less than or equal to 0.09 g/(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 or equal to 570MPa at 700 ℃, δp 0.2 is more than or equal to 220MPa, δ is more than or equal to 380MPa, τ is more than or equal to 50MPa, δb is more than or equal to 420MPa at 800 ℃, δp 0.2 is more than or equal to 280MPa, δ is more than or equal to 240MPa, τ is more than or equal to 22MPa, δb is more than or equal to 330MPa at 900 ℃, δp 0.2 is more than or equal to 140MPa, τ is more than or equal to 50MPa, δb is more than or equal to 200MPa at 980 ℃, δp 0.2 is more than or equal to 88MPa, τ is more than or equal to 35MPa at 850 ℃ and δmax is more at 850 ℃ is more than 1×10 7.
Detailed Description
The invention provides an oxidation-resistant corrosion-resistant cobalt-based superalloy, which comprises the following chemical components in percentage by mass: c: 0.3-0.6%, cr: 26-30%, ni: 8.5-10.5%, W: 7-10%, B: 0.003-0.006%, mn less than or equal to 1.5%, si less than or equal to 1.5% and the balance Co.
The oxidation-resistant corrosion-resistant cobalt-based superalloy provided by the invention comprises the following components in percentage by mass: 0.3 to 0.6%, preferably 0.3 to 0.5%, more preferably 0.4 to 0.5%. The invention can reduce the oxygen content in the alloy by adding a certain amount of C element.
The oxidation-resistant corrosion-resistant cobalt-based superalloy provided by the invention comprises the following components in percentage by mass: 26 to 30%, preferably 26 to 28%, more preferably 27 to 28%. 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 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 cobalt-based superalloy provided by the invention comprises the following components in percentage by mass: 8.5 to 10.5%, preferably 9 to 10.5%, more preferably 9.5 to 10.5%. In the invention, ni element exists in a matrix in a solid solution state, the Ni element can increase the volume fraction of gamma' in the cobalt-based superalloy to improve the alloy strength, and meanwhile, the addition of Ni is also beneficial to improving the tissue stability.
The oxidation-resistant corrosion-resistant cobalt-based superalloy provided by the invention comprises the following components in percentage by mass: 7 to 10%, preferably 7.5 to 9%. In the present invention, the W element is a matrix solid solution strengthening element in a superalloy, and the strength of the alloy can be improved by adding the W element, but excessive W element promotes TCP formation, which is very disadvantageous in terms of alloy structure stability, and thus the amount thereof needs to be controlled.
The oxidation-resistant corrosion-resistant cobalt-based superalloy provided by the invention comprises the following components in percentage by mass: 0.003 to 0.006%, preferably 0.004 to 0.005%.
The oxidation-resistant corrosion-resistant cobalt-based superalloy provided by the invention comprises less than or equal to 1.5% of Mn, preferably 0.5-0.8%, and more preferably 0.7-0.8%. According to the invention, the addition of Mn element can promote the fluidity of the alloy in the casting process, improve the welding performance and inhibit the hot cracking tendency of the alloy in a high-temperature environment; by controlling the amount of Mn element, the problem that the alloy strength is reduced due to the formation of harmful inclusions in the casting process caused by excessive Mn element content and the grain boundary is gradually embrittled in the long-term use process is avoided.
The oxidation-resistant corrosion-resistant cobalt-based superalloy provided by the invention comprises less than or equal to 1.5% of Si, preferably 0.5-0.8%, and more preferably 0.7-0.8%. In the invention, the addition of Si element can promote the fluidity of the alloy in the casting process, improve the welding performance and inhibit the hot cracking tendency of the alloy in a high-temperature environment; by controlling the dosage of Si element, the problem that the alloy strength is reduced due to the formation of harmful impurities in the casting process caused by excessive content of Si element and the grain boundary is gradually embrittled in the long-term use process is avoided.
The oxidation-resistant corrosion-resistant cobalt-based superalloy provided by the invention preferably further comprises less than or equal to 2% of Ta, more preferably 0.5-2%, and even more preferably 1-2%. 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 cobalt-based superalloy provided by the invention preferably further comprises less than or equal to 1% of Mo, and more preferably 0.5-1%. In the invention, the small addition of Mo is favorable for improving the mismatching degree and achieving the effect of interface strengthening, meanwhile, TCP is not formed to damage the tissue stability, and meanwhile, the small addition of Mo element does not damage the hot corrosion resistance of the superalloy.
The oxidation-resistant corrosion-resistant cobalt-based superalloy provided by the invention preferably further comprises the following components in percentage by mass: y is not more than 0.2%, more preferably 0.005 to 0.15%. In the invention, the Y element can promote the selective oxidation with Cr element, and reduce the oxidation rate of the alloy; meanwhile, the Y element can inhibit the sulfur effect and the like by reducing holes at the interface of the oxide film and the alloy, so that the anti-stripping capability of the oxide film on the surface of the alloy is improved; by controlling the dosage of the Y element and the compound addition form of the trace elements, the alloy achieves the complete oxidation resistance at 1000 ℃, and the problems that the oxidation condition of the alloy is not obviously improved due to too little element and the oxidation resistance of the alloy is deteriorated due to too much content are avoided.
The oxidation-resistant corrosion-resistant cobalt-based superalloy provided by the invention comprises the balance Co in percentage by mass. In the invention, co element is a matrix element of the alloy, so that the alloy has good hot corrosion resistance, and meanwhile, the structure stability and the high-temperature strength can be improved.
The Co element is used as a matrix element of the alloy, so that the alloy has good hot corrosion resistance, and meanwhile, the structure stability and the high-temperature strength can be improved; 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, 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 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 Mn element can promote the fluidity of the alloy in the casting process, improve the welding performance and inhibit the hot cracking tendency of the alloy in a high-temperature environment; the Si element can promote the fluidity of the alloy in the casting process, improve the welding performance and inhibit the hot cracking tendency of the alloy in a high-temperature environment; the problem that the alloy strength is reduced due to the formation of harmful inclusions in the casting process caused by excessive content of Mn and Si elements is avoided by controlling the content of Mn and Si elements, and the grain boundary is gradually embrittled in the long-term use process is avoided; ta is not only a gamma ' -phase forming element, but also a gamma-phase strengthening element, 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 addition of a small amount of Mo is beneficial to improving the degree of mismatching and achieving the effect of interface reinforcement, meanwhile, TCP is not formed to damage the tissue stability, and meanwhile, the addition of a small amount of Mo element does not damage the hot corrosion resistance of the high-temperature alloy; the Y element can promote the selective oxidation of Cr element, and reduce the oxidation rate of the alloy; meanwhile, the Y element can inhibit the sulfur effect and the like by reducing holes at the interface of the oxide film and the alloy, so that the anti-stripping capability of the oxide film on the surface of the alloy is improved; by controlling the dosage of the Y element and the compound addition form of the trace elements, the alloy achieves the complete oxidation resistance at 1000 ℃, and the problems that the oxidation condition of the alloy is not obviously improved due to too little element and the oxidation resistance of the alloy is deteriorated due to too much content are avoided.
According to the invention, through optimizing the chemical components of the cobalt-based superalloy, the problem of poor structural stability of the alloy caused by poor combination capability of high Wen Kangxing elements and environmental resistance elements in the prior art is solved, so that the comprehensive performance of the alloy can be fully exerted, the oxidation resistance and corrosion resistance of the superalloy are greatly improved, and the service life of the superalloy is longer.
The invention provides a preparation method of the antioxidation corrosion-resistant cobalt-based superalloy, which comprises the following steps:
(1) Mixing a nickel source, a chromium source, a cobalt source, a tungsten source and a part of carbon source, and then sequentially carrying out low-temperature smelting, high-temperature smelting and high-temperature refining to obtain a first alloy melt;
(2) Adding a residual carbon source, a silicon source and a boron source into the first alloy melt obtained in the step (1) to perform secondary smelting to obtain a second alloy melt;
(3) Adding a manganese source into the second alloy melt obtained in the step (2), and then refining and pouring in sequence to obtain an alloy cast ingot;
(4) Performing precision casting on the alloy cast ingot obtained in the step (3) to obtain an oxidation-resistant corrosion-resistant cobalt-based superalloy;
When Ta and Mo are included in the prepared oxidation-resistant corrosion-resistant cobalt-based superalloy, the tantalum source and the molybdenum source are mixed with a nickel source, a chromium source, a cobalt source, a tungsten source and a part of carbon source;
when Y is included in the prepared oxidation-resistant corrosion-resistant cobalt-based superalloy, the yttrium source and the manganese source are added into the second alloy melt together.
The specific sources of the raw materials used in the preparation process are not particularly limited, and commercially available products known to those skilled in the art may be used. The specific dosage of the raw materials used in the preparation process is not particularly limited, and the components of the oxidation-resistant corrosion-resistant cobalt-based superalloy can meet the requirements.
According to the invention, a nickel source, a chromium source, a cobalt source, a tungsten source and a part of carbon source are mixed and then subjected to low-temperature smelting, high-temperature smelting and high-temperature refining in sequence to obtain a first alloy melt.
In the present invention, when Ta and Mo are included in the prepared oxidation-resistant corrosion-resistant cobalt-based superalloy, the tantalum source and the molybdenum source are mixed together with a nickel source, a chromium source, a cobalt source, a tungsten source, and a part of a carbon source.
In the present invention, the partial carbon source is preferably 1/3 of the total mass of the carbon source. In the present invention, the nickel source is preferably electrolytic nickel, more preferably Ni9996; the chromium source is preferably metallic chromium, more preferably GCCr-1; the cobalt source is preferably metallic cobalt, more preferably Co9995; the tungsten source is preferably metallic tungsten, more preferably TW-1; the molybdenum source is metallic molybdenum, more preferably Mo-1; the boron source is preferably a nickel boron master alloy, more preferably a Ni- (18 wt%) B master alloy; the carbon source is preferably a spectrographite electrode (TSG); the tantalum source is preferably a tantalum rod, more preferably TD-tex; the yttrium source is preferably Y99.99; the manganese source is preferably DJMnG. The specific dosage of the raw materials is not particularly limited, and the chemical components of the finally obtained oxidation-resistant corrosion-resistant cobalt-based superalloy can meet the requirements.
In the present invention, the mixing is preferably performed in a crucible. 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 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 power of the low-temperature smelting is preferably 80-85 kW; the low-temperature smelting time is preferably 50-60 min; the power of the high-temperature smelting is preferably 140-160 kW, more preferably 150kW; the high-temperature smelting time is preferably 60-80 min, more preferably 60-70 min. In the invention, the smelting atmosphere of the low-temperature smelting and the high-temperature smelting is independently preferably vacuum smelting; the vacuum degree of the vacuum melting is preferably < 0.1Pa. The invention can reduce the burning loss of raw materials by the smelting mode.
After the high-temperature smelting is finished, the invention preferably heats the high-temperature smelting product to the high-temperature refining temperature for high-temperature refining. The rate of the temperature rise and the manner of the temperature rise are not particularly limited in the present invention, and may be determined according to the technical knowledge of those skilled in the art.
In the invention, the temperature of the high-temperature refining is preferably 1620-1650 ℃; the time for the high-temperature refining is preferably 60 minutes. The invention can avoid segregation of refractory elements and break short-range order of carbide forming elements by high-temperature refining, thereby playing a role in reducing the size of carbide elements and enhancing dispersion strengthening.
After the high-temperature refining is finished, the invention preferably cools the high-temperature refined product to obtain the first alloy melt. The cooling rate and the cooling mode are not particularly limited, and can be determined according to the technical common knowledge of the person skilled in the art. In the present invention, the temperature of the first alloy melt is preferably 1450 to 1480 ℃. The invention is convenient for subsequent smelting by controlling the temperature of the first alloy melt.
After the first alloy melt is obtained, the method adds the residual carbon source and the silicon source into the first alloy melt for secondary smelting to obtain a second alloy melt. In the present invention, the silicon source is preferably Si-1.
In the invention, the power of the second smelting is preferably 140-160 kW, more preferably 150kW; the time for the second smelting is preferably 10 minutes. By adopting the smelting process, the invention can ensure that the components are mixed more uniformly.
After the second alloy melt is obtained, the manganese source is added into the second alloy melt, and then refining and pouring are sequentially carried out, so that an alloy cast ingot is obtained.
In the invention, when Y is included in the prepared oxidation-resistant corrosion-resistant cobalt-based superalloy, the yttrium source and the manganese source are added into the second alloy melt together.
In the present invention, the refining atmosphere is preferably argon, and the pressure of the argon is preferably 1500 to 3000pa, more preferably 2000 to 2500pa. In the present invention, the argon is preferably added before the yttrium source and the manganese source are added. In the invention, the refining power is preferably 140-160 kW, more preferably 150kW; the refining time is preferably 5 minutes. The invention can further reduce the content of oxygen and nitrogen in the alloy by controlling the refining atmosphere.
In the present invention, the casting temperature is preferably at least 1550 ℃. The concrete operation of the pouring is not particularly limited, and conventional operation is adopted.
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 excircle into segments are not particularly limited, and can be determined according to the technical common knowledge of the person skilled in the art
After the alloy ingot is obtained, the alloy ingot is precisely cast to obtain the oxidation-resistant corrosion-resistant cobalt-based superalloy.
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 1000-1050 ℃; 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.
According to the invention, partial carbon is added during charging so as to remove oxygen elements adsorbed by raw materials, the inner wall of a furnace body and the inner wall of a crucible in the refining process, and then smelting is carried out under different powers, so that the crucible can be prevented from discharging oxygen due to rapid temperature rise, and meanwhile, the slow temperature rise process is beneficial to increasing the gas removal effect of Sievert's law; the segregation of refractory elements can be avoided through high-temperature refining, short-range order of carbide forming elements is broken, the size of carbide elements is reduced, and dispersion strengthening is enhanced; 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 cobalt-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 antioxidation corrosion-resistant cobalt-based superalloy provided by the invention has the characteristics of antioxidation, corrosion resistance and long service life, and the prepared gas turbine guide vane can still have good mechanical properties at 1000 ℃.
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 antioxidant corrosion-resistant cobalt-based superalloy comprises the following steps:
(1) Coating a yttrium oxide coating on the surface of a crucible in a smelting furnace, firstly adding Ni9996, GCCr-1, co9995, TW-1 and partial spectrum graphite electrode (TSG) into the crucible, mixing, sequentially carrying out low-temperature smelting, high-temperature smelting and high-temperature refining, and finally cooling to 1450 ℃ to obtain a first alloy melt; the power of the low-temperature smelting is 80kW, and the time of the low-temperature smelting is 60min; the power of the high-temperature smelting is 150kW, and the time of the high-temperature smelting is 60min; the high-temperature refining temperature is 1650 ℃, and the high-temperature refining time is 60min; the mass of the partial spectrum graphite electrode (TSG) is 1/3 of that of the total partial spectrum graphite electrode (TSG); the smelting atmosphere of the low-temperature smelting and the high-temperature smelting is vacuum smelting, and the vacuum degree of the vacuum smelting is less than 0.1Pa;
(2) Adding a residual spectrum graphite electrode (TSG) and Si-1 into the first alloy melt obtained in the step (1) to perform secondary smelting to obtain a second alloy melt; the power of the second smelting is 150kW, and the time of the second smelting is 10min;
(3) Introducing argon into the second alloy melt obtained in the step (2) until the pressure is 2000Pa, then adding DJMnG, refining and pouring in sequence, and finally polishing and cutting the excircle into sections to obtain alloy ingots; the refining power is 150kW, and the refining time is 5min; the casting temperature is 1550 ℃;
(4) Performing precision casting on the alloy cast ingot obtained in the step (3) in an isometric crystal furnace to obtain an antioxidant corrosion-resistant cobalt-based superalloy; the casting temperature of the precision casting is 1550 ℃, the shell temperature during the precision casting is 1050 ℃, and the cooling time of the precision casting is 20min.
The chemical compositions of the oxidation-resistant corrosion-resistant cobalt-based superalloy prepared in example 1 are shown in table 1:
TABLE 1 chemical composition of the antioxidant corrosion resistant cobalt-based superalloy prepared in EXAMPLE 1
| Chemical composition | C | Cr | Ni | W | B | Mn | Si | Ta | Mo | Y | Co |
| wt.% | 0.5 | 26 | 10.5 | 7.5 | 0.006 | 0.8 | 0.8 | 0 | 0 | 0 | Allowance of |
Example 2
Y99.99 and DJMnG were added in step (3), and the other conditions were the same as in example 1.
The chemical compositions of the oxidation-resistant corrosion-resistant cobalt-based superalloy prepared in example 2 are shown in table 2:
TABLE 2 chemical compositions of the antioxidant corrosion resistant cobalt-based superalloy prepared in EXAMPLE 2
| Chemical composition | C | Cr | Ni | W | B | Mn | Si | Ta | Mo | Y | Co |
| wt.% | 0.5 | 28 | 9.5 | 9 | 0.005 | 0.7 | 0.7 | 0 | 0 | 0.01 | Allowance of |
Example 3
In step (1), ni9996, GCCr-1, co9995, TW-1, TD-specific and partial spectrum graphite electrode (TSG) were added to the crucible, and Y99.99 and DJMnG were added to step (3), under the same conditions as in example 1.
The chemical compositions of the oxidation-resistant corrosion-resistant cobalt-based superalloy prepared in example 3 are shown in table 3:
TABLE 3 chemical composition of the antioxidant corrosion resistant cobalt-based superalloy prepared in EXAMPLE 3
| Chemical composition | C | Cr | Ni | W | B | Mn | Si | Ta | Mo | Y | Co |
| wt.% | 0.3 | 26 | 9 | 7 | 0.005 | 0.7 | 0.7 | 2 | 1 | 0.01 | Allowance of |
The oxidation resistance and corrosion resistance of the oxidation-resistant corrosion-resistant cobalt-based superalloy prepared in examples 1 to 3 at high temperature were tested, and the test standards were: 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 4:
table 4 high temperature Oxidation resistance and Corrosion resistance of the antioxidant corrosion resistant cobalt-based superalloy prepared in examples 1 to 3
As can be seen from Table 3, the antioxidation corrosion-resistant cobalt-based superalloy prepared by the invention has excellent antioxidation and corrosion resistance at the temperature of less than or equal to 1000 ℃, and can have better antioxidation performance at the moment although the oxidation rate can be increased when the temperature reaches over 1100 ℃.
The tensile properties of the oxidation-resistant corrosion-resistant cobalt-based superalloy prepared in examples 1 to 3 at high temperature were tested respectively, and the test standards were: HB5195 "Metal high temperature tensile test method", the results are shown in tables 5 to 7:
TABLE 5 high temperature tensile Properties of the antioxidant corrosion resistant cobalt-based superalloy prepared in example 1
| Temperature (temperature) | δb/MPa | δp0.2/MPa |
| 20℃ | 680 | 458 |
| 700℃ | 598 | 253 |
| 800℃ | 450 | 300 |
| 900℃ | 350 | 240 |
| 1000℃ | 220 | 120 |
TABLE 6 high temperature tensile Properties of the antioxidant corrosion resistant cobalt-based superalloy prepared in example 2
| Temperature (temperature) | δb/MPa | δp0.2/MPa |
| 20℃ | 650 | 432 |
| 700℃ | 570 | 220 |
| 800℃ | 420 | 280 |
| 900℃ | 330 | 220 |
| 1000℃ | 200 | 112 |
TABLE 7 high temperature tensile Properties of the antioxidant corrosion resistant cobalt-based superalloy prepared in example 3
| Temperature (temperature) | δb/MPa | δp0.2/MPa |
| 20℃ | 710 | 480 |
| 700℃ | 620 | 270 |
| 800℃ | 480 | 330 |
| 900℃ | 375 | 265 |
| 1000℃ | 230 | 140 |
In tables 5 to 7, 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 5 to 7, the anti-oxidation corrosion-resistant cobalt-based superalloy prepared by the invention has excellent high-temperature tensile property at the temperature of less than or equal to 1000 ℃.
The oxidation-resistant corrosion-resistant cobalt-based superalloy prepared in examples 1 to 3 was tested for durability at high temperature, respectively, with the test criteria: HB5150 "method for high temperature endurance test of metals", the results are shown in tables 8 to 10, respectively:
TABLE 8 high temperature durability of the oxidation resistant corrosion resistant cobalt-based superalloy prepared in EXAMPLE 1
| Temperature (temperature) | δ/MPa | τ/MPa |
| 700℃ | 380 | 58 |
| 750℃ | 310 | 37.5 |
| 800℃ | 240 | 23.3 |
| 900℃ | 140 | 54.5 |
| 980℃ | 88 | 41 |
TABLE 9 high temperature durability of the oxidation resistant corrosion resistant cobalt-based superalloy prepared in example 2
| Temperature (temperature) | δ/MPa | τ/MPa |
| 700℃ | 380 | 50 |
| 750℃ | 310 | 35 |
| 800℃ | 240 | 22.5 |
| 900℃ | 140 | 50 |
| 980℃ | 88 | 37 |
Table 10 high temperature durability of the oxidation resistant corrosion resistant cobalt-based superalloy prepared in example 3
| Temperature (temperature) | δ/MPa | τ/MPa |
| 700℃ | 380 | 64 |
| 750℃ | 310 | 41 |
| 800℃ | 240 | 30 |
| 900℃ | 140 | 60 |
| 980℃ | 88 | 50 |
In tables 8 to 10, δ is the loading stress at the time of the endurance test; τ is the permanent break time. As can be seen from tables 8 to 10, the high-temperature durability of the anti-oxidation corrosion-resistant cobalt-based superalloy prepared by the invention is continuously reduced along with the increase of temperature, but the high-temperature durability still has excellent high-temperature durability at 980 ℃, which indicates that the anti-oxidation corrosion-resistant cobalt-based superalloy prepared by the invention can work for a long time at the high temperature of about 1000 ℃.
The high cycle fatigue performance of the anti-oxidation corrosion-resistant cobalt-based superalloy prepared in examples 1 to 3 at high temperature was tested, and the test standards were: 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 tables 11 to 13:
Table 11 high cycle fatigue properties of the oxidation-resistant corrosion-resistant cobalt-based superalloy prepared in example 1
| Temperature (temperature) | δmax/MPa | Nf |
| 800℃ | 400 | ＞1×107 |
Table 12 high cycle fatigue properties of the oxidation-resistant corrosion-resistant cobalt-based superalloy prepared in example 2
| Temperature (temperature) | δmax/MPa | Nf |
| 800℃ | 400 | 6.8×106 |
Table 13 high cycle fatigue properties of the oxidation-resistant corrosion-resistant cobalt-based superalloy prepared in example 3
| Temperature (temperature) | δmax/MPa | Nf |
| 800℃ | 400 | ＞1×107 |
In tables 11 to 13, δmax is the maximum value of cyclic stress, and Nf is the number of cycles. As can be seen from tables 11-13, the antioxidation corrosion-resistant cobalt-based superalloy prepared by the invention has good fatigue performance while ensuring certain durability and good antioxidation 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. The oxidation-resistant corrosion-resistant cobalt-based superalloy comprises the following chemical components in percentage by mass: c: 0.3-0.6%, cr: 26-30%, ni: 8.5-10.5%, W: 7-10%, B: 0.003-0.006%, mn less than or equal to 1.5%, si less than or equal to 1.5% and the balance Co.
2. The oxidation-resistant corrosion-resistant cobalt-based superalloy according to claim 1, comprising the following chemical components in mass percent: c: 0.3-0.5%, cr: 26-28%, ni: 9-10.5%, W: 7.5-9%, B: 0.003-0.006%, mn: 0.5-0.8%, si: 0.5-0.8% and the balance of Co.
3. The oxidation-resistant corrosion-resistant cobalt-based superalloy according to claim 1 or 2, wherein the chemical composition of the oxidation-resistant corrosion-resistant cobalt-based superalloy further comprises, in mass percent: ta is less than or equal to 2%, mo is less than or equal to 1% and Y is less than or equal to 0.2%.
4. The method for preparing the oxidation-resistant corrosion-resistant cobalt-based superalloy according to any of claims 1 to 3, comprising the following steps:
(1) Mixing a nickel source, a chromium source, a cobalt source, a tungsten source and a part of carbon source, and then sequentially carrying out low-temperature smelting, high-temperature smelting and high-temperature refining to obtain a first alloy melt;
(2) Adding a residual carbon source, a silicon source and a boron source into the first alloy melt obtained in the step (1) to perform secondary smelting to obtain a second alloy melt;
(3) Adding a manganese source into the second alloy melt obtained in the step (2), and then refining and pouring in sequence to obtain an alloy cast ingot;
(4) Performing precision casting on the alloy cast ingot obtained in the step (3) to obtain an oxidation-resistant corrosion-resistant cobalt-based superalloy;
When Ta and Mo are included in the prepared oxidation-resistant corrosion-resistant cobalt-based superalloy, the tantalum source and the molybdenum source are mixed with a nickel source, a chromium source, a cobalt source, a tungsten source and a part of carbon source;
when Y is included in the prepared oxidation-resistant corrosion-resistant cobalt-based superalloy, the yttrium source and the manganese source are added into the second alloy melt together.
5. The preparation method according to claim 4, wherein the power of low-temperature smelting in the step (1) is 80-85 kW, and the time of low-temperature smelting is 50-60 min.
6. The preparation method of claim 4, wherein the power of high-temperature smelting in the step (1) is 140-160 kw, and the time of high-temperature smelting is 60-80 min.
7. The preparation method of claim 4, wherein the high-temperature refining in the step (1) is performed at 1620-1650 ℃ for 60min.
8. The preparation method of claim 4, wherein the power of the second smelting in the step (2) is 140-160 kw, and the time of the second smelting is 10min.
9. The method according to claim 4, wherein the casting temperature of the precision casting in the step (4) is 1500-1550 ℃, the shell temperature of the precision casting is 1000-1050 ℃, and the cooling time of the precision casting is 15-25 min.
10. Use of the oxidation-resistant corrosion-resistant cobalt-based superalloy according to any of claims 1 to 3 or the oxidation-resistant corrosion-resistant cobalt-based superalloy prepared by the preparation method according to any of claims 4 to 9 in a gas turbine guide vane.
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