CN110952016A - High-strength high-toughness oxidation-resistant iron-nickel-based high-temperature alloy and preparation method thereof - Google Patents
High-strength high-toughness oxidation-resistant iron-nickel-based high-temperature alloy and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-strength high-toughness oxidation-resistant iron-nickel-based high-temperature alloy and a preparation method thereof, wherein the iron-nickel-based high-temperature alloy comprises, by weight, 35-45% of Fe, 15-21% of Cr, 0.5-1.4% of Mo, 0.1-0.8% of W, 1.8-2.5% of Ti, 0.8-2.5% of Al, less than or equal to 1.0% of Mn, less than or equal to 0.1% of Nb, less than or equal to 2% of Co, less than or equal to 0.05% of Si, 0.03-0.10% of C, 0.001-0.005% of B, less than or equal to 0.01% of P. The weight percentage of Cr + Ni is more than 50 percent, and the weight percentage of W + Mo is 0.6-1.5 percent. The iron-nickel-based high-temperature alloy has high endurance strength, high impact toughness and good steam oxidation resistance; gamma' phase and M23C6Is the primary strengthening phase; compared with the prior art, the composite material has the advantages of equivalent processing performance, low material cost, excellent structural stability, high-temperature strength and impact toughness, and can be used for manufacturing main steam pipelines and main steam collectors of ultra-supercritical thermal power generating units at the temperature of 650 ℃ and aboveHigh temperature components such as a box and a high temperature section rotor.
Description
Technical Field
The invention relates to the technical field of high-temperature metal structural materials, in particular to a high-strength high-toughness oxidation-resistant iron-nickel-based high-temperature alloy and a preparation method thereof.
Background
The coal-fired thermal power generating unit provides over 70% of domestic electric power, but the domestic thermal power generating unit has low average power generation efficiency and high energy consumption and is a main emission source of sulfur dioxide, nitride NOx, carbon dioxide and mercury. With the increase of environmental protection requirements, the emission of carbon dioxide needs to be greatly reduced on the basis of the existing unit GDP. In the field of coal and electricity, the adoption of a high-parameter and high-capacity thermal power generating unit is one of the most direct, economic and effective measures for realizing the clean and efficient utilization of coal. At present, advanced ultra supercritical (A-USC) coal-fired power generation technology is actively developed in developed countries in the world, China and India at 700 ℃. However, the 700 ℃ ultra-supercritical power generation technology has great challenges on high-temperature materials, no mature high-temperature material system exists at home and abroad, and the nickel-based high-temperature alloy is still in the research, development and verification stages.
Because the nickel-based high-temperature alloy required by the 700 ℃ ultra-supercritical unit needs a higher preparation technology and is expensive, the factors such as the efficiency, the cost, the localization level and the preparation capacity of a power plant, the safe operation and the maintenance of the unit and the like are comprehensively considered, the key development direction in the future is to utilize optimized or newly developed heat-resistant steel and iron-nickel-based high-temperature alloy with high cost performance to gradually improve the parameters of the commercial power plant unit to 650 ℃, and the heat efficiency can reach about 50 percent.
The high-temperature structural material is the most important material foundation for realizing the advanced ultra-supercritical power generation technology, and the service environment requires that the high-temperature structural material has excellent high-temperature strength, toughness, steam oxidation resistance, smoke corrosion resistance, structural stability and the like. For a 650 ℃ ultra-supercritical unit, key high-temperature components, such as a final superheater and a reheater, a main steam pipeline, a header, a high-temperature section rotor and the like, reach or exceed the service temperature upper limit of austenitic heat-resistant steel, and a material with higher temperature-bearing capacity must be selected. At present, a material system of a key high-temperature part of a 650 ℃ ultra-supercritical unit is not mature, candidate materials are mainly Sanicro25, Inconel617, HR6W and the like abroad, and the material for the key high-temperature part of the 650 ℃ ultra-supercritical unit with the domestic proprietary intellectual property is basically blank.
Compared with high-grade austenitic heat-resistant steel (such as HR3C), the novel iron-nickel-based high-temperature alloy has higher temperature bearing capacity, good high-temperature performance, limited increase of material cost and high comprehensive cost performance, and is expected to be applied to key high-temperature components of 650 ℃ ultra-supercritical units, but no mature iron-nickel-based high-temperature alloy system in the prior art can meet the requirements of 650 ℃ units.
Disclosure of Invention
Aiming at the service requirements of key high-temperature components of next-generation high-parameter (650 ℃) ultra-supercritical thermal power generating units and the shortage of temperature bearing capacity of commercial high-grade austenitic heat-resistant steel, the invention provides the high-strength high-toughness oxidation-resistant iron-nickel-based high-temperature alloy and the preparation method thereof.
The invention is realized by the following technical scheme:
the high strength and high toughness oxidation resistant Fe-Ni based high temperature alloy consists of Fe 35-45 wt%, Cr 15-21 wt%, Mo 0.5-1.4 wt%, W0.1-0.8 wt%, Ti1.8-2.5 wt%, Al 0.8-2.5 wt%, Mn not more than 1.0 wt%, Nb not more than 0.1 wt%, Co not more than 2 wt%, Si not more than 0.05 wt%, C0.03-0.10 wt%, B0.001-0.005 wt%, P not more than 0.01 wt%, and Ni for the rest; the weight percentage of Cr + Ni is more than 50 percent, and the weight percentage of W + Mo is 0.6-1.5 percent.
Preferably, the weight percentage of the Cr is 15-18%, and the weight percentage of the C is 0.03-0.08%.
Preferably, the weight percentage of Mo is 0.6-1.2%, and the weight percentage of W is 0.1-0.5%.
Preferably, the weight percentage of Fe is 37-45%.
Preferably, the weight percentage of Ti is 1.8-2.3%, and the weight percentage of Al is 1.0-2.1%.
Preferably, the weight percentage of Mn is less than or equal to 0.5 percent, and the weight percentage of Nb is less than or equal to 0.08 percent.
Preferably, the weight percentage of Si is less than or equal to 0.04 percent.
Preferably, the percentage by weight of B is 0.001-0.003%.
A preparation method of high-strength high-toughness oxidation-resistant iron-nickel-based high-temperature alloy comprises the following steps,
step 1, melting the raw materials of any one of the components in the scheme under vacuum, and casting into an alloy ingot;
step 2, homogenizing the alloy ingot at 1170 ℃ of 1100-50 hours, and then thermally deforming the homogenized alloy ingot at 1120 ℃ of 1020-80 percent, wherein the total deformation is 60-80 percent, and the final primary deformation is not lower than 25 percent;
and 3, carrying out solid solution treatment on the alloy after thermal deformation at 1080-1120 ℃ for 30-60 minutes, then carrying out air cooling, then carrying out aging at 650-800 ℃ for 8-20 hours, and carrying out water cooling to obtain the high-strength high-toughness oxidation-resistant iron-nickel-based high-temperature alloy.
Preferably, the iron-nickel-based superalloy has a matrix of austenite with a disordered face-centered cubic structure, a main strengthening phase of gamma' and M at a grain boundary23C6(ii) a Grain size of 70-125 μmThe yield strength at 650 ℃ and 700 ℃ is more than 500MPa, and the elongation is more than 10%.
Compared with the prior art, the invention has the following beneficial technical effects:
the iron-nickel-based high-temperature alloy disclosed by the invention has the advantages that the steam oxidation resistance and the smoke corrosion resistance are improved by containing higher Cr in the alloy; proper Mo and W play a role in solid solution strengthening; a proper amount of Ni, Ti and Al can form a strengthening phase gamma' which is dispersed and distributed in the crystal; proper amount of Co can improve the endurance quality of the material; cr and C may form discontinuous carbides at grain boundaries to strengthen the grain boundaries; B. p can reduce the coarsening rate of carbide at the grain boundary, can also reduce the interface energy of the grain boundary, improve the bonding strength of the grain boundary and improve the toughness of the alloy; the optimization of the alloy components ensures that the alloy has high strength and high toughness at 600-700 ℃, and excellent structural stability and steam oxidation resistance. Under the condition of 650-700 ℃ water vapor, the iron-nickel-based high-temperature alloy forms a continuous, uniform, compact and stable Cr-rich oxide layer on the surface to protect a matrix; the hot processing performance is good, the forming is easy, and the hot-forming die can be suitable for manufacturing parts which are in service in the environments of high temperature, high pressure, ultra-supercritical water vapor and corrosive flue gas, such as a main steam pipeline, a header and a high-temperature section rotor of a 650 ℃ ultra-supercritical thermal power unit boiler; the cost performance is superior to that of similar foreign alloys, such as Sanicro25, Inconel617, HR6W and the like.
Drawings
FIG. 1 is a structural feature of an iron-nickel-based superalloy prepared in example 1 of the present invention.
FIG. 2 shows the morphology of the intragranular precipitation strengthening phase γ' of the iron-nickel-based superalloy prepared in example 1 of the present invention.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The iron-nickel-based high-temperature alloy obtained by the invention has the characteristics of high strength, high toughness and steam oxidation resistance, the matrix of the iron-nickel-based high-temperature alloy is austenite (gamma) with a disordered face-centered cubic structure, the main strengthening phase is gamma', and M is arranged at the grain boundary23C6When the grain size is in the range of 70-125 μm, the yield strength at 650 ℃ and 700 ℃ is more than 500MPa, and the elongation is more than 10%.
Example 1
1. Composition of alloy
Table 1 shows the chemical composition of example 1 of the present invention. Alloy # 1 for the test is an iron-nickel based superalloy of example 1 of the present invention, and for comparison with the currently highest temperature bearing austenitic heat resistant steel, Sanicro25 alloy (developed by Sandvik, Sweden), the composition of Sanicro25 is also shown.
TABLE 1 chemical composition (wt%; balance Ni) of inventive example 1 and comparative example (Sanicro25)
2. Melting and hot deformation of alloys
According to weight percentage, 35 to 45 percent of Fe, 15 to 21 percent of Cr, 0.5 to 1.4 percent of Mo, 0.1 to 0.8 percent of W, 1.8 to 2.5 percent of Ti, 0.8 to 2.5 percent of Al, less than or equal to 1.0 percent of Mn, less than or equal to 0.1 percent of Nb, less than or equal to 2 percent of Co, less than or equal to 0.05 percent of Si, 0.03 to 0.10 percent of C, 0.001 to 0.005 percent of B, less than or equal to 0.01 percent of P, the balance of Ni, more than 50 percent of Cr and more than 1.5 percent of W and Mo are added into a vacuum induction furnace to be smelted and cast into alloy ingots.
Homogenizing the alloy ingot at the temperature of 1100-1170 ℃ for 30-50 hours, and then thermally deforming (hot forging or hot rolling) the homogenized alloy ingot at the temperature of 1020-1120 ℃, wherein the total deformation amount is 60-80%, and the final secondary deformation amount is not less than 25%. The alloy of example 1 has good hot workability, and no defects such as cracks appear during hot working.
3. Heat treatment of alloys
And carrying out solution treatment on the alloy after thermal deformation at 1080-1120 ℃ for 30-60 minutes, then air cooling, aging at 650-800 ℃ for 8-20 hours, and water cooling to obtain the high-strength high-toughness oxidation-resistant iron-nickel-based high-temperature alloy.
4. Structural features of the alloy
The grain size of the alloy is in the range of 70-125 μm, and its typical structure is characterized as shown in FIG. 1. A small amount of primary carbide exists in the crystal and the crystal boundary, the main strengthening phase in the crystal is gamma' precipitated during aging heat treatment, and discontinuous carbide M exists in the crystal boundary23C6And (4) phase(s).
5. Mechanical properties of the alloy
5.1 tensile Properties
The room temperature tensile properties of the alloy # of example 1 are all better than indicated by Sanicro25 (materials handbook of Sandvik, Sweden). With the increase of the temperature, the yield strength of the iron-nickel-based high-temperature alloy is not obviously reduced, the tensile strength is obviously reduced, and the yield strength is still more than 700MPa at 700 ℃. The yield strength and tensile strength of the example # 1 alloy at 650 c and 700 c are both much higher than 199MPa and 550MPa of Sanicro25 at 600 c. Indicating that the example alloys have excellent room temperature and high temperature strength. (Property data of Sanicro25 is from the materials Property Manual of Sandvik corporation)
TABLE 2 tensile Properties of example 1# alloy with Sanicro25
5.2 impact at room temperature
The room temperature impact work of the alloy # of example 1 after 1000 hours of thermal exposure at 700 c is shown in table 3. The impact work after thermal exposure of the alloy # of example 1 was 66J/cm249J/cm higher than Sanicro252About 35%.
Table 3 impact energy at room temperature of alloy # 1 from example 1 and saiicro 25 after 1000 hours of thermal exposure
5.3 permanent Strength
The alloy of example 1 has higher endurance strength at 700 ℃ and 750 ℃. Table 4 shows that the alloy of example 1 has a durability strength substantially better than Sanicro25 compared to the durability of the alloy of example 1 and Sanicro25 under three different stress conditions of 700 ℃ and 750 ℃.
TABLE 4 endurance life (h) of alloy # 1 of example 1 with Sanicro25 at 700 deg.C
| Alloy (I) | 700℃/250MPa | 700℃/200MPa | 750℃/150MPa |
| 1# | 2730 | >6000 | 2936 |
| Sanicro25 | 600 | 2000 | 700 |
In conclusion, compared with Sanicro25 of Sandvik corporation in Sweden, the iron-nickel-based high-temperature alloy of the invention has good hot workability, easy molding and lower cost, and simultaneously has excellent high-temperature strength, high toughness and high-temperature structure stability. The iron-nickel-based high-temperature alloy is suitable for manufacturing parts working under the conditions of high temperature, high pressure and ultra-supercritical water vapor at the temperature of 650 ℃ and above, such as a main steam pipeline, a header, a high-temperature section rotor and the like in an ultra-supercritical coal-fired power generating unit (A-USC) at the temperature of 650 ℃ and above.
Examples 2 to 9
The chemical composition of the alloys of examples 2-9 of the present invention is shown in Table 5.
Table 5 is the chemical composition of the alloys of examples 2-9 of the present invention, wherein the contents of example 1 are added for statistical comparison, all in weight percent.
| Examples | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
| Fe | 40 | 35 | 38 | 42 | 45 | 41 | 39 | 37 | 36 |
| Cr | 16 | 19 | 20 | 21 | 21 | 19 | 18 | 17 | 15 |
| Mo | 0.6 | 1.2 | 1.0 | 0.6 | 1.0 | 1.3 | 1.0 | 1.4 | 0.5 |
| W | 0.3 | 0.1 | 0.5 | 0.8 | 0.1 | 0.2 | 0.4 | 0.1 | 0.1 |
| Ti | 1.8 | 2.0 | 2.1 | 2.3 | 2.0 | 2.1 | 2.4 | 2.5 | 1.9 |
| Al | 1.6 | 1.8 | 2.0 | 1.0 | 0.9 | 2.1 | 2.2 | 0.8 | 2.5 |
| Mn | 0.1 | 0.2 | 0.2 | 0.5 | 0.1 | 0.1 | 0.2 | 1.0 | 0.8 |
| Nb | 0.05 | 0.05 | 0.06 | 0.06 | 0.03 | 0.03 | 0.04 | 0.08 | 0.1 |
| Si | 0.025 | 0.03 | 0.03 | 0.02 | 0.02 | 0.03 | 0.04 | 0.05 | 0.01 |
| C | 0.05 | 0.06 | 0.06 | 0.08 | 0.08 | 0.09 | 0.10 | 0.04 | 0.03 |
| B | 0.002 | 0.003 | 0.003 | 0.004 | 0.003 | 0.005 | 0.003 | 0.002 | 0.001 |
| P | ≤0.01 | ≤0.01 | ≤0.01 | ≤0.01 | ≤0.01 | ≤0.01 | ≤0.01 | ≤0.01 | ≤0.01 |
| Co | 1 | 1.5 | 1.8 | 1.7 | 0.5 | 1.5 | 2.0 | 0.2 | 1.3 |
| Ni | Balance of | Balance of | Balance of | Balance of | Balance of | Balance of | Balance of | Balance of | Balance of |
Because the components, the structure and the performance of the high-temperature material are closely related, the high-temperature strength of the alloy can be kept and the high-temperature strength alloy has good toughness and steam oxidation resistance through the component optimization of the alloy.
Claims (10)
1. The high-strength high-toughness oxidation-resistant iron-nickel-based high-temperature alloy is characterized by comprising the following components, by weight, 35-45% of Fe, 15-21% of Cr, 0.5-1.4% of Mo, 0.1-0.8% of W, 1.8-2.5% of Ti, 0.8-2.5% of Al, less than or equal to 1.0% of Mn, less than or equal to 0.1% of Nb, less than or equal to 2% of Co, less than or equal to 0.05% of Si, 0.03-0.10% of C, 0.001-0.005% of B, less than or equal to 0.01% of P, and the balance; the weight percentage of Cr + Ni is more than 50 percent, and the weight percentage of W + Mo is 0.6-1.5 percent.
2. The high-strength high-toughness oxidation-resistant iron-nickel-based high-temperature alloy according to claim 1, which is characterized in that: the weight percentage of the Cr is 15-18%, and the weight percentage of the C is 0.03-0.08%.
3. The high-strength high-toughness oxidation-resistant iron-nickel-based high-temperature alloy according to claim 1, which is characterized in that: the weight percentage of Mo is 0.6-1.2%, and the weight percentage of W is 0.1-0.5%.
4. The high-strength high-toughness oxidation-resistant iron-nickel-based high-temperature alloy according to claim 1, which is characterized in that: the weight percentage of the Fe is 37-45%.
5. The high-strength high-toughness oxidation-resistant iron-nickel-based high-temperature alloy according to claim 1, which is characterized in that: the weight percentage of Ti is 1.8-2.3%, and the weight percentage of Al is 1.0-2.1%.
6. The high-strength high-toughness oxidation-resistant iron-nickel-based high-temperature alloy according to claim 1, which is characterized in that: the weight percentage of Mn is less than or equal to 0.5 percent, and the weight percentage of Nb is less than or equal to 0.08 percent.
7. The high-strength high-toughness oxidation-resistant iron-nickel-based high-temperature alloy according to claim 1, which is characterized in that: the weight percentage of Si is less than or equal to 0.04 percent.
8. The high-strength high-toughness oxidation-resistant iron-nickel-based high-temperature alloy according to claim 1, which is characterized in that: the weight percentage of B is 0.001-0.003%.
9. A preparation method of high-strength high-toughness oxidation-resistant iron-nickel-based high-temperature alloy is characterized by comprising the following steps of,
step 1, melting raw materials of the components of any one of claims 1 to 8 under vacuum, and casting the raw materials into an alloy ingot;
step 2, homogenizing the alloy ingot at 1170 ℃ of 1100-50 hours, and then thermally deforming the homogenized alloy ingot at 1120 ℃ of 1020-80 percent, wherein the total deformation is 60-80 percent, and the final primary deformation is not lower than 25 percent;
and 3, carrying out solid solution treatment on the alloy after thermal deformation at 1080-1120 ℃ for 30-60 minutes, then carrying out air cooling, then carrying out aging at 650-800 ℃ for 8-20 hours, and carrying out water cooling to obtain the high-strength high-toughness oxidation-resistant iron-nickel-based high-temperature alloy.
10. The method for preparing the high-strength high-toughness oxidation-resistant iron-nickel-based high-temperature alloy according to claim 9, wherein the matrix of the iron-nickel-based high-temperature alloy is austenite with a disordered face-centered cubic structure, the main strengthening phase is gamma', and M is arranged at a grain boundary23C6(ii) a When the grain size is 70-125 μm, the yield strength is more than 500MPa at 650 ℃ and 700 ℃, and the elongation is more than 10%.
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| PCT/CN2020/136131 WO2021121185A1 (en) | 2019-12-16 | 2020-12-14 | High-strength and high-toughness antioxidant iron-nickel-based high-temperature alloy, and preparation method thereof |
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| CN111394638A (en) * | 2020-05-08 | 2020-07-10 | 华能国际电力股份有限公司 | High-strength high-temperature alloy for thermal power generating unit and processing technology thereof |
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| CN112359296A (en) * | 2020-11-10 | 2021-02-12 | 华能国际电力股份有限公司 | Precipitation strengthening iron-based high-temperature alloy and preparation method thereof |
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| WO2021121185A1 (en) * | 2019-12-16 | 2021-06-24 | 西安热工研究院有限公司 | High-strength and high-toughness antioxidant iron-nickel-based high-temperature alloy, and preparation method thereof |
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| CN111394638B (en) * | 2020-05-08 | 2021-11-16 | 华能国际电力股份有限公司 | High-strength high-temperature alloy for thermal power generating unit and processing technology thereof |
| WO2021223760A1 (en) * | 2020-05-08 | 2021-11-11 | 华能国际电力股份有限公司 | High-strength high-temperature alloys for thermal power units and processing technique therefor |
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| CN116024481B (en) * | 2023-01-18 | 2024-07-02 | 华能国际电力股份有限公司 | Low-chromium-nickel-iron-based superalloy and preparation method thereof |
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| CN110952016B (en) | 2021-03-30 |
| WO2021121185A1 (en) | 2021-06-24 |
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