EP4490331A1 - Procédé de fabrication d'un composant à partir du produit semi-fini d'un alliage nickel-chrome-aluminium - Google Patents

Procédé de fabrication d'un composant à partir du produit semi-fini d'un alliage nickel-chrome-aluminium

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Publication number
EP4490331A1
EP4490331A1 EP23711661.1A EP23711661A EP4490331A1 EP 4490331 A1 EP4490331 A1 EP 4490331A1 EP 23711661 A EP23711661 A EP 23711661A EP 4490331 A1 EP4490331 A1 EP 4490331A1
Authority
EP
European Patent Office
Prior art keywords
content
alloy
chromium
max
weld seams
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP23711661.1A
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German (de)
English (en)
Inventor
Heike Hattendorf
Benedikt NOWAK
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
VDM Metals International GmbH
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VDM Metals International GmbH
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Publication date
Application filed by VDM Metals International GmbH filed Critical VDM Metals International GmbH
Publication of EP4490331A1 publication Critical patent/EP4490331A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • 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
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/50—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for welded joints
    • 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
    • C22C19/053—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 30% but less than 40%
    • 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%
    • 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
    • C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W

Definitions

  • the invention relates to a method for producing a component from the semi-finished product of a nickel-chromium-aluminum wrought alloy with excellent high-temperature corrosion resistance, good creep resistance and good processability.
  • Austenitic nickel-chromium-aluminum wrought alloys with different nickel, chromium and aluminum contents have long been used in furnace construction and in the chemical and petrochemical industries. For this use, good high-temperature corrosion resistance, even in carburizing atmospheres that produce metal dusting, and good high-temperature strength/creep resistance are required.
  • the high-temperature corrosion resistance of the alloys listed in Table 1 increases with increasing chromium content. All of these alloys form a chromium oxide layer (Cr20s) with an underlying, more or less closed, aluminum oxide layer (AI2O3) with the corresponding aluminum contents. Small additions of elements with a strong affinity for oxygen, such as yttrium or cerium, improve the oxidation resistance. The chromium content is slowly consumed over the course of use in the area of application to build up the protective layer.
  • a higher chromium content increases the lifespan of the material, since a higher content of the element chromium, which forms the protective layer, delays the point in time at which the chromium content is below the critical limit and oxides other than pure chromium oxides (Cr20s) form, which is, for example, iron - and nickel-containing oxides.
  • Cr20s pure chromium oxides
  • a further increase in high-temperature corrosion resistance can be achieved by adding aluminum and silicon. Above a certain minimum content, these elements form a closed layer beneath the chromium oxide layer and thus reduce the consumption of chromium.
  • carburizing atmospheres CO, H2, CH4, CO2, H2O mixtures with possibly other process-related non-oxidizing components
  • carbon can penetrate into the material, which can lead to the formation of internal carbides. These cause a loss of notched impact strength.
  • the melting point can also drop to very low values (up to 350°C) and conversion processes can occur due to chromium depletion of the matrix.
  • Nickel alloys are therefore generally more resistant to carburization than iron alloys because both carbon diffusion and carbon solubility are lower in nickel than in iron.
  • Increasing the chromium content results in greater carburization resistance by forming a protective chromium oxide layer, unless the oxygen partial pressure in the gas is too low to form this protective chromium oxide layer.
  • materials containing silicon or aluminum can be used, which form a layer of silicon oxide or the even more stable aluminum oxide, which forms at significantly lower oxygen partial pressures compared to chromium oxide.
  • metal dusting can occur in nickel, iron or cobalt alloys.
  • the alloys can absorb large amounts of carbon Segregation processes that take place on carbon-supersaturated alloys lead to material destruction.
  • the alloy breaks down into a mixture of metal particles, graphite, carbides and/or oxides. This type of material destruction occurs in the temperature range of approximately 500 to 750°C.
  • Typical conditions for the occurrence of “metal dusting” are strongly carburizing CO, H2 and/or CFU gas mixtures, such as those that occur in ammonia synthesis, in methanol plants, in metallurgical processes, but also in hardening furnaces.
  • the resistance to “metal dusting” tends to increase as the nickel content of the alloy increases, although nickel alloys are not resistant to “metal dusting” either.
  • the chromium and aluminum content have a significant influence on the corrosion resistance under “metal dusting” conditions (see Figure 2).
  • Nickel alloys with low chromium content such as the alloy Alloy 600 (N06600) (see Table 1), show comparatively high corrosion rates under “metal dusting” conditions.
  • the nickel alloys Alloy 602 CA (N06025) with a chromium content of 25% and an aluminum content of 2.3% and Alloy 690 (N06690) with a chromium content of 30% are significantly more resistant (Hermse, C.G.M. and van Wortei, J.C.: Metal dusting: Relationship between alloy composition and degradation rate. Corrosion Engineering, Science and Technology 44 (2009), pp. 182 - 185).
  • the resistance to “metal dusting” increases with the sum of chromium and aluminum (Cr + AI).
  • the high-temperature strength or creep resistance at the specified temperatures is improved, among other things, by a high carbon content.
  • high contents of solid solution strengthening elements such as chromium, aluminum, silicon, molybdenum and tungsten also improve the high-temperature strength and creep resistance.
  • additions of aluminum, titanium and/or niobium can improve strength by precipitation of the y' and/or Y" phase.
  • Alloys such as Alloy 602 CA (N06025), Alloy 693 (N06693) or Alloy 603 (N06603) have long been recognized for their excellent corrosion resistance compared to Alloy 600 (N06600) or Alloy 601 (N06601) due to the high aluminum content of more than 1 .8% known.
  • Alloy 602 CA (N06025), Alloy 693 (N06693), Alloy 603 (N06603) and Alloy 690 (N06690) show due to their high Chromium and/or aluminum content ensures excellent carburization resistance or “metal dusting” resistance.
  • alloys such as Alloy 602 CA (N06025), Alloy 693 (N06693) or Alloy 603 (N06603) show excellent high-temperature strength or creep resistance in the temperature range in which “metal dusting” occurs due to the high carbon or aluminum content.
  • Alloy 602 CA (N06025) and Alloy 603 (N06603) still have excellent high-temperature strength and creep resistance even at temperatures above 1000°C.
  • the processability is impaired, among other things, by the high aluminum content, with the impairment becoming greater the higher the aluminum content is (Alloy 693 - N06693).
  • the cold formability in particular is limited by a high proportion of primary carbides.
  • WO 2013/182177 A1 discloses (in weight%) 24 to 33% chromium, 1.8 to 4.0% aluminum, 0.10 to 7.0% iron, 0.001 to 0.50% silicon, 0.005 to 2.0% manganese, 0.00 to 0.60% titanium, 0.0002 to 0.05% each magnesium and/or calcium, 0.005 to 0.12% carbon, 0.001 to 0.050% nitrogen, 0.0001 - 0.020 % oxygen, 0.001 to 0.030% phosphorus, max. 0.010% sulfur, max. 2.0% molybdenum, max. 2.0% tungsten, the balance nickel and the usual process-related impurities, whereby the following relationships must be met:
  • the US 6623869 B1 discloses a metallic material consisting of not more than 0.2% C, 0.01 - 4% Si, 0.05 - 2.0% Mn, not more than 0.04% P, not more than 0.015% S, 10 - 35% Cr, 30 - 78% Ni, 0.005 - 4.5% Al, 0.005 - 0.2% N, and one or both of 0.015 - 3% Cu and 0.015 - 3% Co, with the rest being 100% iron.
  • the value of 40Si+Ni+5AI+40N+10(Cu+Co) is not less than 50, where the symbols of the elements mean the content of the corresponding elements in mass%.
  • the material has excellent corrosion resistance in an environment where metal dusting can occur and can therefore be used for stovepipes, pipe systems, heat exchanger tubes, etc. used in petroleum refineries or petrochemical plants and can significantly improve the lifespan and safety of the plant.
  • EP 0 508 058 A1 discloses an austenitic nickel-chromium-iron alloy consisting of (in weight%) C: 0.12 - 0.3%, Cr: 23 - 30%, Fe: 8 - 11%, AI 1.8 - 2.4%, Y: 0.01 - 0.15%, Ti: 0.01 - 1.0%, Nb: 0.01 - 1.0%, Zr: 0.01 - 0 .2%, Mg: 0.001 - 0.015%, Ca: 0.001 - 0.01%, N: max. 0.03%, Si: max. 0.5%, Mn: max. 0.25%, P: max 0.02%, S: max. 0.01%, Ni: remainder including unavoidable impurities caused by melting.
  • EP 0 234 200 A1 discloses a method and a device for the heat treatment of longitudinally welded pipes made of austenitic, ferritic or austenitic-ferritic stainless steels, the pipes being annealed after the longitudinal seam has been welded.
  • the procedure is through characterized in that the pipes are only partially solution annealed in the area of the weld seam and the heat affected zone, while the remaining areas are heat treated at a lower temperature.
  • annealing is carried out at a temperature greater than 1100 ° C, preferably greater than 1250 ° C, with the annealing temperature being maintained for longer than 5 s, preferably approx. 25 s.
  • the US 3865639 A discloses a method for producing a welded assembly, the welded parts of which withstand operating temperatures in the range of approximately 900 to 1050 ° C, the parts consisting of at least one high-alloy austenitic steel alloyed with chromium, nickel and / or cobalt and contains less than 60% iron by weight, up to 0.5% carbon by weight and low concentrations of additional elements such as manganese and silicon.
  • the specified parts are subjected to welding, the welding leading to the formation of at least one weld seam which has a solidification front corresponding to a physical and chemical discontinuity in the seam, the weld seam also consisting of a high-alloy austenitic steel and then being treated in such a way that that the solidification front becomes chemically homogeneous, whereby the carbides of the weld are present in the precipitated state to a maximum extent and in a fine, uniform distribution, with the result that the creep strength and the tensile strength of the weld are increased to values similar to those of the non-welded parts all are at least approximately the same by subjecting at least the seam and the adjacent areas of the welded parts to a homogenization heat treatment at a temperature between about 1100 to 1200 ° C for a period of several minutes to several hours, after which at least the seam and the adjacent areas to to about 800 ° C at a temperature decrease rate of about 100 ° C / h and then cooled to room temperature with air cooling.
  • the US 3046167 A describes a process for the heat treatment of welded, hardenable chrome-nickel stainless steels in order to then give them a high degree of ductility and toughness in the hardened state, the process comprising the successive steps of welding and converting the welded products by annealing a structure which is essentially martensitic but contains some ferrite, subsequently restoring the structure of the steel which is essentially austenitic although it contains some ferrite. This is done by annealing at a temperature and for a time sufficient to re-austenitize the martensite and ferrite and break up the original cast structure of the weld.
  • US 4168190 A describes a method and apparatus for local solution annealing of austenitic stainless steel that has been partially sensitized, for example, by a local temperature increase, without producing a sensitized structure at the thermal boundaries between the locally treated portion and the rest of the material, comprising the Steps: (a) rapid heating of the sensitized parts of the material to a temperature at which the carbides go into solution; and (b) rapid quenching of the heated material.
  • the object on which the invention is based is to design a method for producing a component from the semi-finished product of a wrought nickel-chromium-aluminum alloy, whereby the component contains weld seams and/or the installation of this component in a system is carried out partially or entirely with weld seams .
  • This task is solved by a process for producing a component, partly or entirely made from a semi-finished product of a nickel-chromium-aluminum alloy, with (in mass%) greater than 18 to 33% chromium, 1.8 to 4.0% Aluminum, 0.01 to 7.0% iron, 0.001 to 0.50% silicon, 0.001 to 2.0% manganese, 0.00 to 0.60% titanium, 0.0 to 0.05% magnesium each and/or or calcium, 0.005 to 0.12% carbon, 0.0005 to 0.050% nitrogen, 0.0001 - 0.020% oxygen, 0.001 to 0.030% phosphorus, max. 0.010% sulfur, max. 2.0% molybdenum, max.
  • the component contains weld seams of the same type and/or the component is partially or completely provided with weld seams of the same type for installation in a system, whereby only after welding the identical weld seams and the heat-affected zones are subjected to annealing between greater than 980 and 1250 ° C for times of 0.05 minutes to 24 hours to homogenize the weld seams and / or to reduce stresses, followed by cooling in static protective gas or air, moving (blown) protective gas or air, with the result that this annealing improves the creep strength and creep ductility of the weld seams, whereby the following relationships must be met:
  • Metal semi-finished products are semi-finished products, such as sheets, strips, bars, forgings, pipes and wires.
  • a component can be assembled from two or more machined semi-finished products and/or other components.
  • the joining can be done using a fusion welding process, if necessary with extra welding filler metal.
  • a welding filler metal can be supplied during welding, for example via welding rods or wires.
  • a welding filler material of the same type has a comparable composition to one of the adjacent processed semi-finished products and/or components.
  • a welding filler of the same type can also consist of a part of at least one of the adjacent semi-finished products to be welded, provided the weld seam geometry is designed accordingly.
  • the nickel-chromium-aluminum wrought alloy used in this invention is preferably melted openly in an electric furnace or an arc furnace, followed by treatment in a VOD (Vacuum, Oxidizing, Deoxidizing) or VLF (Vacuum Ladle Furnace) facility. But melting and casting in a vacuum is also possible.
  • the alloy is then cast in blocks, electrodes or as continuous casting to form a preliminary product. If necessary, the preliminary product is then annealed at temperatures between 900 and 1270 ° C for 0.1 hour to 70 hours.
  • the alloy is then shaped into the desired semi-finished product shape. For this will if necessary annealed at temperatures between 900 and 1270°C for 0.1 hour to 70 hours, then hot formed, if necessary with intermediate annealing between 900 and 1270°C for 0.05 hour to 70 hours. If necessary, the surface of the material can be chemically and/or mechanically removed (even several times) in between and/or after the end of hot forming for cleaning.
  • ESU electro-slag remelting plant
  • VAR vacuum arc remelting
  • cold forming with degrees of deformation up to 98% into the desired semi-finished product shape possibly with intermediate annealing between 800 and 1250 ° C for 0.05 minutes to 70 hours, if necessary under protective gas, such as argon or hydrogen, followed by a Cooling takes place in air, in the moving annealing atmosphere or in a water bath.
  • protective gas such as argon or hydrogen
  • solution annealing takes place in the temperature range from 800 to 1250 ° C for 0.05 minutes to 70 hours, if necessary under protective gas, such as. B. Argon or hydrogen, followed by cooling in air, in the moving annealing atmosphere or in a water bath.
  • chemical and/or mechanical cleaning of the material surface can be carried out in between and/or after the last annealing.
  • Solution annealing preferably takes place between the following temperatures:
  • Solution annealing preferably takes place in the following time ranges:
  • the wrought nickel-chromium-aluminum alloy (Alloy NiCrAl-H) used in this invention can be easily manufactured and used in the semi-finished forms of strip, sheet, bar, forgings, wire, longitudinally welded pipe and seamless pipe.
  • the parts required for the component are cut or separated from the semi-finished product, processed accordingly and then connected using a fusion welding process under inert gas.
  • the fusion welding process may be, for example, one of the following processes:
  • Tungsten inert gas welding Tungsten inert gas welding
  • MIG Metal inert gas welding
  • the protective gas can preferably be argon or argon and hydrogen or argon and nitrogen.
  • the welding filler material of the same type is preferably a nickel-chromium-aluminium alloy with (in mass%) greater than 18 to 33% chromium, 1.8 to 4.0% Aluminum, 0.01 to 7.0% iron, 0.001 to 0.50% silicon, 0.001 to 2.0% manganese, 0.00 to 0.60% titanium, 0.0 to 0.05% magnesium each and/or or calcium, 0.005 to 0.12% carbon, 0.0005 to 0.050% nitrogen, 0.0001 - 0.020% oxygen, 0.001 to 0.030% phosphorus, max. 0.010% sulfur, max. 2.0% molybdenum, max. 2 .0% tungsten, remainder nickel greater than or equal to 50% and the usual process-related impurities, whereby the following relationships must be met:
  • the spread range for the element chromium is between 18 and 33%, with preferred ranges being set as follows:
  • the aluminum content is between 1.8 and 4.0%, although here too, depending on the area of application of the alloy, preferred aluminum contents can be set as follows:
  • the iron content is between 0.01 and 7.0%, whereby, depending on the area of application, preferred contents can be set within the following ranges:
  • the silicon content is between 0.001 and 0.50%.
  • Si can preferably be set in the alloy within the spread range as follows:
  • the titanium content is between 0.00 and 0.60%.
  • Ti can preferably be set in the alloy within the spread range as follows:
  • Magnesium and/or calcium is also contained in levels of 0.00 to 0.05%. It is preferably possible to set these elements in the alloy as follows:
  • the alloy contains 0.005 to 0.12% carbon. This can preferably be set in the alloy within the spread range as follows:
  • the alloy also contains oxygen in levels between 0.0001 and 0.020%, in particular 0.0001 to 0.010%.
  • the alloy also contains phosphorus in levels between 0.001 and 0.030%. Preferred contents can be given as follows:
  • the element sulfur is present in the alloy as follows: max. 0.010%
  • Molybdenum and tungsten are contained individually or in combination in the alloy with a maximum content of 2.0% each. Preferred contents can be given as follows:
  • Nickel is the remainder.
  • the remainder can preferably be specified as follows:
  • Mass% are. Preferred areas can be set with:
  • Preferred ranges can be set with: Fp ⁇ 38.4 (2b)
  • the element niobium can be set in the alloy in contents of 0.0 to 1.10%.
  • Niobium can preferably be set in the alloy within the spread range as follows: 0.001 to ⁇ 1.10% 0.001 to 1.0 or ⁇ 1.0% 0.001 to 0.70 or ⁇ 0.70% 0.001 to 0.50 or ⁇ 0.50% 0.001 to 0.30 or ⁇ 0.30% 0.01 to 0.30 or ⁇ 0.30% If niobium is contained in the alloy, the formula (3a) must be supplemented with a term containing niobium as follows:
  • the zirconium content can be between 0.0 and 0.20%.
  • Zirconium can preferably be set in the alloy within the expansion range as follows:
  • the element yttrium can optionally be set in contents of 0.0 to 0.20% in the alloy.
  • Yttrium can preferably be adjusted in the alloy within the spread range as follows: 0.0 to 0.15 or ⁇ 0.15% 0.0 to 0.10% or ⁇ 0.10% 0.0 to 0.08 or ⁇ 0.08% 0.001 to ⁇ 0.045% 0.01 to 0.04 or ⁇ 0.04%
  • the element lanthanum can be set in the alloy in contents of 0.0 to 0.20%.
  • Lanthanum can preferably be adjusted in the alloy within the spread range as follows: 0.0 to 0.15 or ⁇ 0.15% 0.0 to 0.10 or ⁇ 0.10% 0.0 to 0.08 or ⁇ 0 .08% 0.001 to 0.04 or ⁇ 0.04% 0.01 to 0.04 or ⁇ 0.04%
  • the element cerium can be set in the alloy in contents of 0.0 to 0.20%.
  • Cerium can preferably be adjusted in the alloy within the spread range as follows:
  • cerium mixed metal can optionally be used in contents of 0.0 to 0.20%.
  • Cerium mixed metal can preferably be set in the alloy within the expansion range as follows:
  • the element hafnium can be set in the alloy in contents of 0.0 to 0.20%.
  • Hafnium can preferably be adjusted in the alloy within the spreading range as follows:
  • the alloy can also contain 0.001 to 0.60% tantalum.
  • Preferred tantalum contents can be as follows: 0.001 to 0.50 or ⁇ 0.50%
  • the element boron can optionally be contained in the alloy as follows:
  • the alloy can contain between 0.0 and 5.0% cobalt if necessary, which can also be limited as follows:
  • the alloy can optionally contain a maximum of 0.5% copper.
  • the copper content can also be limited as follows:
  • the alloy can optionally contain a maximum of 0.5% vanadium.
  • the vanadium content can also be limited as follows:
  • the annealing of the weld seams and the heat-affected zones can be done, for example, using heating mats, infrared radiators, lasers or inductive electrical heating.
  • parts of the rest of the structure can be cooled at the same time.
  • weld seams of the same type either by annealing the entire component containing the weld seams or by annealing only the weld seams of the same type and the heat-affected zones, to repeat this annealing, optionally by annealing the entire component containing the same type Weld seams contained in the component or by annealing only the weld seams and heat-affected zones of the same type.
  • the order of partial annealing of only identical weld seams and heat-affected zones and the annealing of the entire component is arbitrary.
  • Annealing after welding preferably takes place between the following temperatures:
  • the annealing after welding preferably takes place in the following time ranges: 0.05 minutes to 16 hours 0.05 minutes to 8 hours 0.05 minutes to 4 hours 0.1 minutes to 1 hour 1 minute to 1 hour
  • the protective gas for annealing after welding can preferably consist of the following gases, if not in air:
  • the improvement in the creep strength and creep ductility of the weld seams of the same type takes place in particular in the area of the y'-level, which covers the temperature range less than or equal to 750 ° C.
  • the surface can be optionally cleaned by brushing, pickling, blasting, grinding, Turning, peeling and/or milling can be cleaned or processed.
  • One or more such processing operations can optionally take place after welding.
  • material-removing processing after the final annealing by grinding, turning, peeling and milling improves the corrosion resistance, especially the “metal dusting” resistance, of the annealed surfaces, especially the weld seams and the heat-affected zones.
  • the components produced according to the invention should preferably be used in areas in which highly corrosive conditions, such as heavily carburizing conditions, atmospheres that produce “metal dusting” prevail, such as components in the petrochemical industry. In addition, they are also suitable for oven construction.
  • Figure 1a on the left shows sketches of the semi-finished products in the form of sheet metal (1), strip (2), rod (3), tube (4), wire or welding filler in wire form (5) in top view and cross section.
  • Figure 1 a on the right shows an example of how a product or preliminary product (7) is created by, for example, cutting out and chamfering (ii) two components (1 a, 1 b) from the semi-finished sheet metal and then shaping them by fusion welding (iii) with a welding filler metal of wire (5) can be joined using a V-seam (6a) (iv).
  • Figure 1 b on the left shows another example of the creation of a product or preliminary product (7), in which, for example, two pipe components (4a, 4b) are cut off and chamfered (ii) from the semi-finished pipe and then by fusion welding (iii) with a welding filler in the form of wire (5) using a V-seam (6b) (iv).
  • Figure 1 b middle shows another example of the creation of a product or preliminary product (7), in which a hole is milled (ii) through a semi-finished sheet metal product or a sheet metal component (1 c), into which a semi-finished pipe product or a pipe component (1 3c) is used and is inserted by fusion welding (iii) with a welding filler in the form of wire (5) by means of a fillet weld (6c) (iv).
  • Figure 1 b on the right shows a further example of the creation of a product or a preliminary product (7), in which two strip sections (2a, 2b) (ii) cut out of the semi-finished strip, the edges of which were machined to fit, by fusion welding (iii ) with part of the edges as a welding filler (9) butt-joined (6d) (iv).
  • the phases occurring in equilibrium were calculated for the different alloy variants using the JMatPro program from Thermotech.
  • the database TTNI7 for nickel alloys from Thermotech was used as the basis for the calculations.
  • the creep strength is determined in a non-interrupted uniaxial creep test with strain measurement under tensile stress according to DIN EN ISO 204. To do this, the sample is installed in a creep testing machine and loaded with a constant test force. The rupture time tu and the time rupture elongation Au b are determined. The rupture time is a measure of the creep strength and the time rupture elongation is a measure of the creep ductility. The tests were carried out on round samples with a diameter of 10 mm in the measuring range and an initial reference length L r o of 50 mm. The sampling was carried out transversely to the forming direction of the semi-finished product.
  • the nickel-chromium-aluminum alloy NiCrAI-H used in this invention has, in addition to excellent corrosion resistance in highly corrosive conditions, here for example excellent “metal dusting” resistance, good phase stability and creep resistance.
  • various embrittling TCP phases Topicologically Closed Packed phases
  • the calculation of the equilibrium phase proportions depending on the temperature, for example for N06690, batch 111389 (see Table 2 for the compositions used here) shows mathematically the formation of a-chromium (BCC phase in Figure 3) below 720 ° C (Ts BCC). large quantities. Since this phase is analytically very different from the base material, the formation of this phase is generally made more difficult. However, if the formation temperature Ts BCC of this phase is very high, so it can certainly occur, as for example in “E. Slevolden, JZ Albertsen.
  • the formation temperature Ts BCC should be less than or equal to 939 ° C - the lowest formation temperature Ts BCC among the alloy examples 693 in Table 2 (from US 4882125 Table 1).
  • Tables 3a and 3b show the analyzes of industrially melted batches of Alloy NiCrAl-H alloys used in this invention from which sheets and welding rods were made. For these batches, the formula (2a) AI + Cr > 28 is met and thus the requirement for “metal dusting” resistance is met. For the compositions in Tables 3a and 3b, the value for Fp was also calculated according to formula (3a). Fp is less than 39.9 as required.
  • the 25 mm thick sheets had a grain size of around 89 pm
  • the 16 mm thick sheets had a grain size of around 82 pm.
  • the 25 mm sheet and the 16 mm sheet therefore have a comparable grain size.
  • the wire rod was also blasted, pickled and ground and then cold drawn to final thickness with intermediate annealing between 800 and 1250 ° C for 0.05 minutes to 70 hours.
  • the wire is then solution annealed under hydrogen in a temperature range of 800 to 1250 ° C for 0.05 minutes to 70 hours and processed into welding rods with a diameter of 2.0 and 2.4 mm.
  • Sheet metal sections were cut from the 25 mm thick solution-annealed semi-finished sheet metal, which were annealed at 980 ° C for 3 hours with subsequent air cooling. Samples for creep tests transverse to the rolling direction were made from the only solution annealed and the additionally annealed sheets or sheet sections manufactured. The results of the creep tests according to DIN EN ISO 204 are shown in Table 5.
  • Sheet metal sections measuring 150 x 500 mm were cut from the 16 mm thick semi-finished sheet metal. Two pieces each were welded with a 70° V-seam using TIG manual welding under pure argon using the 2.0 and 2.4 mm thick welding rods from batch 318385 as welding filler with the welding parameters given in Table 4. The weld seam and heat affected zone were brushed immediately after welding. Some sections of the welded sheets produced in this way were annealed at 980 ° C for 3 hours with subsequent air cooling, others with 1100 ° C for 40 minutes with subsequent air cooling and others with 1100 ° C for 3 hours with subsequent air cooling. Some received no annealing. Seams or seam sections were also produced that were sanded or not treated at all. Samples for creep tests were made from the welded sheets or the welded and annealed sheets or sheet sections transversely to the weld seam. The results of the creep tests according to DIN EN ISO 204 are shown in Table 5.
  • an additional annealing of the welded section from which the creep samples are made at 980 ° C for 3 hours followed by air cooling has no noticeable effect on the rupture time tu, but noticeably reduces the rupture elongation Au b .
  • an additional annealing according to the invention produces the welded Section from which the creep samples are made, at 1100 ° C for 40 minutes followed by air cooling (sample 250W or 503W), in each case a significant increase in the rupture time tu by a factor of approximately 3 and an increase in the rupture elongation Au b partially above the Value of the samples not annealed after welding (sample 302W or 303W).
  • an additional annealing according to the invention of the welded section from which the creep samples are made at 1100 ° C for 3 hours followed by air cooling produces a further increase in the rupture time tu and an increase in the rupture elongation Au b fast on the value of the creep test on only solution-annealed, non-welded sheet metal (sample 19 23B or 19 7B).
  • a creep test (sample 306W) transverse to the weld seam without further annealing (state of the art T) also shows, as at 600°C, a reduced fracture time tu compared to the creep test on sheet metal that has only been solution-annealed (sample 30 34B). Additional annealing of the welded section from which the creep specimens are made at 980°C for 3 hours followed by air cooling (sample 248W) again produces a slight reduction in fracture time tu compared to sample 306W, which was not annealed after welding.
  • an additional annealing according to the invention of the welded section from which the creep samples are made at 1100 ° C for 40 minutes followed by air cooling produces an increase in the fracture time tu by a factor of approximately 2 as well as an increase in the time fracture elongation Au b significantly higher than the value of the sample that was not annealed after welding (306W).
  • an additional annealing according to the invention of the welded section from which the creep samples are made at 1100 ° C for 3 hours followed by air cooling produces a further increase in the fracture time tu beyond the fracture time of the creep test on the only solution-annealed sheet.
  • sample 19 49B additional annealing at 980°C for 3 hours followed by air cooling (Sample 19 49B) of a solution-annealed sheet produces a similar fracture time tu compared to the solution-annealed sheet only (Sample 19 22B).
  • a creep test (sample 309W) transverse to the weld seam without further annealing (state of the art T) also has a similar fracture time tu compared to the creep test on sheet metal that has only been solution-annealed (sample 19 22B).
  • chromium content is too low, the chromium concentration below the oxide layer drops very quickly below the critical limit when the alloy is used in a corrosive atmosphere, so that a closed chromium oxide layer can no longer form. Therefore, 18% chromium is the lower limit for chromium. Chromium contents that are too high impair the phase stability of the alloy, especially with high aluminum contents of > 1.8%. Therefore, 33% chromium is to be regarded as the upper limit. The formation of an aluminum oxide layer beneath the chromium oxide layer reduces the oxidation rate. Below 1.8% aluminum, the aluminum oxide layer is too patchy to fully develop its effect. Too high aluminum contents impair the processability of the alloy. Therefore, an aluminum content of 4.0% is the upper limit.
  • the cost of the alloy increases as the iron content is reduced. Below 0.01% the costs increase disproportionately because special raw materials have to be used. Therefore, 0.01% iron is to be viewed as the lower limit for cost reasons. As the iron content increases, the phase stability decreases (formation of embrittling phases), especially with high chromium and aluminum contents. Therefore, 7% iron is a sensible upper limit to ensure the phase stability of the alloy according to the invention.
  • Silicon is required in the production of the alloy. A minimum content of 0.001% is therefore necessary. Contents that are too high, in turn, affect the processability and phase stability, especially with high aluminum and chromium contents. The silicon content is therefore limited to 0.50%.
  • a minimum content of 0.001% manganese is necessary to improve processability.
  • Manganese is limited to 2.0% because this element reduces resistance to oxidation.
  • Titanium increases high temperature strength. From 0.60% the oxidation behavior can deteriorate, which is why 0.60% is the maximum value.
  • magnesium contents and/or calcium contents improve processing by binding sulfur, which prevents the occurrence of low-melting NiS eutectics. If the content is too high, intermetallic Ni-Mg phases or Ni-Ca phases can occur, which significantly worsen the processability.
  • the magnesium content and/or calcium content is therefore limited to a maximum of 0.05%. A minimum carbon content of 0.005% is necessary for good creep resistance. Carbon is limited to a maximum of 0.12%, as above this level this element reduces processability due to the excessive formation of primary carbides.
  • Nitrogen is limited to a maximum of 0.05% because this element reduces processability through the formation of coarse carbonitrides.
  • the oxygen content must be ⁇ 0.020% to ensure the alloy can be manufactured. Too low an oxygen content increases costs. The oxygen content is therefore > 0.0001%.
  • the phosphorus content should be less than or equal to 0.030%, as this surface-active element impairs oxidation resistance. Too low a phosphorus content increases costs. The phosphorus content is therefore > 0.001%.
  • Sulfur contents should be kept as low as possible since this surface-active element impairs oxidation resistance. A maximum of 0.010% sulfur is therefore specified.
  • Molybdenum is limited to a maximum of 2.0% as this element
  • Tungsten is limited to a maximum of 2.0% as this element
  • Nickel is the remaining element. Too low a nickel content reduces phase stability, especially at high chromium contents. Nickel must therefore be greater than or equal to 50%. For highly corrosive conditions, but especially for good metal dusting resistance, it is advantageous if the following relationship between Cr and Al is met:
  • the oxidation resistance can be further improved with the addition of oxygen-affinous elements such as yttrium, lanthanum, cerium, cerium mixed metal, zirconium, hafnium. They do this by being incorporated into the oxide layer and blocking the diffusion paths of oxygen on the grain boundaries.
  • oxygen-affinous elements such as yttrium, lanthanum, cerium, cerium mixed metal, zirconium, hafnium. They do this by being incorporated into the oxide layer and blocking the diffusion paths of oxygen on the grain boundaries.
  • Yttrium increases oxidation resistance.
  • the upper limit is off
  • Cerium increases oxidation resistance.
  • the upper limit is set at 0.20% for cost reasons.
  • Cerium mixed metal increases oxidation resistance.
  • the upper limit is set at 0.20% for cost reasons.
  • niobium can be added, as niobium also increases high-temperature strength. Higher salaries increase costs significantly. The upper limit is therefore set at 1.10%.
  • the alloy can also contain tantalum, since tantalum also increases high-temperature strength and oxidation resistance. Higher salaries increase costs significantly.
  • the upper limit is therefore set at 0.60%. A minimum level of 0.001% is required to have an effect.
  • the alloy can also contain zirconium.
  • Zirconium increases high-temperature strength and oxidation resistance.
  • the upper limit is set at 0.20% zirconium.
  • the alloy can also contain hafnium.
  • Hafnium increases high-temperature strength and oxidation resistance.
  • the upper limit is set at 0.20% hafnium.
  • boron can be added to the alloy because boron improves creep resistance. Therefore there should be a content of at least 0.0001%. At the same time, this surface-active element impairs the oxidation resistance. A maximum of 0.008% boron is therefore specified.
  • Cobalt can be contained in this alloy up to 5.0%. Higher contents noticeably reduce the oxidation resistance.
  • Copper is limited to a maximum of 0.5% as this element reduces resistance to oxidation.
  • Vanadium is limited to a maximum of 0.5% as this element reduces oxidation resistance.
  • Lead is limited to a maximum of 0.002% as this element reduces resistance to oxidation. The same applies to zinc and tin.
  • Annealing under inert gas reduces oxidation of the material during annealing and thus material loss.
  • Fig. 1 a Left: Sketches in plan and cross section of the semi-finished shapes sheet 1, strip 2, rod 3, tube 4, and wire or welding filler in wire form 5.
  • Fig. 1 b Example production of components 7.
  • Left chamfering of two pipes at one end 4a, 4b and joining by fusion welding with a welding filler in wire form 5 using a V-seam 6b.
  • Middle Milling a hole in a sheet 1c and inserting and joining a pipe 4c by fusion welding with a welding filler in wire form 5 using a fillet weld 6c.
  • Right Joining two strip sections 2a, 2b with the edges to fit with part of the edges as a welding filler 9 butt-jointed by fusion welding 6d.
  • Fig. 2 Metal loss through “metal dusting” as a function of aluminum
  • Table 1 Some alloys according to ASTM B 168-11. All information in mass%.
  • Table 2 Compositions of some alloys according to ASTM B 168-11. All information in mass%.
  • Table 3a Composition of the industrially melted batches (G) of the nickel-chromium-aluminum alloy NiCrAl-H used in this invention, part 1. All information in mass%. (H: Examples of the nickel-chromium-aluminum alloy NiCrAl-H used in this invention, G: melted on an industrial scale)
  • Table 3b Composition of the industrially smelted batches (G) of the nickel-chromium-aluminium alloy NiCrAI-H used in this invention, part 2. All information in mass% (applies to all alloys: Pb: max. 0.002%, Zn : max. 0.002%, Sn: max. 0.002%; meaning of H, G: see Table 3a).
  • Table 4 Welding parameters for welding the 16 mm thick sheets (batch 319144) with welding rods from batch 318385, the nickel-chromium-aluminum alloy NiCrAI-H used in this invention.
  • Table 5 Results of the creep tests according to DIN EN ISO 204 on i) 25 mm thick solution-annealed sheets (1100 ° C / 40 min / LK, grain size 89 pm) from batch 319144 (BM) and ii) 16 mm welded with welding rods from batch 318385 thick, solution-annealed sheets (1100°C / 40 min/LK, grain size 82 pm) from batch 319144 (S). LK

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Abstract

L'invention concerne un procédé de production d'un composant, partiellement ou entièrement formé à partir d'un produit semi-fini d'un alliage nickel-chrome-aluminium, avec (en % en poids) plus de 18 à 33 % de chrome, 1,8 à 4,0 % d'aluminium, 0,01 à 7,0 % de fer, 0,001 à 0,50 % de silicium, 0,001 à 2,0 % de manganèse, 0,00 à 0,60 % de titane, respectivement 0,0 à 0,05 % de magnésium et/ou de calcium, 0,005 à 0,12 % de carbone, 0,0005 à 0,050 % d'azote, 0,0001 à 0,020 % d'oxygène, 0,001 à 0,030 % de phosphore, 0,010 % max. de soufre, 2,0 % max. de molybdène, 2,0 % max. de tungstène, le reste étant supérieur ou égal à 50 % de nickel et les impuretés liées au procédé habituelles, le composant contenant des cordons de soudure du même type et/ou le composant étant pourvu partiellement ou entièrement de cordons de soudure du même type pour l'installation dans un système, et après l'opération de soudage, seuls les cordons de soudure du même type et les zones affectées par la chaleur subissent un recuit entre plus de 980 et 1 250 °C pendant des temps de 0,05 minute jusqu'à 24 heures afin d'homogénéiser les cordons de soudure et/ou de réduire la contrainte, suivi d'un refroidissement dans un gaz protecteur inerte ou de l'air, de déplacement (soufflage) de gaz protecteur ou d'air, de sorte que la résistance au fluage et la ductilité au fluage des cordons de soudure sont améliorées avec cette opération de recuit, les conditions suivantes devant être satisfaites : (1a) : Cr + AI ≥ 28; et (2a) : Fp ≤ 39,9, avec (3a) : Fp = Cr + 0,272*Fe + 2,36*AI + 2,22*Si + 2,48*Ti + 0,374*Mo + 0,538*W - 11,8*C, où Cr, Fe, AI, Si, Ti, Mo, W et C sont les concentrations des éléments respectifs en % en poids.
EP23711661.1A 2022-03-10 2023-03-03 Procédé de fabrication d'un composant à partir du produit semi-fini d'un alliage nickel-chrome-aluminium Pending EP4490331A1 (fr)

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DE102022105658.9A DE102022105658A1 (de) 2022-03-10 2022-03-10 Verfahren zur Herstellung eines Bauteils aus dem Halbzeug einer Nickel-Chrom-Aluminium-Legierung
PCT/DE2023/100169 WO2023169628A1 (fr) 2022-03-10 2023-03-03 Procédé de fabrication d'un composant à partir du produit semi-fini d'un alliage nickel-chrome-aluminium

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WO2026095287A1 (fr) 2024-10-30 2026-05-07 주식회사 엘지에너지솔루션 Dispositif de soudage de capuchon supérieur d'élément de batterie cylindrique et procédé de soudage de capuchon supérieur d'élément de batterie cylindrique utilisant ce dernier

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US3046167A (en) 1960-05-19 1962-07-24 Armco Steel Corp Heat-treating method and product
BE794848A (fr) 1972-12-15 1973-05-29 Pompey Acieries Procede de fabrication ameliorant la tenue de pieces soudees en aciers refractaires
US4168190A (en) 1976-04-27 1979-09-18 Daiichi Koshuha Kogyo Kabushiki Kaisha Method for locally solution-treating stainless material
EP0234200B1 (fr) 1986-01-21 1990-12-05 Siemens Aktiengesellschaft Procédé et dispositif pour le traitement thermique de tubes sondés longitudinalement
US4882125A (en) 1988-04-22 1989-11-21 Inco Alloys International, Inc. Sulfidation/oxidation resistant alloys
DE4111821C1 (fr) 1991-04-11 1991-11-28 Vdm Nickel-Technologie Ag, 5980 Werdohl, De
JP3952861B2 (ja) 2001-06-19 2007-08-01 住友金属工業株式会社 耐メタルダスティング性を有する金属材料
DE102012011161B4 (de) * 2012-06-05 2014-06-18 Outokumpu Vdm Gmbh Nickel-Chrom-Aluminium-Legierung mit guter Verarbeitbarkeit, Kriechfestigkeit und Korrosionsbeständigkeit
US9840752B2 (en) * 2014-05-27 2017-12-12 Keystone Engineering Company Method and apparatus for performing a localized post-weld heat treatment on a thin wall metallic cylinder
JP6571937B2 (ja) * 2015-01-21 2019-09-04 株式会社クボタ 耐熱管の溶接構造
DE102015008322A1 (de) 2015-06-30 2017-01-05 Vdm Metals International Gmbh Verfahren zur Herstellung einer Nickel-Eisen-Chrom-Aluminium-Knetlegierung mit einer erhöhten Dehnung im Zugversuch
DE102020132193A1 (de) * 2019-12-06 2021-06-10 Vdm Metals International Gmbh Verwendung einer Nickel-Chrom-Eisen-Aluminium-Legierung mit guter Verarbeitbarkeit, Kriechfestigkeit und Korrosionsbeständigkeit
JP2021167439A (ja) * 2020-04-09 2021-10-21 日本製鉄株式会社 オーステナイト系耐熱合金溶接継手

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DE102022105658A1 (de) 2023-09-14
WO2023169628A1 (fr) 2023-09-14
US20250236941A1 (en) 2025-07-24

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