EP4069873A1 - Alliage de nickel-chrome-aluminium présentant de bonnes aptitude au traitement, résistance au fluage et résistance à la corrosion et son utilisation - Google Patents

Alliage de nickel-chrome-aluminium présentant de bonnes aptitude au traitement, résistance au fluage et résistance à la corrosion et son utilisation

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Publication number
EP4069873A1
EP4069873A1 EP20839221.7A EP20839221A EP4069873A1 EP 4069873 A1 EP4069873 A1 EP 4069873A1 EP 20839221 A EP20839221 A EP 20839221A EP 4069873 A1 EP4069873 A1 EP 4069873A1
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EP
European Patent Office
Prior art keywords
content
alloy according
alloy
chromium
aluminum
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
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EP20839221.7A
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German (de)
English (en)
Inventor
Heike Hattendorf
Benedikt NOWAK
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VDM Metals International GmbH
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VDM Metals International GmbH
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Publication of EP4069873A1 publication Critical patent/EP4069873A1/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
    • 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
    • C22C19/055—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
    • C22C19/051—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%
    • 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
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S40/00—Safety or protection arrangements of solar heat collectors; Preventing malfunction of solar heat collectors
    • F24S40/20—Cleaning; Removing snow
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S80/00—Details, accessories or component parts of solar heat collectors not provided for in groups F24S10/00-F24S70/00
    • F24S80/10—Materials for heat-exchange conduits
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S80/00—Details, accessories or component parts of solar heat collectors not provided for in groups F24S10/00-F24S70/00
    • F24S80/20—Working fluids specially adapted for solar heat collectors
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S20/00—Solar heat collectors specially adapted for particular uses or environments
    • F24S20/20—Solar heat collectors for receiving concentrated solar energy, e.g. receivers for solar power plants

Definitions

  • Nickel-chromium-aluminum alloy with good processability, creep resistance and corrosion resistance as well as their use
  • the invention relates to a wrought nickel-chromium-aluminum alloy with good high-temperature corrosion resistance, good creep resistance and improved processability.
  • nickel alloys with different nickel, chromium and aluminum contents have not only been used for a long time in the chemical and petrochemical industries as well as in furnace construction, but are also of great interest with regard to use in solar tower power plants.
  • These systems consist of an array of mirrors (heliostats) that are arranged around a high tower.
  • the mirrors concentrate the sunlight on the absorber (solar receiver) mounted in the tip.
  • the absorber consists of a pipe system in which a heat transfer medium is heated. This medium circulates in a circuit with intermediate storage tanks and a heat exchanger system converts the heat energy into electricity in a secondary circuit with the help of a generator.
  • the heat transfer medium is primarily a salt mixture of sodium and potassium nitrate salt melts, which results in a maximum operating temperature of the salt of around 600 ° C, depending on the alloy used for the components [Kruizenga et al., 2013, Materials Corrosion of High Temperature Alloys Immersed in 600 ° C Binary Nitrate Salt, SANDIA report, SAND 2013-2526].
  • the maximum operating temperature of the salts must be increased. This is possible through the use of, for example, chloride and / or carbonate salts as a heat transfer medium [Mehos et al., 2017, Concentrating Solar Power Gen3 Demonstration Roadmap, National Renewable Energy Lab. (NREL)]. These do not decompose at temperatures above about 600 ° C like the sodium and potassium nitrate salts, but have a maximum operating temperature of up to 1000 ° C. The disadvantage of using these salt systems is the stronger corrosive attack at higher temperatures compared to the sodium and potassium nitrate salts, especially in the area of the solar receiver or the heat absorption pipes, which transport the salt and represent the hottest point in the salt cycle.
  • An essential prerequisite for using an alloy in the environment described above is good high-temperature corrosion resistance in chloride and / or carbonate molten salts. This is determined not only by a continuous chromium oxide layer (Cr 2 O 3 ), but in particular by an underlying as closed as possible, ie continuous and gapless aluminum oxide layer (Al 2 O 3 ). Under certain conditions, the chromium ions preferentially dissolve in the molten salt. A certain aluminum content in the alloy can slow down this process through the formation of a closed Al 2 O 3 layer [George Y. Lai, 1990, High-Temperature Corrosion of Engineering Alloys, ASM International, p. 100, Fig. 6.11].
  • the chromium content should not be too low, since the absorber pipes are exposed to the salt on the inside but to the ambient air on the outside. This means that a certain chromium content is necessary to ensure oxidation resistance at the elevated temperatures of up to 1000 ° C in ambient air.
  • the heat resistance 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 heat resistance. In the range from 500 ° C. to 900 ° C., additions of aluminum, titanium and / or niobium can improve the strength by eliminating the ⁇ ′ and / or ⁇ ”phase.
  • Another important parameter with regard to the fatigue load of the material due to the daily sun and cloud cycles calculated over the entire service life of the solar receiver is the alternating strength.
  • Alloy 602CA (N06025) and Alloy 603 (N06603) have excellent heat resistance and creep resistance even at temperatures above 1000 ° C. However, the processability is impaired, among other things, by the high aluminum content, the impairment being the greater the higher the aluminum content (such as in Alloy 214 (UNS N07214)).
  • Alloy 602CA (N06025) or Alloy 603 (N06603) in particular, the cold formability is reduced due to a high content of primary carbides compared to alloys such as Alloy 601 (N06601).
  • This means that the aluminum content must be high enough so that a closed Al 2 O 3 layer is formed, but it must not be too high either, since otherwise the processability is adversely affected. This requirement also applies to chrome. This makes it clear that an exact coordination of the aluminum or chromium content is of decisive importance for the corrosion resistance in chloride and / or carbonate salt melts at elevated temperatures.
  • WO 2019/075177 A1 discloses an improved solar tower system that has absorber tubes, a storage tank and a heat exchanger, all of which are as Heat transfer medium contain a molten salt at temperatures> 650 ° C, whereby the improvement includes that at least one of the components (absorber tubes, storage tank and heat exchanger) is made of an alloy that (in mass%) 25 - 45% Ni, 12 - 32% Cr, 0.1 - 2.0% Nb, up to 4% Ta, up to 1% Va, up to 2% Mn, up to 1, 0% AI, up to 5% Mo, up to 5% W, up to 0.2% Ti, up to 2% Zr, up to 5% Co, up to 0.1% Y, up to 0.1% La, up to 0.1% Cs, up to 0.1% other rare earths, up to 0.20% C, up to 3% Si, N 0.05 - 0.50%, up to 0.02% B and the remainder Fe and impurities.
  • EP 549286 discloses a Ni-Cr-Al alloy containing 0.005-0.5% C, 0.0001-0.1% N, 19-25% Cr, 55-65% Ni, 0-1% Mn, 0 , 1 - 1, 5% Si, 0.15 - 1% Ti, 1 - 4.5% Al, 0 - 0.5% Zr, 0 - 10% Co, 0.045 - 0.3% Y, 0.0001 - 0.1 % B and the remainder of Fe and impurities, among other things in the field of thermal
  • WO 00/34540 discloses a high-temperature alloy containing 27-35% Cr, 0-7% Fe, 3-4.4% Al, 0-0.4% Ti, 0.2-3% Nb, 0.12 - 0.5% C, 0 - 0.05% Zr, 0.002 - 0.05% Ce and Y, as well as 0 - 1% Mn, 0 - 1% Si, 0 - 0.5% Ca + Mg, 0 - 0.1% B and the remainder of Ni and impurities, which is used, among other things, in the field of thermal process applications such as furnace construction, e.g. as a material for the production of furnace muffles and similar components for
  • the object on which the invention is based is to produce a nickel-chromium-aluminum alloy
  • a nickel-chromium-aluminum alloy with (in mass%) 12 to 30% chromium, 1.8 to 4.0% aluminum, 0.1 to 7.0% iron, 0.001 to 0, 50% silicon, 0.001 to 2.0% manganese, 0.00 to 1.00% titanium, 0.00 to 1.10% niobium, 0.00 to 0.5% copper, 0.00 to 5.00% Cobalt, each 0.0002 to 0.05% magnesium and / or calcium, 0.001 to 0.12% carbon, 0.001 to 0.050% nitrogen, 0.001 to 0.030% phosphorus, 0.0001 to 0.020% oxygen, max. 0.010% sulfur , max. 2.0% molybdenum, max.
  • alloy contents are in% by mass.
  • the spread range for the element chromium is between 12 and 30%, whereby preferred ranges can be set as follows:
  • the aluminum content is between 1.8 and 4.0%, although here too, depending on the application of the alloy, preferred aluminum contents can be set as follows:
  • the iron content is between 0.1 and 7.0%, whereby, depending on the area of application, preferred contents can be set within the following spread ranges:
  • the silicon content is between 0.001 and 0.50%.
  • Si can be adjusted in the alloy within the spread range as follows:
  • the element manganese which can be contained in the alloy at 0.001 to 2.0%.
  • the following spread range is also conceivable: 0.001-1.0%
  • Ti is between 0.00 and 1.0%.
  • Ti can be set in the alloy within the spread range as follows:
  • Nb content is between 0.00 and 1.1%.
  • Nb can be adjusted in the alloy within the spread range as follows:
  • the alloy contains 0.00 to 0.50% copper. This can preferably be set in the alloy within the spread range as follows: a maximum of 0.20% a maximum of 0.10%
  • the alloy can contain between 0.0 and 5.00% cobalt.
  • the cobalt content can also be restricted as follows:
  • Magnesium and / or calcium are also contained in levels of 0.0002 to 0.05%. There is preferably the option of setting these elements in the alloy as follows:
  • the alloy contains 0.001 to 0.12% carbon. This can preferably be set in the alloy within the spread range as follows: 0.001 - 0.10%
  • the alloy also contains phosphorus in contents between 0.001 and 0.030%. Preferred contents can be given as follows:
  • the alloy also contains oxygen in contents between 0.0001 and 0.020%, in particular contains 0.0001 to 0.010%.
  • the element sulfur is given 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:
  • the nickel content is greater than or equal to 50%. It can preferably be set as follows:
  • the element yttrium can be set in the alloy in contents of 0.001 to 0.20%.
  • Y can be set in the alloy within the spread range as follows: 0.001 -0.15%
  • the element lanthanum can be set in the alloy in contents of 0.001 to 0.20%.
  • Lanthanum can preferably be used within the
  • Spread range can be set in the alloy as follows:
  • the element cerium can be set in the alloy with a content of 0.001 to 0.20%.
  • cerium can be set in the alloy within the spread range as follows:
  • cerium mischmetal can also be used in contents of 0.001 to 0.20%.
  • Cerium mischmetal can preferably be set in the alloy within the spread range as follows:
  • the zirconium content is optionally between 0.001 and 0.20%.
  • Zirconium can preferably be adjusted in the alloy within the spread range as follows: 0.001-0.15%
  • hafnium content is between 0.001 and 0.20%.
  • Hafnium can preferably be adjusted in the alloy within the spread range as follows:
  • the alloy can also contain 0.001 to 0.60% tantalum.
  • Tantalum can preferably be set in the alloy within the spread range as follows:
  • the element boron can be contained in the alloy as follows:
  • the alloy can contain a maximum of 0.5% vanadium.
  • the vanadium content can also be limited as follows: max. 0.20% max. 0.10% max. 0.05%
  • the alloy according to the invention is preferably melted openly, followed by a treatment in a VOD (vacuum oxygen decarburization) or VLF (vacuum ladle furnace) system. But melting and pouring in a vacuum is also possible.
  • VOD vacuum oxygen decarburization
  • VLF vacuum ladle furnace
  • the alloy is annealed in the desired semi-finished form, if necessary at temperatures between 900 ° C and 1270 ° C for 0.1 hours to 100 hours, then hot-formed, if necessary with intermediate anneals between 900 ° C and 1270 ° C for 0.05 hours to 100 hours.
  • the surface of the material can be removed chemically and / or mechanically in between and / or at the end for cleaning (also several times).
  • cold forming with degrees of deformation up to 98% into the desired semi-finished product shape, if necessary with intermediate annealing between 700 ° C and 1250 ° C for 0.1 minutes to 70 hours, if necessary under protective gas, such as e.g. B. argon or hydrogen, followed by cooling in air, in the agitated annealing atmosphere or in a water bath.
  • protective gas such as e.g. B. argon or hydrogen
  • a solution heat treatment takes place in the temperature range from 700 ° C to 1250 ° C for 0.1 minutes to 70 hours, possibly under protective gas, such as. B. argon or hydrogen, followed by cooling in air, in the agitated annealing atmosphere or in a water bath.
  • chemical and / or mechanical cleaning of the material surface can take place in between and / or after the last annealing.
  • the alloy according to the invention can be easily manufactured and used in the product forms strip, sheet metal, rod, wire, longitudinally welded tube and seamless tube.
  • the alloy according to the invention should preferably be used in solar tower power plants using chloride and / or carbonate molten salts as the heat transfer medium.
  • the chloride and / or carbonate salt melts can preferably consist of the following mixtures:
  • the mixture can preferably consist of the following compositions: 60-75% zinc chloride, 2-15% sodium chloride and 15-30% potassium chloride 30-50% magnesium chloride and 50-70% potassium chloride 25-40% sodium carbonate, 25-40% potassium carbonate and 25 - 40% lithium carbonate
  • the salt mixtures can also be used under a pure CO 2 atmosphere.
  • the minimum application temperature of the salt mixture is 250 ° C. It can be restricted as follows: min. 290 ° C min. 300 ° C min. 350 ° C min. 400 ° C min. 450 ° C min. 500 ° C min. 550 ° C min. 600 ° C
  • the maximum operating temperature of the salt mixture is 1000 ° C. It can be restricted as follows: max. 950 ° C max. 900 ° C max. 850 ° C max. 830 ° C ⁇ 830 ° C max. 800 ° C
  • the oxidation resistance can be further improved.
  • a gap in the Al 2 O 3 layer offers a preferred point of attack for corrosion in environments containing chloride and / or carbonate salt. Chlorine and chloride ions lead to accelerated corrosion. The mechanism is described in detail by Grabke et al. [Grabke et al., 1995, Effects of chlorides, hydrogen chlorides, and sulfur dioxide in the oxidation of steels below deposits, Corrosion Science, 37 (7), 1023-1043]. According to [Kruizenga, 2012, Corrosion Mechanisms in Chloride and Carbonate Salts, SANDIA report, SAND 2012-7594], the chromium content should not be too high, since Cr ions preferentially migrate as a solution into the molten salt under certain conditions. A sufficiently high aluminum content can slow down this process by forming a closed Al 2 O 3 layer [George Y. Lai, 1990, High-Temperature Corrosion of Engineering Alloys, ASM International, p. 100, FIG. 6.11].
  • the chromium content should also not be too low, since the absorber pipes are exposed to the salt on the inside, but the ambient air on the outside.
  • the chromium content is slowly consumed in the course of use in the application area to build up the protective layer. Therefore, a higher chromium content increases the service life of the material, as a higher content of the element chromium, which forms the protective layer, delays the point in time when the chromium content is below the critical limit and oxides other than Cr 2 O 3 are formed, which e.g. and / or oxides containing nickel. These oxides have a significantly lower resistance to oxidation than a protective passive layer made of Cr 2 O 3 .
  • a sufficiently high chromium content is therefore necessary to ensure oxidation resistance at the elevated temperatures of up to 1000 ° C in ambient air.
  • alloys with increasing nickel content show improved corrosion resistance in chlorine-containing atmospheres, whereby the addition of molybdenum can lead to catastrophic corrosion [Indacochea et al., 2001, High-Temperature Oxidation and Corrosion of Structural Materials in Molten Chlorides , Oxidation of Metals, 55 (1), 1-16].
  • thermodynamic calculations were carried out with the JMatPro version 11 simulation program from Thermotech. With the help of the program, time-temperature-conversion (TTT) diagrams were calculated for various alloy contents (see Figure 1). This diagram shows the time after which a certain content (here 0.1%) of a phase is eliminated at a certain temperature. This is calculated for each phase without taking into account the consumption of alloying elements by other phases. In the ZTU diagram, each phase has a minimum time until this phase is eliminated. This minimum time t ⁇ '1 became for the ⁇ '-phase (GAMMA_PRIME in Figure 1) intended for different alloy compositions.
  • TTTT time-temperature-conversion
  • the ⁇ '-phase causes a strong increase in solidification and hardness with a simultaneous reduction in elongation. If it forms too quickly in too large quantities, this can lead to cracks during processing (e.g. hot forming, welding).
  • Formula (2) where Fe, Cr, Al, Ti and Nb are the concentration of the respective elements in mass%.
  • Formula (2) is only valid for compositions with a content of Cr ⁇ 31%, AI ⁇ 5%, Fe ⁇ 18%, Ti ⁇ 1, 5% and Nb ⁇ 4%.
  • Table 2 shows the composition, the time t ⁇ '1 and F v of alloys according to the prior art (T) together with the alloy compositions according to the invention (E) and those not according to the invention.
  • Table 2a the time t ⁇ '1 was calculated using JMatPro for the compositions A001 to A018 and the alloys according to the state of the art (see penultimate column), as well as the value for F v calculated using formula (2) (see last column) .
  • Table 2b is the continuation of Table 2a with regard to the composition of the alloys according to the prior art and the compositions A001 to A018.
  • Table 2c shows the continuation of Table 2a with the compositions A019 to A032.
  • Table 2d is the continuation of Table 2c with regard to the compositions A019 to A032.
  • compositions A001 to A004 have an increasing aluminum content, starting from 2.0 to 4.0%.
  • the others have an increasing aluminum content, starting from 2.0 to 4.0%.
  • compositions A005 to A007 have an increasing chromium content (18, 20 and 23%).
  • the time t ⁇ '1 'nd F v also decrease with increasing chromium content, but the effect is far less than with aluminum.
  • compositions A008 to A011 have a falling iron content, as a result of which the time t ⁇ '1 and the value for F v become smaller. That is, the addition of iron improves the workability because the time t ⁇ '1 becomes longer.
  • compositions A012 and A018 have a different titanium content, the compositions A012 to A014 having an increasing titanium content.
  • the compositions A016 to A018 have an increasing titanium content with an iron content of 10%.
  • compositions A019 and A025 in Table 2c have a different niobium content, the compositions A019 to A021 having an increasing niobium content.
  • compositions A023 to A025 have an increasing niobium content at a chromium concentration of 23%.
  • compositions A026 to A031 have a different content of yttrium, lanthanum, hafnium and tantalum. Since F v > 0.9 applies to all compositions, they are easy to process, since the time t ⁇ '1 is sufficiently long.
  • the alloy compositions (E) according to the invention are within the analytical limits worked out above , meet condition (1) and formula (2) with regard to the value for F v and thus have a sufficiently long time t ⁇ '1 and are therefore good are processable. These are the compositions A001 to A003, A005 to A007, A009 to A013, A019 to A020 and A026 to A032. In the case of the state-of-the-art alloys in Table 2a, the alloys H214 and IN702 have a value for F v ⁇ 0.9.
  • alloy H214 In the case of the alloy H214, this can be attributed to the increased aluminum content (4.5%) and in the case of IN702 to the increased aluminum content (3.25%) in combination with the increased titanium content (0.38%). This means that the alloys H214 and IN702 have too short a time t ⁇ '1 and thus poor processability.
  • the other alloys according to the prior art have a value of F v > 0.9 and are therefore easy to process, since t ⁇ '1 is sufficiently large. This can be attributed to the lower aluminum content (2.78% for Alloy 603, or even lower for the others) and the limited titanium and niobium content in combination with aluminum.
  • Fine-grain hardening results in an increase in the high-temperature strength as well as an increase in ductility and toughness in the lower temperature range. At higher temperatures, however, this proves to be an unsuitable measure for increasing the strength, since in the creep range (T> 0.4
  • HCF High Cycle Fatigue
  • the setting of a suitable grain size is therefore of crucial importance in order to ensure a reasonable compromise with regard to creep and fatigue strength.
  • the alloys according to the invention therefore typically have an average grain size of 10 to 500 ⁇ m.
  • the grain size can preferably be within the following limits:
  • Too low a chromium content means that the chromium concentration at the oxide-metal interface falls very quickly below the critical limit when the alloy is used in a corrosive atmosphere, so that if the oxide layer is damaged, a closed, pure chromium oxide layer can no longer form, but also may form other less protective oxides (e.g. nickel and / or iron oxides). Therefore 12% is the lower limit for chromium. This is particularly important because the absorber tubes are exposed to the salt on the inside but to the ambient air on the outside. This means that a certain chromium content is necessary to ensure oxidation resistance at the elevated temperatures of up to 1000 ° C in ambient air. Too high Chromium contents worsen the phase stability of the alloy, especially with the high aluminum contents of ⁇ 1.8%. Therefore, 30% chromium is to be regarded as the upper limit.
  • the cost of the alloy increases as the iron content is reduced. Below 0.1%, the costs rise disproportionately because special starting material has to be used. Therefore 0.1% iron is the lower limit for reasons of cost. 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 in order to ensure the phase stability of the alloy according to the invention.
  • Silicon is required in the manufacture of the alloy. A minimum content of 0.001% is therefore necessary. Too high contents, in turn, impair the processability and the phase stability, especially with high aluminum and chromium contents. The silicon content is therefore limited to 0.50%.
  • a minimum manganese content of 0.001% is necessary to improve processability. Manganese is limited to 2.0% as this element reduces oxidation resistance.
  • Titanium increases the high temperature strength. From 1.00% the oxidation behavior can be worsened, which is why 1.00% is the maximum value.
  • magnesium and / or calcium contents improve processing by setting sulfur, which causes the occurrence of low melting nickel-sulfur eutectics is avoided.
  • a minimum content of 0.0002% is therefore required for magnesium and / or calcium. If the contents are too high, intermetallic nickel-magnesium phases or nickel-calcium phases can occur, which again significantly worsen the processability.
  • the magnesium and / or calcium content is therefore limited to a maximum of 0.05%.
  • a minimum carbon content of 0.001% is necessary for good creep resistance. Carbon is limited to a maximum of 0.12%, since above this level this element reduces the workability due to the excessive formation of primary carbides.
  • Nitrogen is limited to a maximum of 0.05%, as this element reduces the processability through the formation of coarse carbonitrides.
  • the oxygen content must be ⁇ 0.020% in order to guarantee the manufacturability of the alloy. Too low an oxygen content increases the costs. The oxygen content is therefore ⁇ 0.0001%.
  • the phosphorus content should be less than or equal to 0.030%, since this surface-active element impairs the resistance to oxidation. Too low a phosphorus content increases the costs. The phosphorus content is therefore ⁇ 0.001%.
  • the sulfur content should be set as low as possible, since this surface-active element impairs the resistance to oxidation. A maximum of 0.010% sulfur is therefore specified.
  • Molybdenum is limited to a maximum of 2.0%, as this element is the
  • Oxidation resistance reduced. Tungsten is limited to a maximum of 2.0%, as this element is the
  • the oxidation resistance can be further improved by adding elements with an affinity for oxygen, such as, for example, yttrium, lanthanum, cerium, cerium, mischmetal. They do this by being built into the oxide layer and blocking the diffusion paths of oxygen on the grain boundaries.
  • elements with an affinity for oxygen such as, for example, yttrium, lanthanum, cerium, cerium, mischmetal. They do this by being built into the oxide layer and blocking the diffusion paths of oxygen on the grain boundaries.
  • a minimum yttrium content of 0.001% is necessary in order to maintain the yttrium's oxidation resistance increasing effect.
  • the upper limit is set at 0.20% for cost reasons.
  • a minimum content of 0.001% lanthanum is necessary in order to maintain the lanthanum's oxidation resistance increasing effect.
  • the upper limit is set at 0.20% for cost reasons.
  • a minimum content of 0.001% cerium is necessary in order to maintain the effect of cerium, which increases the resistance to oxidation.
  • the upper limit is set at 0.20% for cost reasons.
  • a minimum content of 0.001% cerium mischmetal is necessary in order to maintain the oxidation resistance-increasing effect of the cerium mischmetal.
  • the upper limit is set at 0.20% for cost reasons.
  • niobium can be added, since niobium also increases the high temperature strength. Higher contents increase the costs very much.
  • the upper limit is therefore set at 1, 10%.
  • the alloy can also contain tantalum, since tantalum also increases the high-temperature strength. Higher contents increase the costs very much.
  • the upper limit is therefore set at 0.60%. A minimum content of 0.001% is required to have an effect.
  • the alloy can also contain zirconium. A minimum content of 0.001% zirconium is necessary in order to maintain the effect of the zirconium, which increases the high temperature strength and the oxidation resistance. For cost reasons, the upper limit is set at 0.20% zirconium.
  • the alloy can also contain hafnium.
  • a minimum content of 0.001% hafnium is necessary in order to maintain the hafnium's high-temperature strength and oxidation resistance-enhancing effect.
  • the upper limit is set at 0.20% hafnium.
  • boron can be added to the alloy because boron improves creep resistance. Therefore a content of at least 0.0001% should be present. At the same time, this surface-active element worsens the resistance to oxidation. 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 resistance to oxidation.
  • Copper is limited to a maximum of 0.5%, as this element reduces the resistance to oxidation.
  • Vanadium is limited to a maximum of 0.5%, as this element also reduces the resistance to oxidation.

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Abstract

L'invention concerne un alliage de nickel-chrome-aluminium comprenant (en % en masse) 12 à 30 % de chrome, 1,8 à 4,0 % d'aluminium, 0,1 à 7,0 % de fer, 0,001 à 0,50 % de silicium, 0,001 à 2,0 % de manganèse, 0,00 à 1,00 % de titane, 0,00 à 1,10 % de niobium, 0,00 à 0,5 % de cuivre, 0,00 à 5,00 % de cobalt, dans chaque cas, 0,0002 à 0,05 % de magnésium et/ou de calcium, 0,001 à 0,12 % de carbone, 0,001 à 0,050 % d'azote, 0,001 à 0,030 % de phosphore, 0,0001 à 0,020 % d'oxygène, au maximum 0,010 % de soufre, au maximum 2,0 % de molybdène, au maximum 2,0 % de tungstène et le reste de nickel en une teneur minimale ≥ 50 % et des impuretés liées au procédé habituelles, destiné à être utilisé dans des tours solaires, utilisant des masses fondues de sel de type chlorure et/ou carbonate en tant que milieu caloporteur. Afin d'assurer une bonne aptitude au traitement, la condition suivante doit être satisfaite : Fv ≥ 0,9 avec Fv = 4,88050 - 0,095546*Fe - 0,0178784*Cr - 0,992452*Al - 1,51498*Ti - 0,506893*Nb + 0,0426004*AI*Fe, Fe, Cr, AI, Ti et Nb étant les concentrations des éléments respectifs en % en masse.
EP20839221.7A 2019-12-06 2020-12-04 Alliage de nickel-chrome-aluminium présentant de bonnes aptitude au traitement, résistance au fluage et résistance à la corrosion et son utilisation Pending EP4069873A1 (fr)

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DE102019133293 2019-12-06
DE102020132219.4A DE102020132219A1 (de) 2019-12-06 2020-12-03 Verwendung einer Nickel-Chrom-Aluminium-Legierung mit guter Verarbeitbarkeit, Kriechfestigkeit und Korrosionsbeständigkeit
PCT/DE2020/101026 WO2021110218A1 (fr) 2019-12-06 2020-12-04 Alliage de nickel-chrome-aluminium présentant de bonnes aptitude au traitement, résistance au fluage et résistance à la corrosion et son utilisation

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JP (1) JP7479472B2 (fr)
KR (1) KR20220099565A (fr)
CN (1) CN114787402B (fr)
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WO (1) WO2021110218A1 (fr)

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US11639957B2 (en) * 2021-07-02 2023-05-02 Northrop Grumman Systems Corporation Planar ring radiation barrier for cryogenic wafer test system
CN114309586B (zh) * 2021-12-31 2024-01-26 西安稀有金属材料研究院有限公司 一种高熵合金/炭黑复合电磁吸波材料及其制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4882125A (en) * 1988-04-22 1989-11-21 Inco Alloys International, Inc. Sulfidation/oxidation resistant alloys
US5997809A (en) 1998-12-08 1999-12-07 Inco Alloys International, Inc. Alloys for high temperature service in aggressive environments
JP3644532B2 (ja) 1999-07-27 2005-04-27 住友金属工業株式会社 熱間加工性、溶接性および耐浸炭性に優れたＮｉ基耐熱合金
KR100372482B1 (ko) * 1999-06-30 2003-02-17 스미토모 긴조쿠 고교 가부시키가이샤 니켈 베이스 내열합금
DE102012002514B4 (de) 2011-02-23 2014-07-24 VDM Metals GmbH Nickel-Chrom-Eisen-Aluminium-Legierung mit guter Verarbeitbarkeit
JP5146576B1 (ja) * 2011-08-09 2013-02-20 新日鐵住金株式会社 Ｎｉ基耐熱合金
DE102012011162B4 (de) * 2012-06-05 2014-05-22 Outokumpu Vdm Gmbh Nickel-Chrom-Legierung mit guter Verarbeitbarkeit, Kriechfestigkeit und Korrosionsbeständigkeit
DE102012011161B4 (de) * 2012-06-05 2014-06-18 Outokumpu Vdm Gmbh Nickel-Chrom-Aluminium-Legierung mit guter Verarbeitbarkeit, Kriechfestigkeit und Korrosionsbeständigkeit
DE102014001328B4 (de) * 2014-02-04 2016-04-21 VDM Metals GmbH Aushärtende Nickel-Chrom-Eisen-Titan-Aluminium-Legierung mit guter Verschleißbeständigkeit, Kriechfestigkeit, Korrosionsbeständigkeit und Verarbeitbarkeit
DE102016111736B4 (de) * 2016-06-27 2020-06-18 Heraeus Nexensos Gmbh Hülse zur Abdeckung eines Temperatursensors, Temperaturmessvorrichtung mit einer derartigen Hülse, Verfahren zum Verbinden einer derartigen Hülse mit einer Temperaturmessvorrichtung und Verwendung einer Legierung
US11976346B2 (en) 2017-10-13 2024-05-07 Haynes International, Inc. Solar tower system containing molten chloride salts
DE102018107248A1 (de) * 2018-03-27 2019-10-02 Vdm Metals International Gmbh Verwendung einer nickel-chrom-eisen-aluminium-legierung

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US20230020446A1 (en) 2023-01-19
JP7479472B2 (ja) 2024-05-08
CN114787402B (zh) 2023-10-31
CN114787402A (zh) 2022-07-22
JP2023504562A (ja) 2023-02-03
US20230160040A2 (en) 2023-05-25
WO2021110218A1 (fr) 2021-06-10
KR20220099565A (ko) 2022-07-13

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