CN103966476B - A kind of nickel base superalloy of the anti-fused salt corrosion of excellent performance - Google Patents
A kind of nickel base superalloy of the anti-fused salt corrosion of excellent performance Download PDFInfo
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- CN103966476B CN103966476B CN201310041486.9A CN201310041486A CN103966476B CN 103966476 B CN103966476 B CN 103966476B CN 201310041486 A CN201310041486 A CN 201310041486A CN 103966476 B CN103966476 B CN 103966476B
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- 230000007797 corrosion Effects 0.000 title claims abstract description 34
- 238000005260 corrosion Methods 0.000 title claims abstract description 34
- 150000003839 salts Chemical class 0.000 title claims abstract description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 12
- 229910000601 superalloy Inorganic materials 0.000 title claims abstract description 9
- 238000005275 alloying Methods 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 5
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 abstract description 57
- 239000000956 alloy Substances 0.000 abstract description 57
- 239000000463 material Substances 0.000 abstract description 3
- 239000007769 metal material Substances 0.000 abstract description 2
- 230000005855 radiation Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 23
- 238000002844 melting Methods 0.000 description 22
- 230000008018 melting Effects 0.000 description 22
- 238000005266 casting Methods 0.000 description 12
- 238000011056 performance test Methods 0.000 description 12
- 230000006698 induction Effects 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910000856 hastalloy Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910001199 N alloy Inorganic materials 0.000 description 1
- 230000003471 anti-radiation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- Turbine Rotor Nozzle Sealing (AREA)
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Abstract
The invention discloses a kind of nickel base superalloy of the anti-fused salt corrosion of excellent performance, belong to technical field of metal material.By weight percentage, the alloying component is：C≤0.08%（Preferred scope 0.03~0.06%）, Fe0.5 ~ 5%, Cr6.0 ~ 8.0%, Mo12 ~ 18%, Ta≤2.0%, Ti≤2.0%, Nb≤2.0%, Ni surpluses；Wherein：1%≤Ti+Nb+Ta≤2%.The alloy not only has excellent temperature-room type plasticity, high temperature microstructure stability and mechanical behavior under high temperature higher, while have good anti-fused salt corrosion performance, can meet has fused salt compared with operation at high temperature and performance requirement, radiation environment to use needs.Suitable for the high-temperature structural material of fused salt nuclear reactor.
Description
Technical field
The present invention relates to technical field of metal material, and in particular to a kind of nickel-base high-temperature of the anti-fused salt corrosion of excellent performance
Alloy.
Background technology
Using fused salt as cooling medium forth generation nuclear reactor, in the presence of serious fluoride molten salt etching problem,
Therefore different from other types of reactor, alloy is while high strength at high temperature is ensured, in addition it is also necessary to have good anti-fluoride to melt
Salt corrosion performance.In the development of anti-fluoride molten salt corrosion high temperature alloy, China is external current at present also in the starting stage
The alloy of anti-fused salt corrosion is mainly Hastelloy N alloys, also exists compared with external anti-fluoride molten salt resistant alloy
A certain distance.
Be this present invention for the low problem of anti-fluoride corrosion alloy property, develop with anti-fused salt corrosion performance with
External alloy is Ni-based higher than the anti-fluoride molten salt corrosion of the high-performance of Hastelloy N performances compared to slightly higher but enduring quality
High temperature alloy.
The content of the invention
It is an object of the invention to provide a kind of nickel base superalloy of the anti-fused salt corrosion of excellent performance, the alloy is not only
With excellent temperature-room type plasticity, high temperature microstructure stability and mechanical behavior under high temperature higher, while having good anti-fused salt rotten
Corrosion energy, can meet has fused salt compared with operation at high temperature and performance requirement, radiation environment to use needs.It is anti-suitable for fused salt core
Answer the high-temperature structural material of heap.
The technical scheme is that：
A kind of nickel base superalloy of the anti-fused salt corrosion of excellent performance（GH3535）, by weight percentage, the alloy
Composition is：C≤0.08%, Fe0.5 ~ 5%, Cr6.0~8.0%, Mo12 ~ 18%, Ta≤2.0%, Ti≤2.0%, Nb≤
2.0%, Ni surplus；Wherein：1%≤Ti+Nb+Ta≤2%；The preferred scope of C is 0.03~0.06%.
By weight percentage, following control of element scope in alloy of the present invention：Co ＜ 0.15%；B ＜ 0.002%；W ＜
0.15%；Al ＜ 0.2%；S≤0.01%, P≤0.005%, Si≤0.8%, Mn≤0.8%, V≤1%, Cu≤0.1%.
The alloy of the present invention designed according to mentioned component is deformation nickel base superalloy, due to Ti, Nb, Ta and C combination shapes
Into more stable carbide, the enduring quality of alloy can be more improved, and the stabilization of carbide is also beneficial to alloy corrosion
And anti-radiation performance, therefore, the present invention is in the content range of precise control C element, while in adding Ti, Nb and Ta at least
One kind, and control under conditions of 1≤Ti+Nb+Ta≤2, then the content 6.0 for controlling the content 12.0~18.0wt%, Cr of Mo
~ 8.0wt%, further increases alloying level, improves alloy property.
The present invention has the beneficial effect that：
1st, the present invention is developed with anti-fused salt corrosion performance and state for the low problem of anti-fluoride corrosion alloy property
Outer alloy is closed compared to raising, enduring quality also above the nickel-base high-temperature that the anti-fluoride molten salt of the high-performance of Hastelloy N corrodes
Gold.
2nd, alloy of the present invention has excellent temperature-room type plasticity, high temperature microstructure stability and mechanical behavior under high temperature higher, together
When with good anti-fused salt corrosion performance, it is adaptable to the high-temperature structural material of fused salt nuclear reactor, 650-700 DEG C work temperature
Excellent combination property is shown under degree.
Specific embodiment
With reference to embodiment in detail the present invention is described in detail, in following embodiment：
Heat treating regime is：1177 DEG C are warming up to stove be incubated 1 hour, water quenching.
Etching condition is as follows：
1st, graphite crucible
Graphite crucible inwall and parts（Peg, lid, bolt and nut）It is true at 700 DEG C after being cleaned by ultrasonic in ethanol
Sky dries 24h, standby in fast transfer to glove box after being cooled to room temperature.
The graphite parameter list of table 1
2nd, fused salt prepares
Fused salt is ingot casting shape FLiNaK（46.5-11.5-42mol%）, impurity content is：Acid ion（SO4 2-+PO4 3-+
NO3 -）Less than 20ppm；Total oxygen content（Including acid group, oxide and water）Less than 750ppm；Metal ion is about 100ppm.Place
It is standby in glove box.
3rd, preparation of samples
Alloy sample is polished to 1200# step by step, oil removing, water removal, cold wind drying have been marked, and are 0.01mg's with precision
Scales/electronic balance weighing is standby.
4th, etching condition
Corrosion temperature：700 DEG C, etching time：400 hours, weigh weight loss.
Performance test conditions：650 DEG C, 324MPa tests creep rupture life.
Embodiment 1
The present embodiment alloy（No.1 alloys）Composition is shown in Table 2, and the composition alloy is after vacuum induction melting（20 kilograms of melting
Ingot shape）, casting ingot-forming, then it is forged intoBar.The bar that will have been forged is heat-treated, the examination that will be heat-treated
Rod is processed into performance test sample and corrosion sample, then carries out enduring quality test and corrosive nature test, and test result is shown in
Table 3 and table 4.
The embodiment 1-11 alloying components of table 2, wt%
| Alloy | Cr | Fe | Mo | Ti | Ta | Nb | C | Si | Mn | Ni |
| No.1 | 6.2 | 3.8 | 12.5 | 1.2 | 0.3 | 0 | 0.032 | 0.48 | 0.67 | It is remaining |
| No.2 | 7.0 | 4.3 | 14.2 | 1.8 | 0.1 | 0.1 | 0.042 | 0.48 | 0.67 | It is remaining |
| No.3 | 7.9 | 4.8 | 14.2 | 1.0 | 0.5 | 0.5 | 0.048 | 0.49 | 0.71 | It is remaining |
| No.4 | 7.0 | 4.3 | 14.2 | 0.5 | 1.3 | 0.15 | 0.042 | 0.48 | 0.67 | It is remaining |
| No.5 | 7.9 | 4.8 | 15.2 | 0.5 | 0.8 | 0.7 | 0.058 | 0.68 | 0.77 | It is remaining |
| No.6 | 7.0 | 4.1 | 16.2 | 0.1 | 1.9 | 0 | 0.058 | 0.68 | 0.77 | It is remaining |
| No.7 | 7.0 | 4.1 | 17.2 | 0.1 | 0 | 1.85 | 0.058 | 0.68 | 0.77 | It is remaining |
| No.8 | 6.8 | 3.5 | 17.8 | 0.4 | 0.1 | 1.5 | 0.058 | 0.68 | 0.77 | It is remaining |
| No.9 | 6.8 | 4.2 | 16.8 | 0.6 | 0.3 | 0.3 | 0.058 | 0.68 | 0.77 | It is remaining |
| No.10 | 7.2 | 4.2 | 16.8 | 0.8 | 0.1 | 0.2 | 0.048 | 0.48 | 0.57 | It is remaining |
| No.11 | 6.2 | 3.8 | 15.8 | 0.6 | 0.3 | 0.2 | 0.038 | 0.48 | 0.57 | It is remaining |
Embodiment 2
The present embodiment alloy（No.2 alloys）Composition is shown in Table 2, and the composition alloy is after vacuum induction melting（20 kilograms of melting
Ingot shape）, casting ingot-forming, then it is forged intoBar.The bar that will have been forged is heat-treated, the examination that will be heat-treated
Rod is processed into performance test sample and corrosion sample, then carries out enduring quality test and corrosive nature test, and test result is shown in
Table 3 and table 4.
Embodiment 3
The present embodiment alloy（No.3 alloys）Composition is shown in Table 2, and the composition alloy is after vacuum induction melting（20 kilograms of melting
Ingot shape）, casting ingot-forming, then it is forged intoBar.The bar that will have been forged is heat-treated, the examination that will be heat-treated
Rod is processed into performance test sample and corrosion sample, then carries out enduring quality test and corrosive nature test, and test result is shown in
Table 3 and table 4.
Embodiment 4
The present embodiment alloy（No.4 alloys）Composition is shown in Table 2, and the composition alloy is after vacuum induction melting（20 kilograms of melting
Ingot shape）, casting ingot-forming, then it is forged intoBar.The bar that will have been forged is heat-treated, the examination that will be heat-treated
Rod is processed into performance test sample and corrosion sample, then carries out enduring quality test and corrosive nature test, and test result is shown in
Table 3 and table 4.
Embodiment 5
The present embodiment alloy（No.5 alloys）Composition is shown in Table 2, and the composition alloy is after vacuum induction melting（20 kilograms of melting
Ingot shape）, casting ingot-forming, then it is forged intoBar.The bar that will have been forged is heat-treated, the examination that will be heat-treated
Rod is processed into performance test sample and corrosion sample, then carries out enduring quality test and corrosive nature test, and test result is shown in
Table 3 and table 4.
Embodiment 6
The present embodiment alloy（No.6 alloys）Composition is shown in Table 2, and the composition alloy is after vacuum induction melting（20 kilograms of melting
Ingot shape）, casting ingot-forming, then it is forged intoBar.The bar that will have been forged is heat-treated, the examination that will be heat-treated
Rod is processed into performance test sample and corrosion sample, then carries out enduring quality test and corrosive nature test, and test result is shown in
Table 3 and table 4.
Embodiment 7
The present embodiment alloy（No.7 alloys）Composition is shown in Table 2, and the composition alloy is after vacuum induction melting（20 kilograms of melting
Ingot shape）, casting ingot-forming, then it is forged intoBar.The bar that will have been forged is heat-treated, the examination that will be heat-treated
Rod is processed into performance test sample and corrosion sample, then carries out enduring quality test and corrosive nature test, and test result is shown in
Table 3 and table 4.
Embodiment 8
The present embodiment alloy（No.8 alloys）Composition is shown in Table 2, and the composition alloy is after vacuum induction melting（20 kilograms of melting
Ingot shape）, casting ingot-forming, then it is forged intoBar.The bar that will have been forged is heat-treated, the examination that will be heat-treated
Rod is processed into performance test sample and corrosion sample, then carries out enduring quality test and corrosive nature test, and test result is shown in
Table 3 and table 4.
Embodiment 9
The present embodiment alloy（No.9 alloys）Composition is shown in Table 2, and the composition alloy is after vacuum induction melting（20 kilograms of melting
Ingot shape）, casting ingot-forming, then it is forged intoBar.The bar that will have been forged is heat-treated, the examination that will be heat-treated
Rod is processed into performance test sample and corrosion sample, then carries out enduring quality test and corrosive nature test, and test result is shown in
Table 3 and table 4.
Embodiment 10
The present embodiment alloy（No.10 alloys）Composition is shown in Table 2, and the composition alloy is after vacuum induction melting（Melting 20 is public
Jin ingot shape）, casting ingot-forming, then it is forged intoBar.The bar that will have been forged is heat-treated, by what is be heat-treated
Coupon is processed into performance test sample and corrosion sample, then carries out enduring quality test and corrosive nature test, test result
It is shown in Table 3 and table 4.
Embodiment 11
The present embodiment alloy（No.11 alloys）Composition is shown in Table 2, and the composition alloy is after vacuum induction melting（Melting 20 is public
Jin ingot shape）, casting ingot-forming, then it is forged intoBar.The bar that will have been forged is heat-treated, by what is be heat-treated
Coupon is processed into performance test sample and corrosion sample, then carries out enduring quality test and corrosive nature test, test result
It is shown in Table 3 and table 4.
The alloy of the present invention of table 3 is contrasted with U.S. HastelloyN alloys enduring quality（650 DEG C, 324MPa）
The different numbering alloy Corrosion results in fluoride molten salt of table 4
〔FLiNaK（46.5-11.5-42mol%）700 DEG C of 400h static corrosions containers of fused salt are graphite crucible)
Claims (2)
1. the nickel base superalloy of the anti-fused salt corrosion of a kind of excellent performance, it is characterised in that：The nickel base superalloy is by weight
Percentages are measured, the alloying component is：C 0.03~0.06%, Fe 0.5~5%, Cr 6.0~7.9%, Mo 12~18%,
Ta≤2.0%, Ti 0.1~2.0%, Nb≤2.0%, Ni surpluses；Wherein：1%≤Ti+Nb+Ta≤2%.
2. the nickel base superalloy of the anti-fused salt corrosion of excellent performance according to claim 1, it is characterised in that：By weight
Percentages, in the alloying component：Co ＜ 0.15%；B ＜ 0.002%；W ＜ 0.15%；Al ＜ 0.2%；S≤0.01%, P≤
0.005%, Si≤0.8%, Mn≤0.8%, V≤0.1%, Cu≤0.1%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106319255B (en) * | 2015-07-06 | 2018-09-21 | 中国科学院金属研究所 | The sublimate smelting process of nickel base superalloy |
| CN106181131B (en) * | 2016-07-15 | 2018-05-29 | 中国科学院上海应用物理研究所 | For the solid core welding wire preparation method of anti-fused salt corrosion nickel base superalloy welding |
| CN106077997B (en) * | 2016-07-15 | 2018-02-09 | 中国科学院上海应用物理研究所 | A kind of solder for anti-fused salt corrosion nickel base superalloy fusion welding |
| CN106191531A (en) * | 2016-08-26 | 2016-12-07 | 桥运精密部件（苏州）有限公司 | A kind of alloy material of acid corrosion-resistant |
| CN106180254B (en) * | 2016-09-26 | 2018-06-29 | 中国科学院上海应用物理研究所 | A kind of preparation method of the nickel of resistance to fused salt corrosion molybdenum evanohm seamless pipe |
| CN106425315A (en) * | 2016-11-15 | 2017-02-22 | 中国科学院上海应用物理研究所 | Preparation method for anti-molten salt corrosion high-temperature alloy seal head |
| CN109055879B (en) * | 2018-09-14 | 2019-11-22 | 中国科学院上海应用物理研究所 | A method of improving the anti-tellurium corrosive nature of UNS N10003 alloy |
| WO2020126053A1 (en) * | 2018-12-21 | 2020-06-25 | Sandvik Intellectual Property Ab | New use of a nickel-based alloy |
| US11708627B2 (en) | 2019-03-29 | 2023-07-25 | Proterial Ltd. | Ni-based superalloy and method for manufacturing Ni-based superalloy |
| CN110355230B (en) * | 2019-07-24 | 2020-06-12 | 浙江久立特材科技股份有限公司 | U-shaped heat exchange tube resistant to high temperature molten salt corrosion |
| CN110643858B (en) * | 2019-11-08 | 2020-10-30 | 中国科学院上海应用物理研究所 | Method for improving tellurium corrosion resistance of nickel-based superalloy and nickel-based superalloy |
| CN112322939A (en) * | 2020-11-04 | 2021-02-05 | 中国科学院上海应用物理研究所 | Nickel-based high-temperature alloy and preparation method thereof |
| CN115679155B (en) * | 2022-08-18 | 2024-06-18 | 上海大学 | Nickel-molybdenum-based alloy material resistant to high-temperature chloride ion molten salt corrosion, preparation method and application thereof |
| CN115595470B (en) * | 2022-10-26 | 2023-09-12 | 西安稀有金属材料研究院有限公司 | Molten salt corrosion resistant nickel-based alloy for spent fuel aftertreatment and preparation method thereof |
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| JPH083665A (en) * | 1994-06-20 | 1996-01-09 | Mitsubishi Materials Corp | Nickel-base superalloy for die excellent in oxidation resistance and high temperature strength |
| CN1101479C (en) * | 1999-01-28 | 2003-02-12 | 住友电气工业株式会社 | Heat-resistant alloy wire |
| JP5248197B2 (en) * | 2008-05-21 | 2013-07-31 | 株式会社東芝 | Ni-base cast alloy and cast component for steam turbine using the same |
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