CN113195758A - New use of nickel alloy - Google Patents
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- CN113195758A CN113195758A CN201880100401.0A CN201880100401A CN113195758A CN 113195758 A CN113195758 A CN 113195758A CN 201880100401 A CN201880100401 A CN 201880100401A CN 113195758 A CN113195758 A CN 113195758A
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- 229910000990 Ni alloy Inorganic materials 0.000 title description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 142
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 68
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 17
- 229910045601 alloy Inorganic materials 0.000 claims description 108
- 239000000956 alloy Substances 0.000 claims description 108
- 239000000203 mixture Substances 0.000 claims description 16
- 229910052735 hafnium Inorganic materials 0.000 claims description 15
- 229910052726 zirconium Inorganic materials 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 13
- 229910052758 niobium Inorganic materials 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 239000011833 salt mixture Substances 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 8
- 150000003839 salts Chemical class 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 239000000523 sample Substances 0.000 description 26
- 239000011651 chromium Substances 0.000 description 16
- 239000010936 titanium Substances 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 13
- 238000005260 corrosion Methods 0.000 description 13
- 239000010955 niobium Substances 0.000 description 13
- 229910052761 rare earth metal Inorganic materials 0.000 description 12
- 150000002910 rare earth metals Chemical class 0.000 description 12
- 229910052715 tantalum Inorganic materials 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000013590 bulk material Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 238000004626 scanning electron microscopy Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000005275 alloying Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 150000001247 metal acetylides Chemical class 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 239000002344 surface layer Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- 229910000423 chromium oxide Inorganic materials 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000012803 melt mixture Substances 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 230000001464 adherent effect Effects 0.000 description 3
- ICYCMCHHVOFCMV-UHFFFAOYSA-L lithium potassium sodium carbonate Chemical class C([O-])([O-])=O.[K+].[Na+].[Li+] ICYCMCHHVOFCMV-UHFFFAOYSA-L 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910000943 NiAl Inorganic materials 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- -1 aluminum nitrides Chemical group 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001513 hot isostatic pressing Methods 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 240000008881 Oenanthe javanica Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910000907 nickel aluminide Inorganic materials 0.000 description 1
- 229910021334 nickel silicide Inorganic materials 0.000 description 1
- RUFLMLWJRZAWLJ-UHFFFAOYSA-N nickel silicide Chemical compound [Ni]=[Si]=[Ni] RUFLMLWJRZAWLJ-UHFFFAOYSA-N 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- MCXBMLBTPQEQJP-UHFFFAOYSA-N potassium;sodium;dinitrate Chemical compound [Na+].[K+].[O-][N+]([O-])=O.[O-][N+]([O-])=O MCXBMLBTPQEQJP-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
Classifications
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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
-
- 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
- C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
- Treatment Of Steel In Its Molten State (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
Abstract
The present disclosure relates to the use of parts made of nickel-based materials alloyed with aluminum in a molten salt environment, in particular a carbonate environment.
Description
Technical Field
The present disclosure relates to the use of components made from nickel-based alloys in a molten salt mixture environment, particularly a carbonate mixture environment.
Background
In the area of renewable energy, Concentrated Solar Power (CSP) has been in the development phase compared to, for example, photovoltaic methods. This is mainly due to the difficulty of obtaining a sufficiently good energy efficiency and the lack of a good qualityTo the thermal storage medium. However, studies have shown that salt melts can act as good thermal storage media and one proposed medium is a sodium-potassium nitrate mixture, commonly referred to as "solar salt". The most serious problem with these solar salts is that they decompose at temperatures in excess of about 550 c, which in turn leads to corrosion of the components used in the plant. Because of these corrosion problems, other salt mixtures have recently been developed. These salt mixtures are more stable and are in the form of carbonates, usually lithium-sodium-and potassium-carbonates (LiNaK; Li)2CO3-Na2CO3-K2CO3) Is based. Although these salt mixtures are more stable, they have been shown to be more corrosive, and studies on corrosion performed on these salt mixtures to date have not provided any promising results.
It is therefore an aspect of the present disclosure to provide a solution to, or at least mitigate, the above problems.
Disclosure of Invention
The present disclosure relates to the use of components made of dispersion strengthened (dispersion strengthened) nickel based alloys comprising, in weight percent (wt%):
selected from Ta, Zr, Hf, Ti and Nb
0.25 to 2.5 of one or more elements in the group;
one or more elements selected from the group consisting of REM up to 0.5;
the balance being Ni and impurities normally present.
The inventors have surprisingly found that parts made from aluminum oxide-forming nickel-based alloys containing specific elements in specific ranges will have superior corrosion performance over other materials in a molten carbonate mixture environment, even at temperatures up to 750 ℃.
Drawings
Figure 1 shows a cross-section of sample a after exposure. The cross-section shows the surface layer with bulk (bulk) material underneath. Sample a is an alloy according to the present disclosure;
fig. 2 shows a cross-section of sample B after exposure. The cross-section shows the surface layer of the sample with bulk material underneath;
fig. 3 shows a cross-section of sample C after exposure. The cross-section shows the surface layer of the sample with bulk material underneath;
fig. 4A shows a cross-section of sample D after exposure. The cross-section shows the surface layer of the sample with bulk material underneath;
fig. 4B shows a cross-section of sample D after exposure. The cross section shows the region with precipitates below the surface in the sample.
Detailed Description
It was surprisingly found that parts comprising specific nickel-based alloys alloyed with aluminum do not corrode in the carbonate-comprising salt melt mixture. Thus, the present nickel-based alloy as defined above or below is an alumina-forming nickel-based alloy, which has been demonstrated to be capable of pure CO at a temperature of 750 ℃2Protective alumina is formed and maintained in a molten carbonate mixture, such as a LiNaK carbonate mixture.
The nickel-based alloy has the following composition in weight percent (wt%):
selected from Ta, Zr, Hf, Ti and Nb
0.25 to 2.5 of one or more elements in the group;
selected from the group consisting of Rare Earth Metals (REM)
0.5 maximum;
the balance being Ni and impurities normally present.
As mentioned above, it is very surprising that components comprising the present nickel-based alloys are resistant to corrosion in the molten carbonate mixture environment because: firstly The temperature in these environments is too low for The formation of aluminium oxide and secondly The environment has proven to be very corrosive to other similar Alloys as shown by The SERI report SERIIPR-255-2561 entitled "Corrosion of Selected Alloys in eutectic Lithium Sodium Potassium Carbonate at 900 ℃".
Without being bound by any theory, it is believed that the influence of the high creep resistance of the nickel-based alloy as defined above or below, and the surprising formation of a protective aluminum oxide layer, is critical to this corrosion resistance.
The present disclosure also relates to a method of storing heat, the method comprising:
-providing a salt melt mixture comprising a carbonate salt as defined above or below;
-providing a component comprising a dispersion strengthened nickel based alloy as defined above or below.
The component may for example be used for storing the salt melt mixture.
Accordingly, the present disclosure relates to a component comprising a dispersion strengthened nickel based alloy comprising the following elements in weight percent (wt%):
selected from Ta, Zr, Hf, Ti and Nb
0.25 to 2.5 of one or more elements in the group;
one or more selected from the group consisting of REM
Various elements up to 0.5;
the balance being Ni and impurities normally present.
Further, the present disclosure relates to a corrosion-resistant method comprising:
the components are mounted in a position exposed to the environment of the molten carbonate mixture,
wherein the component comprises a dispersion strengthened nickel based alloy, the nickel based alloy comprising the following elements in weight percent (wt%):
selected from Ta, Zr, Hf, Ti and Nb
0.25 to 2.5 of one or more elements in the group;
one or more elements selected from the group consisting of REM up to 0.5;
the balance being Ni and impurities normally present; and is
The present disclosure also relates to a method of improving corrosion performance of a component, the method comprising:
the part is exposed to an environment of a molten carbonate mixture,
wherein the component comprises a dispersion strengthened nickel based alloy, the nickel based alloy comprising the following elements in weight percent (wt%):
selected from the group consisting of Ta, Zr, Hf, Ti and Nb
0.25 to 2.5 of one or more elements;
one or more elements selected from the group consisting of REM up to 0.5;
the balance being Ni and impurities normally present; and is
According to one embodiment, a part exposed to the environment of the molten carbonate mixture will form an outer layer of aluminum oxide on the part.
According to another embodiment, the part is pre-oxidized prior to exposure of the part to the molten carbonate mixture environment, wherein pre-oxidation results in the formation of an outer layer of aluminum oxide on the part.
The elemental composition of the nickel-based alloy is generally as defined above or below, and the function of each alloying element will be further described below. However, the listing of the functions and effects of each alloying element should not be considered complete, but other functions and effects of the alloying elements may exist. The terms wt% and wt% are used interchangeably. According to one embodiment, the nickel-based alloy is composed of all the elements mentioned above or below within the range mentioned above or below.
Carbon (C)
The free form carbon will occupy interstitial sites in the crystal structure, locking in dislocation migration at temperatures up to about 400-500 ℃. Carbon will also form carbides with other elements in the present nickel-based alloy, such as Ta, Ti, Hf, Zr and Nb. In microstructures with finely dispersed carbides, these carbides provide obstacles to dislocation movement, and can be effective even at higher temperatures. Since dislocation migration is a mechanism for generating creep elongation, carbon is an essential element for improving creep strength of the present nickel-based alloy. However, too high a content of C may cause the present nickel-based alloy to become difficult to cold work due to deterioration of ductility at lower temperatures, for example, below 300 ℃. Therefore, the nickel-based alloy contains 0.05 to 0.2 wt% of C.
Silicon (Si)
Silicon may be present in the present nickel-based alloy in a content of up to 1.5 wt.%. Too high a silicon content leads to an increased risk of nickel silicide precipitation, which has an embrittling effect on such alloys. The results of creep tests on similar alloys show that the creep life, i.e. creep rupture time, becomes shorter as the Si content approaches 1.5 wt.%. However, the reason for this is not clear. In view of this, the Si content should preferably be at most 1% by weight. According to one embodiment, the nickel-based alloy as defined above or below comprises Si only in an impurity content, i.e. at most 0.3 wt.%.
Manganese (Mn)
Manganese is present as an impurity in the nickel-based alloy as defined above or below. It is likely that up to 0.5 wt.% Mn may be tolerated without adversely affecting the properties of the present nickel-based alloy, whereby the alloy contains a maximum of 0.5 wt.% Mn. According to one embodiment, the nickel based alloy as defined above or below comprises only Mn with an impurity content, i.e. at most 0.2 wt.%.
Chromium (Cr)
Chromium is an element as follows: has been the primary element for a long time to produce dense and protective oxide scale. Cr below 15 wt% in the austenitic structure tends to result in oxides that do not completely cover the surface and are not dense, thus making the alloy deficient in oxidation resistance. There is also a risk that the material closest to the oxide is depleted of Cr, so that possible damage to the oxide cannot heal, because there is not enough Cr to form a new oxide.
However, nickel-based alloys comprising at least 3 wt.% Al, for example at least 4 wt.% Al, as the present alloy should not comprise more than about 20 wt.% Cr, as higher contents increase the risk of forming gamma-and beta-phases. Therefore, in order to minimize the presence of gamma and beta phases, the nickel-based alloys as defined above or below contain up to 20 wt% Cr. When the Cr content is too high, there may also be a risk of forming other unwanted phases such as sigma phase and chromium-rich ferrite, and further, when the Cr content is high, there may also be a possibility of stabilizing nickel aluminides. Thus, the alloy as defined above or hereinafter comprises 15-20 wt% Cr, such as 17-19 wt% Cr.
Aluminum (Al)
Aluminum is an element that produces a much denser and more protective scale than Cr. However, aluminum cannot replace Cr because aluminum oxide forms more slowly than chromium oxide at lower temperatures. The alloy contains at least 3 wt.% Al, for example at least 4 wt.% Al, which will ensure sufficient oxidation resistance at high temperatures and complete surface coverage with oxides. A relatively high content of Al provides excellent oxidation resistance even at temperatures of about 1100 ℃. When the Al content is higher than 6 wt%, there is a risk that a certain amount of intermetallic phase is formed in the nickel-based matrix so that the ductility of the material is significantly deteriorated. Thus, the alloy should contain 3 to 6 wt.% Al, such as 3.5 to 5.5 wt.%, such as 4 to 5.5 wt.% Al.
Iron (Fe)
It has been shown in accordance with the present disclosure that relatively high levels of Fe in aluminum oxide-forming nickel-based alloys can have a positive effect. The addition of Fe produces a metallic structure which is energetically unfavorable for the formation of embrittlement γ', which in turn leads to a greatly reduced risk of the alloy becoming hard and brittle. Thus, the workability is improved. Thus, the present nickel-based alloy contains at least 15 wt% Fe. However, high levels of iron may lead to the formation of undesirable phases. Therefore, the present nickel-based alloy should not contain more than 25 wt% of Fe.
Further, for certain alloys within the ranges as defined hereinabove or hereinafter, an Fe content of more than about 21-22 wt.% may increase the risk of forming beta phase (NiAl), which may be embrittling in some cases. According to one embodiment, the present alloy may therefore comprise 16 to 21.5 wt% Fe. According to another embodiment, the present alloy comprises 17 to 21 wt% Fe.
Nickel (Ni)
The alloy according to the present disclosure is a nickel-based alloy. Nickel is an element that stabilizes the austenitic structure in the present alloy, counteracting the formation of some brittle intermetallic phases such as sigma. The austenitic structure of the present alloy is beneficial, for example, when welding. The austenitic structure is also shown to contribute to the good creep strength of the present alloy at high temperatures. According to one embodiment, the alloy comprises 52 to 62 wt% Ni, such as 52 to 60 wt% Ni.
Cobalt (Co)
In some commercial alloys, Co may be substituted for a portion of the Ni content in order to improve the mechanical strength of the alloy, as may be the case with the present nickel-based alloys. Thus, part of the Ni content of the present alloy may be replaced by an equal amount of Co. However, this addition of Co must be balanced with the oxidation properties, since the presence of NiAl reduces the activity of Al, thereby deteriorating the ability to form aluminum oxide. However, the Co content should not exceed 10 wt.%. According to one embodiment, the Co content does not exceed 8 wt%. According to another embodiment, the Co content does not exceed 5 wt% and according to yet another embodiment, the Co content is less than 1 wt%.
Nitrogen (N)
Like C, free N occupies interstitial sites in the crystal structure, locking in dislocation migration at temperatures up to about 400-500 ℃. Nitrogen also forms nitrides and/or carbonitrides with other elements in the present nickel-based alloys, such as Ta, Ti, Hf, Zr, and Nb. In the microstructure where these particles are finely dispersed, they can present obstacles to dislocation migration, especially at higher temperatures. Therefore, N is added to improve the creep strength of the present nickel-based alloy. However, when N is added to the aluminum alloyed alloy, the risk of forming secondary aluminum nitrides is high, and thus the N content of the present nickel-based alloy is very limited. The alloy comprises 0.03-0.15 wt% N, such as 0.05-0.10 wt% N.
Oxygen (O)
Oxygen may be present in the present nickel-base alloys as an impurity or as an active addition of up to 0.5% by weight. Oxygen can help increase the creep strength of the present alloys by forming small oxide dispersions (dispersions) with Zr, Hf, Ta and Ti, which can improve the creep strength of the alloys when they are finely distributed in the alloys. These oxide dispersions have a higher dissolution temperature than the corresponding carbides and nitrides, whereby oxygen is preferably added when used at high temperatures. Oxygen may also form a dispersion with Al, elements from group 3 of the periodic table, Sc, Y and La, and the fourteen lanthanide elements, thereby contributing to the creep strength of the present alloy in the same manner as the elements defined above. According to one embodiment, the alloy contains 10 to 2000ppm O, according to another embodiment 20 to 2000ppm O. According to another embodiment, the alloy comprises 10 to 200ppm, 200 to 2000ppm O or 400 to 1000ppm O.
Tantalum, hafnium, zirconium, titanium and niobium (Ta, Hf, Zr, Ti, Nb)
Elements in the group consisting of Ta, Hf and Zr form very small and stable particles with carbon and nitrogen. It is these particles, if they are finely dispersed in the structure, that will help to lock in dislocation motion, thereby increasing creep strength, i.e., providing dispersion strengthening. This effect can also be achieved by adding Ti. However, the addition of Ti can sometimes cause problems, especially during powder metallurgical manufacture of the alloy, since it can form carbides and nitrides already in the melt before atomization, which can block the orifices during atomization. Niobium also forms a stable dispersion with C and/or N and can therefore be suitably added to the present nickel-based alloy.
The alloy comprises one or more elements selected from the group consisting of: ta, Zr, Hf, Ti and Nb.
The alloy may also contain the elements in amounts such that substantially all of the C and N are bonded to the elements Ta, Zr, Hf, Ti and Nb. This will ensure that the risk of formation of chromium carbides, for example during high temperature use of the alloy, is significantly reduced.
According to a preferred embodiment, the nickel based alloy as defined above or below comprises 0.1 to 0.5 wt% Hf. According to another embodiment, the nickel-based alloy includes 0.05 to 0.35 wt% of Zr. According to still another embodiment, the nickel-based alloy includes 0.05 to 0.5 wt% of Ta. According to still another embodiment, the nickel-based alloy includes 0.05 to 0.4 wt% of Ti. According to yet another embodiment, the nickel-based alloy includes 0.1 to 0.8 wt% of Nb.
Rare Earth Metals (REM)
In this context, Rare Earth Metals (REM) refer to elements of group iii of the periodic table, Sc, Y and La, and the fourteen lanthanides. REM affects the oxidation performance by doping the formed oxide. Excessive alloying of these elements often produces oxides that are prone to surface spalling, and too low an amount of these elements added tends to produce oxides that are less adherent to the metal surface. The present nickel-based alloy may comprise one or more elements selected from the group consisting of REM in a total content of up to 0.5 wt.%, for example 0.05 to 0.25 wt.%. According to one embodiment yttrium is added to the alloy as defined above or below in an amount of 0.05 to 0.25 wt%.
The nickel-based alloy as defined above or hereinafter may further include impurities that are generally present as a result of the raw materials used or the selected manufacturing process. Examples of impurities include, but are not limited to, Ca, S, and P. In addition, other alloying elements that do not affect the alloy properties may optionally be added in amounts up to 1 wt.%.
When the term "maximum" is used, the skilled artisan will appreciate that the lower limit of the range is 0 weight percent unless another value is explicitly stated.
The nickel-based alloy as defined above or below may be manufactured according to conventional methods, e.g. casting followed by hot and/or cold working and optionally additional heat treatment. The nickel-based alloy as defined above or below may also be manufactured as a powder product. The process for manufacturing the component may then be for example a hot isostatic pressing process (HIP).
According to the present disclosure, the component may be a tube, a strip, a plate, or a wire. It should be noted that the component may also have any shape, depending on the location and manner in which it is to be used. The component may also be a coating to protect another material, for example the present nickel-based alloy is a coating on a component made of stainless steel.
According to one embodiment of the present disclosure, the component comprising the nickel-based alloy may be pre-oxidized before use.
The disclosure is further illustrated by the following non-limiting examples.
Examples
This example was conducted to investigate the effect of the molten salt mixture on the chromium oxide and aluminum oxide (i.e., chromium oxide and aluminum oxide) forming alloy. The samples (A-D) used are shown in Table 1. Studies were conducted by isothermal and long-term cyclic exposure up to 750 hours at temperatures up to 750 ℃.
The sample material was cut into test specimens, ground to 1200 grit finish (grit finish) with SiC paper, cleaned, weighed and placed into an alumina crucible filled with a salt mixture. The salt mixture was prepared by mixing equal amounts of LiCO using a mortar3、NaCO3And KCO3The components were carefully mixed and freshly prepared for each exposure cycle. The prepared crucible was placed in a heat constant zone (heat constant zone) of a horizontal tube furnace. Under a controlled atmosphere with CO2After purging for at least 8 hours, heating of the crucible was started. The crucible was checked once a week and refilled with the salt mixture. After the target residence time, the furnace was cooled and then removed from the crucible.
After removing the crucible from the furnace, the exposed sample was washed with warm water (60 ℃) and then treated with sonication.
The exposed samples were studied by using optical microscopy and Scanning Electron Microscopy (SEM). SEM was used to identify surface species, scale formation and internal corrosion processes. FIGS. 1-4 show cross-sectional images of SEM studies of samples A, B, C and D.
Figure 1 shows the formation of a thin protective oxide layer on sample a, a sample of the present nickel-based alloy as defined above or below. The oxide layer formed after exposure is adherent, has good surface coverage and is only a few microns thick. Furthermore, SEM studies show that the bulk material under the surface layer is not affected by exposure of the molten carbonate mixture.
Fig. 2 shows a cross-sectional image of sample B, which is a typical FeCrAl alloy. The surface oxide formed is not completely protective. The oxide is relatively thick and not dense.
Fig. 3 shows a cross-sectional image of sample C, which is a high temperature stainless steel. The surface oxide formed is thick and porous and does not adhere. Furthermore, SEM studies have shown that the bulk material below the surface has been affected in regions extending more than 100 microns into the sample.
Fig. 4A shows a cross-sectional image of sample D, which is an example of a nickel-based alloy containing silicon. On this sample, a thick porous and non-adherent oxide was formed on the surface. A closer examination of the bulk material using SEM showed that the bulk material was affected in a region extending more than 100 microns into the sample. In this region, a large number of cliff (precipice) was found to have formed, as shown in FIG. 4B.
Thus, as shown in the results and FIGS. 1 to 4, sample A, which is the present nickel-based alloy, has excellent corrosion resistance in such an aggressive molten carbonate mixture environment. The formed surface oxide is thin and compact, and has adhesiveness and protectiveness. In addition, the microstructure of the bulk material below the surface is not affected by exposure.
As discussed hereinbefore, this is a very surprising result, especially if SERIIPR-255-2561 is reported with reference to the IERI entitled "corrosion of selected alloys in eutectic lithium sodium potassium carbonate at 900 ℃. This report describes the exposure of various alloys to molten carbonate. The exposed samples were alumina forming alloy Cabot 214 (see sample F in Table 1) and chromium oxide forming alloy Cabot 800H (see sample E in Table 1). The result of the exposure was that the Cabot 214 specimen had swelled to the extent that it could not be removed from the sample holder after 9 days (216 hours) of exposure. The Cabot 800H sample swelled large after 14 days to be removed from the sample holder. Thus, the results of this study indicate that the alumina-forming alloy is in an oxygen-free atmosphere (e.g., pure CO)2) Does not function in molten LiNaK carbonate. This is to be compared to the results of the present disclosure, which show that certain alumina-forming nickel-based alloys (i.e., alloys according to the present disclosure) are in pure CO2Will have very good corrosion performance in these carbonate melt mixtures up to 750 ℃.
TABLE 1 alloys used
Claims (12)
1. Use of a component comprising a dispersion strengthened nickel based alloy in the environment of a molten carbonate mixture, said nickel based alloy comprising in weight% (wt%):
the balance being Ni and impurities normally present.
2. Use according to claim 1, wherein the nickel based alloy comprises 16-21.5 wt% Fe.
3. Use according to any one of the preceding claims, wherein the nickel based alloy comprises 17-20 wt% Cr.
4. Use according to any one of the preceding claims, wherein the nickel based alloy comprises up to 0.3 wt% Si.
5. Use according to any one of the preceding claims, wherein the nickel based alloy comprises one or more elements selected from the group consisting of REM in a total content of 0.05 to 0.25 wt%.
6. Use according to any one of the preceding claims, wherein the nickel based alloy comprises one or more elements selected from the group consisting of: ta, Zr, Hf, Ti and Nb.
7. Use according to any one of the preceding claims, wherein the nickel based alloy comprises 52-62 wt% Ni.
8. Use according to any one of the preceding claims, wherein the nickel-based alloy is manufactured by conventional metallurgical methods or by powder technology.
9. Use according to any one of the preceding claims, wherein the carbonate mixture is LiNaK or Li2CO3-Na2CO3-K2CO3A salt mixture.
10. Use according to any one of the preceding claims, wherein the atmosphere of the environment consists of pure CO2And (4) forming.
11. Use according to any one of the preceding claims, wherein the component is selected from: a tube, tape, plate, wire, or coating.
12. Use according to any one of the preceding claims, wherein the component has an arbitrary shape depending on the position and manner in which it is to be used.
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| Application Number | Priority Date | Filing Date | Title |
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| PCT/EP2018/086751 WO2020126053A1 (en) | 2018-12-21 | 2018-12-21 | New use of a nickel-based alloy |
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| US (1) | US20220074026A1 (en) |
| EP (1) | EP3899074B1 (en) |
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| CN102216479A (en) * | 2008-11-19 | 2011-10-12 | 山特维克知识产权股份有限公司 | Aluminium oxide forming nickel based alloy |
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| WO2017142441A1 (en) * | 2016-02-17 | 2017-08-24 | Дмитрий Леонидович МИХАЙЛОВ | Nickel-based corrosion resistant alloy |
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| DE4111821C1 (en) * | 1991-04-11 | 1991-11-28 | Vdm Nickel-Technologie Ag, 5980 Werdohl, De | |
| US20040156737A1 (en) * | 2003-02-06 | 2004-08-12 | Rakowski James M. | Austenitic stainless steels including molybdenum |
| DE102006019590A1 (en) * | 2006-04-27 | 2007-10-31 | Degussa Gmbh | Reaction container, useful for preparing hydrogen sulfide by reacting sulfur and hydrogen, comprises optionally connecting device, armature, measuring- and regulating- device containing a material having aluminum |
| US20190292631A1 (en) * | 2016-05-20 | 2019-09-26 | Sandvik Intellectual Property Ab | An object comprising a pre-oxidized nickel-based alloy |
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2018
- 2018-12-21 US US17/415,197 patent/US20220074026A1/en not_active Abandoned
- 2018-12-21 CN CN201880100401.0A patent/CN113195758B/en active Active
- 2018-12-21 WO PCT/EP2018/086751 patent/WO2020126053A1/en unknown
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| US20010026881A1 (en) * | 2000-01-25 | 2001-10-04 | Kist ( Korea Institute Of Science And Technology) | Internal reforming molten carbonate fuel cell with membrane for intercepting carbonate vapor |
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| CN113195758B (en) | 2022-08-23 |
| EP3899074B1 (en) | 2023-04-26 |
| US20220074026A1 (en) | 2022-03-10 |
| EP3899074A1 (en) | 2021-10-27 |
| WO2020126053A1 (en) | 2020-06-25 |
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