CN110607470A - Oxidation-resistant nickel-based alloy - Google Patents
Oxidation-resistant nickel-based alloy Download PDFInfo
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- CN110607470A CN110607470A CN201910961662.8A CN201910961662A CN110607470A CN 110607470 A CN110607470 A CN 110607470A CN 201910961662 A CN201910961662 A CN 201910961662A CN 110607470 A CN110607470 A CN 110607470A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
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Abstract
The invention discloses a nickel-based alloy, and belongs to the field of oxidation-resistant nickel-based alloys. The alloy comprises the following components in percentage by weight: 0.2-0.5% of C, 26-28% of Cr, 0.5-1.5% of Nb, 3-5% of W, 2-4% of Ti, 1-3% of Al, 0.005-0.012% of B, 0.1-0.5% of Si, 0.01-0.1% of Zr, 0-5% of Fe, 0.01-0.1% of RE and the balance of Ni. Through proper element selection and component design, the alloy has high-temperature mechanical property, excellent high-temperature oxidation resistance and low production cost, and is suitable for manufacturing a glass wool centrifuge working under high temperature and high stress.
Description
Technical Field
The invention relates to a nickel-based alloy, in particular to an oxidation-resistant nickel-based alloy with good high-temperature mechanical property and excellent high-temperature oxidation resistance.
Background
The centrifugal device is a key part for producing glass wool and products thereof by a centrifugal blowing method. The molten glass liquid flows into a high-speed rotating centrifuge through a channel and a bushing plate, under the action of centrifugal force, the glass liquid forms a thin stream through tens of thousands of small holes in the side wall of the centrifuge, and then is further pulled to generate glass wool with the diameter of about 4-8 mu m under the action of high-temperature high-speed gas flow.
Because the working environment is severe and the alloy used for manufacturing the centrifuge is required to have good high-temperature mechanical property, high-temperature oxidation resistance and molten glass corrosion and scouring resistance, the centrifuge is mostly prepared by adopting Ni-based or Co-based oxidation resistant alloy. However, cobalt is expensive and a rare element, and in view of cost, most of the glass wool centrifuges used at present are made of nickel-based oxidation resistant alloy.
With the continuous improvement of the production efficiency and quality requirements of glass wool, the design size, the rotation speed and the working temperature of the centrifuge are also continuously increased. The size of the existing centrifuge is larger (more than phi 400 mm) and the working temperature is higher (1050 ℃ -1080 ℃), which provides new challenges for the mechanical property and oxidation resistance of centrifuge materials at higher temperature. The existing centrifuge alloys such as Inconel 625, ZG40Cr28Ni48W5 and the like have insufficient high-temperature mechanical properties or poor high-temperature oxidation resistance, and are difficult to meet the use requirements under new working conditions. Therefore, an antioxidant nickel-based alloy with high-temperature mechanical property, excellent high-temperature oxidation resistance and low cost is urgently needed to be developed and used for preparing a glass wool centrifuge.
Disclosure of Invention
In view of the above disadvantages of the prior art, the present invention provides an oxidation resistant nickel-based alloy.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the oxidation-resistant nickel-based alloy comprises, by weight, 0.2-0.5% of C, 26-28% of Cr, 0.5-1.5% of Nb, 3-5% of W, 2-4% of Ti, 1-3% of Al, 0.005-0.012% of B, 0.1-0.5% of Si, 0.01-0.1% of Zr, 0-5% of Fe, 0.01-0.1% of rare earth and the balance of Ni.
As a preferred technical scheme: in the oxidation-resistant nickel-based alloy, W + Cr-5C is less than or equal to 31%, Ti/Al is less than or equal to 3.5 and more than or equal to 0.8, wherein W, Cr, C, Ti and Al respectively represent the mass fraction of elements W, Cr, C, Ti and Al in the oxidation-resistant nickel-based alloy.
The chemical composition of the alloy of the invention is designed mainly based on the following reasons:
the alloy of the invention takes Ni as a matrix, and simultaneously can be added with a small amount of Fe to reduce the cost under the condition of ensuring that the high-temperature performance of the alloy is not damaged.
C (carbon) is an important element influencing the high-temperature mechanical property and the wear resistance of the alloy. C forms different types of carbide in the alloy, so that dislocation movement is hindered, and the strength of the alloy is improved. In addition, the carbide has higher hardness, which is beneficial to improving the capability of the alloy for resisting the abrasion of molten glass and high-temperature airflow. However, the carbide is easily oxidized preferentially to form loose pores during high-temperature oxidation, which damages the compactness of the alloy oxide film and affects the high-temperature oxidation resistance of the alloy. Therefore, the content of C in the alloy is controlled to be 0.2-0.5 wt.%.
Cr (Cr) is an important element for influencing the oxidation resistance and molten glass corrosion resistance of the alloy, and can be combined with C to generate a skeleton carbide for strengthening. Cr can also be dissolved in the matrix to play a solid solution strengthening role. Further, W (tungsten) is also an important solid-solution strengthening element. However, too high a content of solid solution elements may decrease the structural stability of the alloy, resulting in precipitation of harmful phases. Comprehensively considering the antioxidation and solid solution strengthening effects of elements, the content of Cr in the alloy is controlled to be 26-28 wt.%, the content of W is controlled to be 3-5 wt.%, and W + Cr-5C is less than or equal to 31%, wherein W, Cr and C respectively represent the mass fractions of the elements W, Cr and C in the antioxidation nickel-based alloy.
Nb (niobium) is an important element affecting the high-temperature mechanical properties of the alloy, and can be combined with C to form MC type carbide NbC. On one hand, the carbide of Nb replaces a part of carbide of Cr, which is beneficial to improving the Cr content in the matrix and enhancing the high-temperature oxidation resistance of the alloy; on the other hand, NbC is distributed in the alloy in a fine and dispersed manner, which is beneficial to improving the high-temperature mechanical property of the alloy. However, excessive Nb causes harmful phase precipitation at the grain boundary of the alloy, so that the content of Nb in the alloy is controlled to be 0.5-1.5 wt.%.
Al (aluminum) is a precipitation strengthening phase gamma' (Ni) in the alloy3Al), and a proper amount of Al contributes to the improvement of the high-temperature strength of the alloy. However, Al generates Al upon high-temperature oxidation2O3And the alloy can react with alkaline molten glass to destroy the integrity of an oxide film, so that the corrosion resistance of the alloy to the molten glass is not facilitated. Ti (titanium) atoms may replace Al atoms in the gamma' phase to form Ni3(Al, Ti) also has a precipitation strengthening effect. In addition, Ti may promote MC type carbideAnd the high-temperature strength of the alloy is improved. However, too high a Ti/Al ratio may decrease the stability of the γ' phase. In addition, Ti belongs to active metal elements, is easy to generate internal oxidation or internal nitridation when the alloy is oxidized at high temperature, and is not beneficial to the high-temperature oxidation resistance of the alloy. By combining the factors, the content of Al is controlled to be 1-3 wt.%, the content of Ti is controlled to be 2-4 wt.%, and Ti/Al is more than or equal to 0.8 and less than or equal to 3.5, wherein Ti and Al respectively represent the mass fractions of elements Ti and Al in the antioxidant nickel-based alloy.
After B (boron) and Zr (zirconium) are added into the alloy, the B (boron) and the Zr (zirconium) are partially polymerized at a crystal boundary, so that the mechanical property of the alloy is improved to a certain extent, and the effect is more obvious when the B (boron) and the Zr (zirconium) are added in a composite way. However, too high B, Zr content lowers the initial melting temperature of the alloy, which is detrimental to the high temperature performance of the alloy. B, Zr elements are simultaneously added into the alloy, and the addition amounts are respectively controlled to be 0.005-0.012 wt.% of B and 0.01-0.1 wt.% of ZrC.
Si (silicon) can improve the appearance of carbide in the alloy and is beneficial to improving the high-temperature wear resistance of the alloy. However, the high-temperature mechanical property of the alloy is damaged due to the excessively high Si content, so that the Si content in the alloy is controlled to be 0.1-0.5 wt%.
RE (rare earth) is added into the alloy, and trace rare earth elements are added into the alloy to form an oxide pinning matrix in the high-temperature oxidation process, so that the adhesion of an oxide film can be improved, and the high-temperature airflow and molten glass liquid erosion resistance of the alloy can be enhanced. Therefore, 0.01-0.1 wt.% of RE is added into the alloy, so that the service performance of the alloy is improved.
The reasonable proportion of the elements is the basis for obtaining excellent comprehensive performance of the alloy. According to different effects of each element on the high-temperature mechanical property and the oxidation resistance of the alloy, the invention determines the appropriate content range of each element through a large number of experimental researches, so that the alloy has both higher high-temperature mechanical property and excellent high-temperature oxidation resistance.
The invention has the advantages that: compared with the alloy for the existing glass cotton centrifuge, the alloy provided by the invention has higher high-temperature mechanical property and excellent high-temperature oxidation resistance, and the large-size glass cotton centrifuge prepared from the alloy provided by the invention is not easy to deform when used at a high temperature of 1050-1080 ℃, so that the service life is obviously prolonged, the alloy cost is low, and the alloy has very good economic benefits.
Drawings
FIG. 1 is a graph comparing the 1080 ℃ oxidation damage depth of the example alloy, and the comparative alloy.
FIG. 2 is a comparison of 1080 ℃ oxidation damage depth for example three, four alloys and a comparison file alloy.
FIG. 3 is a comparison of 1080 ℃ oxidation damage depth for example five and six alloys versus a comparative file alloy.
FIG. 4 shows the oxide layer of an alloy of the embodiment after oxidizing at 1080 ℃ for 150 h.
FIG. 5 shows the oxide layer of the second alloy of the embodiment after oxidizing at 1080 ℃ for 150 h.
FIG. 6 shows the oxide layer of the three alloys of the example after oxidizing at 1080 ℃ for 150 h.
FIG. 7 shows the oxide layer of the four-alloy of the embodiment after oxidizing at 1080 ℃ for 150 h.
FIG. 8 shows the oxide layer of the example V-alloy after oxidizing at 1080 ℃ for 150 h.
FIG. 9 shows the oxide layer of the six-alloy of the embodiment after oxidizing for 150h at 1080 ℃.
FIG. 10 shows the oxide layer of a comparative example-alloy after 150h of oxidation at 1080 ℃.
FIG. 11 shows the oxide layer of the second alloy of the comparative document after oxidizing for 150h at 1080 ℃.
Detailed Description
The invention is described in detail below with reference to the drawings.
The oxidation-resistant nickel-based alloy comprises, by weight, 0.2-0.5% of C, 26-28% of Cr, 0.5-1.5% of Nb, 3-5% of W, 2-4% of Ti, 1-3% of Al, 0.005-0.012% of B, 0.1-0.5% of Si, 0.01-0.1% of Zr, 0-5% of Fe, 0.01-0.1% of rare earth and the balance of Ni.
The first embodiment is as follows:
the contents of the components are C0.2%, Cr 26%, Nb 0.5%, W3%, Ti 2%, Al 1%, B0.005%, Si 0.1%, Zr 0.01%, rare earth 0.01%, and the rest is Ni.
Example two:
the contents of the components are 0.47 percent of C, 27.5 percent of Cr, 1.2 percent of Nb, 4.1 percent of W, 3.2 percent of Ti, 2.1 percent of Al, 0.01 percent of B, 0.3 percent of Si, 0.05 percent of Zr, 4.6 percent of Fe, 0.05 percent of rare earth and the balance of Ni.
Example three:
the contents of the components are 0.42 percent of C, 26.5 percent of Cr, 1.0 percent of Nb, 3.0 percent of W, 3.4 percent of Ti, 2.3 percent of Al, 0.005 percent of B, 0.1 percent of Si, 0.02 percent of Zr, 3.0 percent of Fe, 0.02 percent of rare earth and the balance of Ni.
Example four:
the contents of the components are 0.34 percent of C, 27.3 percent of Cr, 1.2 percent of Nb, 4.7 percent of W, 3.7 percent of Ti, 2.8 percent of Al, 0.008 percent of B, 0.2 percent of Si, 0.03 percent of Zr, 4.2 percent of Fe, 0.08 percent of rare earth and the balance of Ni.
Example five:
the contents of the components are C0.4%, Cr 27%, Nb 1.0%, W5%, Ti 3%, Al 2%, B0.01%, Si 0.3%, Zr 0.05%, Fe 2.5%, rare earth 0.05%, and the rest is Ni.
Example six:
the contents of the components are C0.5%, Cr 28%, Nb 1.5%, W5%, Ti 4%, Al 3%, B0.012%, Si 0.5%, Zr 0.1%, Fe 5%, rare earth 0.1%, and the rest is Ni.
Table 1 alloy of the examples of the invention and comparative documents alloy chemistry comparison table (wt.%):
the nickel-based alloy is smelted by a vacuum induction furnace, then is formed by a precision casting process, and is made into the glass wool centrifuge by the steps of heat treatment, machining and the like.
Compared with the alloy for the existing glass wool centrifuge, the alloy provided by the invention has higher high-temperature mechanical property and excellent high-temperature oxidation resistance.
TABLE 2 comparison of the durability of the alloy of the examples of the invention and the alloy of the comparison document
The alloy of the invention has good durability at high temperature, and the durability life is longer than 110 hours under the stress of 1050 ℃ and 35 MPa.
FIGS. 1-3 are 1080 ℃ oxidative damage depth comparisons of example and comparative file alloys. It can be seen that the alloy of the invention has small oxidation damage depth after different oxidation time at high temperature and excellent high temperature oxidation resistance.
Fig. 4-11 show the oxide layers of the example alloy and the comparative alloy after 150h of oxidation at 1080 ℃. It can be seen that after the alloy is oxidized at high temperature, a layer of relatively complete and compact oxide film can be generated on the surface of the alloy, which is beneficial to preventing the further oxidation of the alloy matrix and the corrosion of molten glass liquid to the matrix. In addition, the alloy has uniform oxidation degree and shows excellent high-temperature oxidation resistance.
TABLE 3 comparison of service life of centrifuges made from alloys of the examples of the invention and comparative documents
The large-size glass wool centrifuge prepared from the alloy is not easy to deform when used at the high temperature of 1050-1080 ℃, and the service life is obviously prolonged. And the alloy has low cost and good economic benefit.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (3)
1. An oxidation-resistant nickel-based alloy, characterized in that: the alloy comprises, by mass, 0.2-0.5% of C, 26-28% of Cr, 0.5-1.5% of Nb, 3-5% of W, 2-4% of Ti, 1-3% of Al, 0.005-0.012% of B, 0.1-0.5% of Si, 0.01-0.1% of Zr, 0-5% of Fe, 0.01-0.1% of rare earth and the balance of Ni.
2. The oxidation resistant nickel-base alloy of claim 1, wherein: in the oxidation-resistant nickel-based alloy, W + Cr-5C is less than or equal to 31%, wherein W, Cr and C respectively represent the mass fractions of elements W, Cr and C in the oxidation-resistant nickel-based alloy.
3. The oxidation resistant nickel-base alloy of claim 1, wherein: in the oxidation-resistant nickel-based alloy, Ti/Al is more than or equal to 0.8 and less than or equal to 3.5, wherein Ti and Al respectively represent the mass fraction of elements Ti and Al in the oxidation-resistant nickel-based alloy.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112375954A (en) * | 2020-11-10 | 2021-02-19 | 华能国际电力股份有限公司 | Low-cost high-strength oxidation-resistant iron-nickel-based alloy and preparation method thereof |
| CN112695264A (en) * | 2020-12-02 | 2021-04-23 | 中国科学院金属研究所 | Method for preparing large equiaxed grains with different orientations |
| CN113278968A (en) * | 2021-06-24 | 2021-08-20 | 南昌大学 | High-temperature oxidation resistant Al-Si composite addition modified nickel-based high-temperature alloy coating and preparation method thereof |
| CN114457261A (en) * | 2020-11-10 | 2022-05-10 | 中国科学院上海应用物理研究所 | Corrosion-resistant nickel-based wrought superalloy for molten salt reactor and preparation method thereof |
| CN116121596A (en) * | 2022-11-01 | 2023-05-16 | 大圆节能材料股份有限公司 | High-temperature-resistant nickel-based alloy for manufacturing glass wool centrifuge |
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| CN110106378A (en) * | 2019-05-15 | 2019-08-09 | 丹阳市华龙特钢有限公司 | A kind of preparation method of nickel base superalloy |
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2019
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US3170789A (en) * | 1961-11-16 | 1965-02-23 | Owens Corning Fiberglass Corp | Nickel-base alloy |
| US5330591A (en) * | 1991-04-25 | 1994-07-19 | Isover Saint-Gobain | Alloy for glass fibre centrifuges |
| WO2005040439A1 (en) * | 2003-10-28 | 2005-05-06 | Ebara Corporation | Incineration apparatus and gasification apparatus |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112375954A (en) * | 2020-11-10 | 2021-02-19 | 华能国际电力股份有限公司 | Low-cost high-strength oxidation-resistant iron-nickel-based alloy and preparation method thereof |
| CN114457261A (en) * | 2020-11-10 | 2022-05-10 | 中国科学院上海应用物理研究所 | Corrosion-resistant nickel-based wrought superalloy for molten salt reactor and preparation method thereof |
| CN112695264A (en) * | 2020-12-02 | 2021-04-23 | 中国科学院金属研究所 | Method for preparing large equiaxed grains with different orientations |
| CN113278968A (en) * | 2021-06-24 | 2021-08-20 | 南昌大学 | High-temperature oxidation resistant Al-Si composite addition modified nickel-based high-temperature alloy coating and preparation method thereof |
| CN116121596A (en) * | 2022-11-01 | 2023-05-16 | 大圆节能材料股份有限公司 | High-temperature-resistant nickel-based alloy for manufacturing glass wool centrifuge |
| CN116121596B (en) * | 2022-11-01 | 2023-08-04 | 大圆节能材料股份有限公司 | High-temperature-resistant nickel-based alloy for manufacturing glass wool centrifuge |
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