US20220145436A1 - Superaustenitic Material - Google Patents
Superaustenitic Material Download PDFInfo
- Publication number
- US20220145436A1 US20220145436A1 US17/413,986 US201917413986A US2022145436A1 US 20220145436 A1 US20220145436 A1 US 20220145436A1 US 201917413986 A US201917413986 A US 201917413986A US 2022145436 A1 US2022145436 A1 US 2022145436A1
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- superaustenitic
- alloy
- material according
- weight
- nitrogen
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- 239000000463 material Substances 0.000 title claims abstract description 45
- 238000005260 corrosion Methods 0.000 claims abstract description 31
- 230000007797 corrosion Effects 0.000 claims abstract description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 92
- 229910045601 alloy Inorganic materials 0.000 claims description 57
- 239000000956 alloy Substances 0.000 claims description 57
- 229910052757 nitrogen Inorganic materials 0.000 claims description 49
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 47
- 239000011651 chromium Substances 0.000 claims description 31
- 239000011572 manganese Substances 0.000 claims description 31
- 239000010949 copper Substances 0.000 claims description 26
- 238000001514 detection method Methods 0.000 claims description 22
- 229910052748 manganese Inorganic materials 0.000 claims description 22
- 229910052750 molybdenum Inorganic materials 0.000 claims description 22
- 239000010955 niobium Substances 0.000 claims description 22
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 20
- 229910052804 chromium Inorganic materials 0.000 claims description 20
- 239000010936 titanium Substances 0.000 claims description 20
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 19
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 19
- 239000011733 molybdenum Substances 0.000 claims description 19
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 229910052758 niobium Inorganic materials 0.000 claims description 12
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 12
- 239000010937 tungsten Substances 0.000 claims description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052796 boron Inorganic materials 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 238000010276 construction Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 229910000831 Steel Inorganic materials 0.000 description 23
- 239000010959 steel Substances 0.000 description 23
- 238000001556 precipitation Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005482 strain hardening Methods 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- GJPVPJBNBCITNZ-UHFFFAOYSA-N [N].[Mn].[Cr] Chemical compound [N].[Mn].[Cr] GJPVPJBNBCITNZ-UHFFFAOYSA-N 0.000 description 3
- OGSYQYXYGXIQFH-UHFFFAOYSA-N chromium molybdenum nickel Chemical group [Cr].[Ni].[Mo] OGSYQYXYGXIQFH-UHFFFAOYSA-N 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000005291 magnetic effect Effects 0.000 description 3
- 238000005204 segregation Methods 0.000 description 3
- 229910000851 Alloy steel Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000005298 paramagnetic effect Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910019932 CrNiMo Inorganic materials 0.000 description 1
- 229910001199 N alloy Inorganic materials 0.000 description 1
- JXMHJWIFEMFZDH-UHFFFAOYSA-N [Mn].[Mo].[Cr] Chemical compound [Mn].[Mo].[Cr] JXMHJWIFEMFZDH-UHFFFAOYSA-N 0.000 description 1
- MPQIMOMLTNCGNB-UHFFFAOYSA-N [N].[Mn].[Ni].[Cr] Chemical compound [N].[Mn].[Ni].[Cr] MPQIMOMLTNCGNB-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- SJKRCWUQJZIWQB-UHFFFAOYSA-N azane;chromium Chemical compound N.[Cr] SJKRCWUQJZIWQB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- -1 chromium nitrides Chemical class 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000004836 empirical method Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000007514 turning Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
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- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
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- C—CHEMISTRY; METALLURGY
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- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
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Definitions
- the invention relates to a superaustenitic material and a method for producing the same.
- Materials of this kind are used, for example, in chemical plant construction, under maritime conditions, or in oilfield or gas field technology.
- materials of this kind are that they must also resist corrosion, in particular corrosion in mediums with high chloride concentrations or in sulfuric acid conditions.
- EP 1 069 202 A1 has disclosed a paramagnetic, corrosion-resistant austenitic steel with a high yield strength, strength, and ductility, which should be corrosion-resistant particularly in mediums with a high chloride concentration; this steel should contain 0.6% by weight to 1.4% by weight nitrogen, and 17 to 24% by weight chromium, as well as manganese and nitrogen.
- WO 02/02837 A1 has disclosed a corrosion-resistant material for use in mediums with a high chloride concentration in oilfield technology.
- it is a chromium-nickel-molybdenum superaustenite, which is embodied with comparatively low nitrogen concentrations, but very high chromium concentrations and very high nickel concentrations.
- chromium-manganese-nitrogen steels By comparison to the previously mentioned chromium-manganese-nitrogen steels, these chromium-nickel-molybdenum steels usually have an even better corrosion behavior. By and large, chromium-manganese-nitrogen steels constitute a rather inexpensive alloy composition, which nevertheless offers an outstanding combination of strength, toughness, and corrosion resistance. The above-mentioned chromium-nickel-molybdenum steels achieve significantly higher corrosion resistances than chromium-manganese-nitrogen steels, but entail significantly higher costs because of the very high nickel content.
- Comparable steel grades are also known for use as shipbuilding steels for submarines; in this case, these are chromium-nickel-manganese-nitrogen steels, which are also alloyed with niobium in order to stabilize the carbon, but this diminishes the notched-bar toughness. Basically, these steels contain less manganese and as a result, have a relatively good corrosion resistance, but they do not yet achieve the strength of pure high nitrogen-alloyed CrMnN steels.
- the object of the invention is to produce a superaustenitic, high-strength, and tough material, which can be produced in a comparatively simple and inexpensive way and is particularly suitable for a corrosive, sulfuric acid environment.
- Another object of the invention is to create a method for producing the material.
- the material is intended for use in shipbuilding and in chemical plant construction or in the combination of the two, in this case particularly in flue-gas desulfurization systems of seagoing vessels. It can also be used in all other areas in which corrosion particularly due to sulfuric acid or acid gas is expected.
- the material has a fully austenitic structure even after an optional cold forming. After the strain hardening, the yield strength should be R p0.2 >1000 MPa.
- the alloy according to the invention comprises the following elements in particular (all values expressed in % by weight):
- the steel according to the invention should exist in a precipitation-free state since precipitation has a negative effect on the toughness and the corrosion resistance.
- the carbon content is particularly limited to 0.50%.
- the copper content is intentionally added to the alloy.
- Carbon can be present in a steel alloy according to the invention at concentrations of up to 0.50%. Carbon is an austenite promoter and has a beneficial effect with regard to high mechanical characteristic values. With regard to avoiding carbide precipitation, the carbon content should be set between 0.01 and 0.25%, preferably between 0.01 and 0.10%.
- Silicon is provided in concentrations of up to 0.5% and mainly serves to deoxidize the steel.
- the indicated upper limit reliably avoids the formation of intermetallic phases. Since silicon is also a ferrite promoter, in this regard as well, the upper limit is selected with a safety range. In particular, silicon can be provided in concentrations of 0.1-0.4%.
- Manganese is present in concentrations of 0.1-5%. In comparison to materials according to the prior art, this is an extremely low value. Up to this point, it has been assumed that manganese concentrations of greater than 19%, preferably greater than 20%, are required for a high nitrogen solubility. With the present alloy, it has surprisingly turned out that even with the very low manganese concentrations according to the invention, a nitrogen solubility is achieved that is greater than what is possible according to the prevailing consensus among experts. In addition, it has been assumed up to this point that a good corrosion resistance is accompanied by very high manganese concentrations, but according to the invention, it has turned out that due to unexplained synergistic effects, this is clearly not necessary with the present alloy.
- the lower limit for manganese can be selected as 0.1, 0.5, 1.0, 2.0, or 2.5%.
- the upper limit for manganese can be selected as 3.0, 3.5, 4.0, 4.5, or 5.0%.
- chromium turns out to be necessary for a higher corrosion resistance.
- a concentration of at least 23% and at most 33% chromium is present.
- concentrations higher than 23% have a disadvantageous effect on the magnetic permeability because chromium is one of the ferrite-stabilizing elements.
- concentrations higher than 23% have a disadvantageous effect on the magnetic permeability because chromium is one of the ferrite-stabilizing elements.
- concentrations higher than 23% have a disadvantageous effect on the magnetic permeability because chromium is one of the ferrite-stabilizing elements.
- the alloy according to the invention it has been determined that even very high chromium concentrations above 23% do not negatively influence the magnetic permeability in the present alloy but instead—as is known—influence the resistance to pitting and stress crack corrosion in an optimal way.
- the lower limit for chromium can be selected as 23, 24, 25, or 26%.
- the upper limit for chromium can be selected as 28, 29, 30, 31, or 32%.
- Molybdenum is an element that contributes significantly to corrosion resistance in general and to pitting corrosion resistance in particular; the effect of molybdenum is intensified by nickel. According to the invention, 2.0 to 5.0% molybdenum is added. It has also turned out that Mo concentrations of >5% and particularly >6% result in powerful segregation behavior, which increases the susceptibility to precipitation of the sigma phase, which in turn would reduce the corrosion resistance.
- the lower limit for molybdenum can be selected as 2.0, 2.2, 2.3, 2.4, 2.5, 3.0, 3.2, 3.3, 3.4, or 3.5%.
- the upper limit for molybdenum can be selected as 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, or 5.0%.
- tungsten is present in concentrations of less than 0.5% and contributes to increasing the corrosion resistance.
- the upper limit for tungsten can be selected as 0.5, 0.4, 0.3, 0.2, 0.1%, or below the detection level (i.e. without any intentional addition to the alloy).
- nickel is present in concentrations of 10 to 20%, which achieves a high stress crack corrosion resistance in mediums containing chloride.
- the lower limit for nickel can be selected as 10, 11, 12, 13, 14, or 15%.
- the upper limit for nickel can be selected as 17, 18, or 19%.
- the literature also mentions that primarily in high nitrogen-alloyed steels, Cu increases the susceptibility to precipitation of unwanted Cr 2 N precipitation, which massively diminishes corrosion properties.
- a Cr 2 N-free structure can be produced despite Cu concentrations >0.5, preferably >1.0 and high N concentrations of >0.40%. This effect, however, reaches saturation after a certain quantity.
- the upper limit for copper was selected to be ⁇ 5%, preferably ⁇ 3% or ⁇ 2.5%, in particular ⁇ 2%.
- the lower limit for copper can be selected to be 0.6, 0.7, 0.8, 0.1, 1, or 1.1%.
- One application field in particular is flue-gas scrubbing, particularly in seagoing vessels, for example. With these concentrations, on the one hand, a good resistance to sulfuric acids and also acid gas corrosion can be achieved and on the other hand, it is possible by means of the overall alloy to by and large prevent the precipitation of chromium nitrides as mentioned above.
- Cobalt can be present in concentrations of up to 5%, particularly in order to substitute for nickel.
- the upper limit for cobalt can be selected as 5, 3, 1, 0.5, 0.4, 0.3, 0.2, 0.1%, or below the detection level (i.e. without any intentional addition to the alloy).
- Nitrogen in concentrations of 0.40 to 0.90% is included in order to ensure a high strength. Nitrogen also contributes to the corrosion resistance and is a powerful austenite promoter, which is why concentrations of greater than 0.40% are beneficial.
- the upper limit of nitrogen is set to 0.90%; it has turned out that despite the very low manganese content, by contrast with known alloys, these high nitrogen concentrations in the alloy can be achieved. Because of the good nitrogen solubility on the one hand and the disadvantages that result from higher nitrogen concentrations, in particular ones above 0.90%, a pressure-induced nitrogen content increase as part of a PESR route is in fact out of the question.
- the ratio of nitrogen to carbon is greater than 15.
- the lower limit for nitrogen can be selected as 0.40 or 0.45%.
- the upper limit for nitrogen can be selected as 0.90, 0.80, 0.70, 0.65, or 0.60%.
- the method according to the invention is also inexpensive since the costly pressure-induced nitrogen content increase is not necessary, which also makes it possible to eliminate the remelting process connected therewith.
- boron, aluminum, and sulfur can be contained as additional alloy components, but they are only optional.
- the present steel alloy does not necessarily contain the alloy components vanadium and titanium. Although these elements do make a positive contribution to the solubility of nitrogen, the high nitrogen solubility according to the invention can be provided even in their absence.
- the alloy according to the invention should not contain niobium since it reduces the toughness and historically, was used only for bonding the carbon, which is not necessary with the alloy according to the invention. Concentrations of up to 0.1% niobium are still tolerable, but should not exceed the concentration of inevitable impurities.
- FIG. 1 shows a very schematic depiction of the production route and its alternatives.
- Table 1 shows the alloy components and percentage ranges for the alloy of the invention.
- Table 2 is a table with three different alloys within the concept according to the invention and the resulting actual values of the nitrogen content compared to the theoretical nitrogen solubility of such alloys according to the prevailing school of thought.
- Table 3 shows the mechanical properties (strengths) of the Examples in Table 2 before a possible strain hardening.
- ESR electroslag remelting
- PESR pressure electroslag remelting
- the MARC formula is optimized to such an effect that it has been discovered that the otherwise usual removal of nickel does not apply to the system according to the invention and the limit of 40 is required.
- cold forming steps are carried out as needed in which a strain hardening takes place, followed by the mechanical processing, which in particular can be a turning, milling, or grinding.
- FIG. 1 shows examples of the possible processing routes for the production of the alloy composition according to the invention.
- VIP vacuum induction melting unit
- molten metal simultaneously undergoes melting and secondary metallurgical processing. Then the molten metal is poured into ingot molds and in them, solidifies into blocks. These are then hot formed in multiple steps. For example, they are pre-forged in the rotary forging machine and are brought into their final dimensions in the multiline rolling mill or are rolled into sheet form in two-high rolling stands. Depending on the requirements, a heat treatment step can also be performed.
- a cold forming step can also be performed.
- a superaustenitic material according to the invention can be produced not only by means of the production routes described (and in particular shown in FIG. 1 ), the advantageous properties of the alloy according to the invention can also be achieved by means of a production route using powder metallurgy.
- Table 2 shows three different variants within the alloy compositions according to the invention, with the respectively measured nitrogen values, which have been produced with the method according to the invention in connection with the alloys according to the invention. These very high nitrogen concentrations contrast with the nitrogen solubility indicated in the subsequent columns according to Stein, Satir, Kowandar, and Medovar from “On restricting aspects in the production of non-magnetic Cr—Mn—N-alloy steels, SaIler, 2005.” In Medovar, different temperatures are indicated. It is clear, however, that the high nitrogen values far exceed the theoretically expected values.
- the invention therefore has the advantage that an austenitic, high-strength material with an increased corrosion resistance and low nickel content is produced, which simultaneously exhibits high strength and paramagnetic behavior. Even after the cold forming, a fully austenitic structure is present so that it has been possible to successfully combine the positive properties of an inexpensive CrMnN steel with the outstanding corrosion-related properties of a CrNiMo steel.
- One special feature of the invention is that because of the high nitrogen content, the strain hardening rate is higher than in other superaustenites in order to thus be able to achieve tensile strengths (R m ) of 2000 MPa. It is thus possible as a last production step to achieve a high strain hardening by means of cold rolling or other cold forming processes with high deformation rates.
- Typical application fields of the materials according to the invention are shipbuilding and chemical plant construction or the combination of the two, in this case particularly in flue-gas desulfurization systems of seagoing vessels, but also in all other areas in which sulfuric acid corrosion is particularly expected.
- the strength can be increased even more by means of cold deformation, as described above.
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DE102018133255.6A DE102018133255A1 (de) | 2018-12-20 | 2018-12-20 | Superaustenitischer Werkstoff |
PCT/EP2019/086385 WO2020127789A1 (de) | 2018-12-20 | 2019-12-19 | Superaustenitischer werkstoff |
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CN115261718B (zh) * | 2022-03-28 | 2023-06-06 | 江西宝顺昌特种合金制造有限公司 | 一种超级奥氏体不锈钢s34565板材及其制备方法 |
CN115992330B (zh) * | 2023-02-17 | 2024-04-19 | 东北大学 | 一种高氮低钼超级奥氏体不锈钢及其合金成分优化设计方法 |
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WO2020127788A1 (de) | 2020-06-25 |
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