CN115772626B - Nickel-based superalloy, and preparation method and application thereof - Google Patents
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 50
- 229910000601 superalloy Inorganic materials 0.000 title claims abstract description 42
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 33
- 239000000956 alloy Substances 0.000 claims description 33
- 238000001816 cooling Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 238000003723 Smelting Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 3
- 238000005728 strengthening Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910001566 austenite Inorganic materials 0.000 description 3
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 101000912561 Bos taurus Fibrinogen gamma-B chain Proteins 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Abstract
A nickel-based superalloy, a preparation method and application thereof belong to the technical field of superalloy for thermal power generating units. The nickel-based superalloy of the present invention comprises the following components in percentage by mass: fe: 28-32%, cr: 14-18%, mn:10-14%, co:2.8 to 3.2 percent of Ti:1.9 to 2.3 percent of Al:1.2 to 1.6 percent, si:0.1 to 0.5 percent, W:0.1 to 0.4 percent, mo:0.3 to 0.7 percent, C:0.05 to 0.09 percent, B:0.001 to 0.005 percent, and the balance of Ni; the mass percentage of Fe+Mn is 40-44%. The nickel-based superalloy has excellent high-temperature toughness while having high-temperature strength.
Description
Technical Field
The invention belongs to the technical field of high-temperature alloy for thermal power generating units, and particularly relates to a nickel-based high-temperature alloy, a preparation method and application thereof.
Background
Thermal power generating units always dominate in power consumption in China, efficiency improvement and pollution reduction are always pursued targets in the technical field of thermal power, and the improvement of the use temperature and the use pressure of main steam is always considered as the most effective method for improving the thermal efficiency. At present, advanced high-efficiency coal-fired power generation technologies developed at home and abroad mainly comprise 650 ℃ level, 700 ℃ level and over 700 ℃ level, wherein the thermal efficiency of a 650 ℃ level secondary reheating ultra-supercritical unit (A-USC) can break through 50%, the power supply coal consumption is lower than 260g/kWh, and the method is a unit scheme with the highest competitive power of considering material technology, station building cost, unit efficiency, energy conservation, emission reduction and the like before 2025 years; however, the elevation of the steam parameters of a 650 ℃ stage double reheat ultra supercritical unit (a-USC) places higher demands on the materials used for its critical components of the thermal path (final superheater and reheater, header, main/reheat steam lines, valves/dampers, cylinders, rotors, blades and fasteners).
For the critical components of the thermal channel of the 650 ℃ ultra-supercritical unit, the common requirements of the materials are excellent high-temperature strength, enough long-time high-temperature durable strength, toughness, tissue structure stability and the like. In addition, the service environments of different high-temperature parts are different, for example, the final stage over/reheater is required to have excellent steam oxidation resistance and smoke corrosion resistance, the main steam pipeline and the header are required to have excellent steam oxidation resistance, and the high-temperature section rotor is required to have low thermal expansion coefficient, good forging property and fatigue property. At present, a critical high-temperature component material system of a 650 ℃ ultra-supercritical unit is still immature, candidate materials at home and abroad mainly comprise nickel-based deformation superalloy and iron-nickel-based deformation superalloy, wherein the nickel-based deformation superalloy is mainly represented by alloys such as CCA617, haynes282 and Nimonic263, and the materials have excellent high-temperature lasting strength and oxidation resistance, but have high price, poor welding performance, high technical requirements on smelting, hot working and the like, and are limited to rapid popularization and application. The iron-nickel base wrought superalloy is mainly represented by foreign alloys such as Sanmicro 25 and HR 6W. The iron-nickel-based superalloy has low high temperature strength although having the advantage of raw material cost.
Disclosure of Invention
Therefore, aiming at the service requirements of critical high-temperature components of the ultra-supercritical thermal power generating unit at 650 ℃ and above, the invention provides the nickel-based superalloy, the preparation method and the application thereof, and the nickel-based superalloy has high-temperature strength and excellent high-temperature toughness.
For this purpose, the invention provides the following technical scheme.
In a first aspect, the present invention provides a nickel-base superalloy comprising, in mass percent: fe: 28-32%, cr: 14-18%, mn:10-14%, co:2.8 to 3.2 percent of Ti:1.9 to 2.3 percent of Al:1.2 to 1.6 percent, si:0.1 to 0.5 percent, W:0.1 to 0.4 percent, mo:0.3 to 0.7 percent, C:0.05 to 0.09 percent, B:0.001 to 0.005 percent, and the balance of Ni; the mass percentage of Fe+Mn is 40-44%.
Further, the mass percentage content of Mn is 11-13%; the mass percentage content of Co is 2.9-3.1%.
Further, at least one of the following conditions is satisfied:
(1) The mass percentage content of Fe is 29-31%;
(2) The mass percentage content of Cr is 15-17%;
(3) The mass percentage content of Ti is 2.1-2.3%;
(4) The mass percentage content of Al is 1.3-1.5%;
(5) The mass percentage content of Si is 0.2-0.4%;
(6) The weight percentage content of W is 0.2-0.3%;
(7) The mass percentage content of Mo is 0.4-0.6%;
(8) The mass percentage content of C is 0.06-0.08%.
In a second aspect, the invention provides a method for preparing a nickel-based superalloy, comprising the steps of:
step 1: smelting raw materials in vacuum, casting into alloy ingots, homogenizing the alloy ingots at 1150-1250 ℃ for 20-30 hours, and then air-cooling to room temperature;
step 2: carrying out thermal deformation on the homogenized alloy ingot at 1050-1150 ℃, wherein the deformation of each pass is not less than 14%, and the final total deformation is 40-60%;
step 3: and carrying out solution treatment on the alloy after thermal deformation at 980-1120 ℃ for 90-180 minutes, and then aging at 600-850 ℃ for 8-16 hours to obtain the nickel-based superalloy.
In step 2, furnace returning and heat preservation are performed after each heat deformation is completed, and then the next heat deformation is performed.
Further, in the step 2, the temperature of heat preservation in each furnace return is 1050-1150 ℃ and the time is 5-15min.
Further, in the step 3, the specific process of solution treatment is as follows: the water is cooled after heat preservation for 60-120 minutes at 1060-1120 ℃, and then the water is cooled after heat preservation for 30-60 minutes at 980-1040 ℃.
Further, in the step 3, the specific process of the aging treatment is as follows: firstly preserving heat at 600-700 ℃ for 6-10 hours, then air-cooling, and then preserving heat at 750-850 ℃ for 2-6 hours, and then air-cooling.
Further, the average grain size of the prepared nickel-base superalloy is 60-130 mu m; the vickers hardness number is greater than 300.
In a third aspect, the invention provides the use of a nickel-base superalloy or a nickel-base superalloy produced according to the method in a thermal power plant.
The technical scheme of the invention has the following advantages:
1. the nickel-based superalloy provided by the invention comprises the following components in percentage by mass: fe: 28-32%, cr: 14-18%, mn:10-14%, co:2.8 to 3.2 percent of Ti:1.9 to 2.3 percent of Al:1.2 to 1.6 percent, si:0.1 to 0.5 percent, W:0.1 to 0.4 percent, mo:0.3 to 0.7 percent, C:0.05 to 0.09 percent, B:0.001 to 0.005 percent, and the balance of Ni; the mass percentage of Fe+Mn is 40-44%.
Based on the design concept of precipitation strengthening alloy, the nickel-based superalloy provided by the invention ensures that the gamma 'strengthening phase has good thermal stability in the service temperature range while ensuring the volume fraction of the gamma' strengthening phase in the crystal by a proper amount of Ti+Al total amount and Ti/A1 ratio; the proper amount of Mo and W plays a solid solution strengthening role; a proper amount of Cr can ensure enough oxidation resistance/corrosion resistance and avoid the formation of harmful phases; proper amounts of C and B can be used for strengthening grain boundaries and improving the toughness of the alloy; the high content of Fe ensures excellent processability and high cost performance; an appropriate amount of Co can reduce the steady state creep rate and increase the number of gamma prime strengthening phases to increase strength. Mn plays a detrimental role in most high-temperature alloys, however, by matching with other elements, the high content of Mn can enlarge the gamma-phase region and stabilize austenite, thereby playing a role in strengthening the alloy.
The nickel-based superalloy of the invention is austenite with a disordered face-centered cubic structure, the main strengthening phase is gamma' phase, and MC (carbide) is arranged at the grain boundary. The alloy of the invention has high strength and high toughness. The yield strength is greater than 600MPa at 650 ℃ and 700 ℃, and the elongation at break is greater than 20% and 14% at 650 ℃ and 700 ℃, respectively.
2. The preparation method of the nickel-based superalloy provided by the invention ensures that the grain size and the like can be effectively regulated and controlled by a simple and proper processing mode. In addition, the grain size and carbide distribution are controlled by adopting graded solution treatment, and the grain diameter and volume fraction of gamma' phase are controlled by adopting graded aging treatment. The alloy has high strength at 600-700 ℃ and excellent toughness, and can be applied to manufacturing final superheaters and reheaters, headers, main/reheat steam pipelines, valves/valves, cylinders, rotors, blades, fasteners and the like of ultra-supercritical thermal power generating unit boilers at 650 ℃ and above.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a grain characterization of the nickel-base superalloy prepared in example 1;
FIG. 2 is an intra-crystalline gamma prime strengthening phase morphology of the nickel-base superalloy prepared in example 1.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
The preparation method of the nickel-based superalloy comprises the following steps:
step 1: the raw materials are smelted and cast into alloy ingots under vacuum, and then the alloy ingots are homogenized for 20-30 hours at 1150-1250 ℃ and then air-cooled to room temperature.
TABLE 1 chemical composition (wt.%)
TABLE 2 homogenization conditions
| Temperature (. Degree. C.) | Time (h) | |
| Example 1 | 1200 | 25 |
| Example 2 | 1150 | 30 |
| Example 3 | 1250 | 20 |
| Example 4 | 1180 | 25 |
| Example 5 | 1150 | 30 |
| Example 6 | 1190 | 25 |
| Example 7 | 1220 | 20 |
And 2, carrying out thermal deformation on the homogenized alloy ingot at 1050-1150 ℃, wherein the deformation amount of each pass is not less than 14%, and carrying out furnace return heat preservation for 5-15min after the thermal deformation of each pass is finished, wherein the final total deformation amount is 40-60%.
TABLE 3 thermal deformation and thermal insulation conditions
The alloys of examples 1-7 had good hot workability and no defects such as cracks were observed during hot working.
And 3, carrying out solution treatment on the alloy after thermal deformation, carrying out water cooling after heat preservation for 60-120 minutes at 1060-1120 ℃, and then carrying out water cooling after heat preservation for 30-60 minutes at 980-1040 ℃. And (3) carrying out aging treatment: firstly preserving heat at 600-700 ℃ for 6-10 hours, then air-cooling, and then preserving heat at 750-850 ℃ for 2-6 hours, and then air-cooling, thus obtaining the high-strength high-toughness nickel-based superalloy.
TABLE 4 solution treatment conditions
TABLE 5 aging conditions
The average grain size of the nickel-based superalloy prepared by the invention is 60-130 mu m, MC carbide particles are arranged at the grain boundary, and the typical grain structure characteristics are shown in figure 1. The matrix is austenite with disordered face-centered cubic structure, the main strengthening phase is gamma 'phase, the size is between 10 and 35nm, and the morphology of the gamma' strengthening phase in the crystal is shown in figure 2.
TABLE 6 average grain size
| Average grain size (μm) | |
| Example 1 | 95 |
| Example 2 | 83 |
| Example 3 | 105 |
| Example 4 | 108 |
| Example 5 | 120 |
| Example 6 | 113 |
| Example 7 | 100 |
Comparative example 1
This comparative example was substantially the same as example 1 except that no Mn element was added thereto and Fe was used instead of Mn, and the composition thereof was as shown in Table 7.
Comparative example 2
The alloy of this comparative example was an austenitic heat-resistant steel Sanmicro 25 having the highest heat-resistant capacity at present, and the composition is shown in Table 7.
Table 7 chemical Components (mass%) of comparative example
Test examples
Tensile property test: the tensile strength and yield strength of the alloys were measured at 650℃and 700℃respectively, and the measurement results are shown in Table 9 and Table 9.
Table 8 alloy properties at 650℃
Table 9 alloy properties at 700℃
As is evident from the comparison of example 1 and comparative examples 1-4, the strength of the alloy of the present invention at 650 ℃ and 700 ℃ is significantly higher than that of comparative Sanmicro 25 (650 ℃ C. Strength is higher than that of Sanmicro 25 at 600 ℃ C.), while having a higher elongation after break. The alloy of the example was shown to have excellent toughness while having excellent high temperature strength.
Table 10 hardness values
| Hardness value | |
| Example 1 | 325 |
| Example 2 | 328 |
| Example 3 | 339 |
| Example 4 | 321 |
| Example 5 | 311 |
| Example 6 | 320 |
| Example 7 | 330 |
| Comparative example 1 | 259 |
| Comparative example 2 | 175 |
In summary, the nickel-based superalloy of the present invention has good hot workability, easy molding, lower cost, high strength and excellent toughness, and can be used for manufacturing final superheaters and reheaters, headers, main/reheat steam pipes, valves/gates, cylinders, rotors, blades, fasteners, etc. of ultra supercritical thermal power generating unit boilers at 650 ℃ and above.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (8)
1. A nickel-base superalloy characterized by comprising, in mass percent: fe: 28-32%, cr: 14-18%, mn:10-14%, co: 2.8-3.2%, ti: 1.9-2.3%, al: 1.2-1.6%, si: 0.1-0.5%, W: 0.1-0.4%, mo: 0.3-0.7%, C: 0.05-0.09%, B: 0.001-0.005%, the balance being Ni; the mass percentage of Fe+Mn is 40-44%;
the preparation method of the nickel-based superalloy comprises the following steps:
step 1: smelting raw materials in vacuum, casting into alloy ingots, homogenizing the alloy ingots at 1150-1250 ℃ for 20-30 hours, and then air-cooling to room temperature;
step 2: carrying out thermal deformation on the homogenized alloy ingot at 1050-1150 ℃, wherein the deformation of each pass is not less than 14%, and the final total deformation is 40-60%;
step 3: carrying out solution treatment on the alloy after thermal deformation at 980-1120 ℃ for 90-180 minutes, and then aging at 600-850 ℃ for 8-16 hours to obtain nickel-based superalloy;
the specific process of solution treatment is as follows: firstly, preserving heat at 1060-1120 ℃ for 60-120 minutes, then cooling with water, and then preserving heat at 980-1040 ℃ for 30-60 minutes, and then cooling with water;
the aging treatment comprises the following specific processes: firstly preserving heat at 600-700 ℃ for 6-10 hours, then air-cooling, and then preserving heat at 750-850 ℃ for 2-6 hours, and then air-cooling.
2. The nickel-base superalloy as in claim 1, wherein the mass percentage content of Mn is 11-13%; the mass percentage content of Co is 2.9-3.1%.
3. The nickel-base superalloy as in claim 1, wherein at least one of the following conditions is satisfied:
(1) The mass percentage content of Fe is 29-31%;
(2) The mass percentage content of Cr is 15-17%;
(3) The mass percentage content of Ti is 2.1-2.3%;
(4) The mass percentage content of Al is 1.3-1.5%;
(5) The mass percentage content of Si is 0.2-0.4%;
(6) The weight percentage content of W is 0.2-0.3%;
(7) The mass percentage content of Mo is 0.4-0.6%;
(8) The mass percentage content of the C is 0.06-0.08%.
4. A method of producing the nickel-base superalloy as claimed in any of claims 1 to 3, comprising the steps of:
step 1: smelting raw materials in vacuum, casting into alloy ingots, homogenizing the alloy ingots at 1150-1250 ℃ for 20-30 hours, and then air-cooling to room temperature;
step 2: carrying out thermal deformation on the homogenized alloy ingot at 1050-1150 ℃, wherein the deformation of each pass is not less than 14%, and the final total deformation is 40-60%;
step 3: carrying out solution treatment on the alloy after thermal deformation at 980-1120 ℃ for 90-180 minutes, and then aging at 600-850 ℃ for 8-16 hours to obtain nickel-based superalloy;
the specific process of solution treatment is as follows: firstly, preserving heat at 1060-1120 ℃ for 60-120 minutes, then cooling with water, and then preserving heat at 980-1040 ℃ for 30-60 minutes, and then cooling with water;
the aging treatment comprises the following specific processes: firstly preserving heat at 600-700 ℃ for 6-10 hours, then air-cooling, and then preserving heat at 750-850 ℃ for 2-6 hours, and then air-cooling.
5. The method of producing a nickel-base superalloy according to claim 4, wherein in step 2, the heat is preserved by returning to the furnace after each heat distortion is completed, and then the next heat distortion is performed.
6. The method for producing a nickel-base superalloy according to claim 5, wherein in step 2, the temperature of the heat preservation is 1050 to 1150 ℃ and the time is 5 to 15 minutes.
7. The method for producing a nickel-base superalloy according to any of claims 4 to 6, wherein the nickel-base superalloy is produced with an average grain size of 60 to 130 μm; the vickers hardness number is greater than 300.
8. Use of the nickel-base superalloy of any of claims 1-3 or the nickel-base superalloy produced according to the method of any of claims 4-6 in a thermal power plant.
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| US4764225A (en) * | 1979-05-29 | 1988-08-16 | Howmet Corporation | Alloys for high temperature applications |
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2022
- 2022-11-17 CN CN202211439667.2A patent/CN115772626B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1067663A (en) * | 1963-03-19 | 1967-05-03 | Apv Paramount Ltd | Improvements in the production of wrought and cast heat-resisting steels and in articles produced therefrom and weld metals for use in the manufacture of weldments |
| US3912503A (en) * | 1973-05-14 | 1975-10-14 | Armco Steel Corp | Galling resistant austenitic stainless steel |
| US4764225A (en) * | 1979-05-29 | 1988-08-16 | Howmet Corporation | Alloys for high temperature applications |
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