EP3757238B1 - Feuerfeste legierung auf nickelbasis und mit hohem chromgehalt, und entsprechendes entwicklungsverfahren - Google Patents

Feuerfeste legierung auf nickelbasis und mit hohem chromgehalt, und entsprechendes entwicklungsverfahren Download PDF

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EP3757238B1
EP3757238B1 EP20181592.5A EP20181592A EP3757238B1 EP 3757238 B1 EP3757238 B1 EP 3757238B1 EP 20181592 A EP20181592 A EP 20181592A EP 3757238 B1 EP3757238 B1 EP 3757238B1
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alloy
niobium
titanium
chromium
nickel
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EP3757238A1 (de
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Manuel ROUSSEL
Antoine FACCO
Meriem ABIKCHI
Mathieu COUVRAT
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Manoir Industries SAS
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Manoir Industries SAS
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/052—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 40%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • 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
    • 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
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/06—Alloys based on chromium

Definitions

  • the present invention relates to the field of austenitic alloys requiring good mechanical and environmental resistance at high temperatures, in particular for use in steam cracking furnaces in the petrochemical industry.
  • it relates to a high-chromium austenitic alloy, which has excellent resistance to corrosion and creep at temperatures above 900°C.
  • Austenitic alloys based on nickel, chromium and iron known as "refractory” have been known for many years for their very high temperature applications (see in particular the document FR2333870 ). Their resistance to corrosion, carburization and coking is ensured by the development of a protective chromium oxide on their surface under conditions of use. However, their service life is limited by their progressive depletion of chromium.
  • the document EP0765948 offers a high chromium alloy with good resistance to corrosion at high temperatures.
  • This alloy includes the following compounds, in mass percentage: 0.1 to 0.5% Carbon, 0 to 4% Silicon, 0 to 3% Manganese, 40 to 50% Chromium, 0 to 10% Iron, 0.01 to 0.6% Titanium, 0.01 to 0.2% Zirconium, at least one of the elements Tungsten, Niobium and Molybdenum respectively 0.5 to 5%, 0.3 to 2% and 0.5 to 3%, and the balance in Nickel and impurities.
  • EP2939808 offers an alloy with good resistance to rupture, creep at high temperature (> 800°C) or corrosion, with an average chromium content (between 20% and 35%).
  • the present invention provides a solution to achieve the above objectives.
  • the invention relates to a high-chromium austenitic alloy, which has excellent environmental and creep resistance and high ductility after aging, at temperatures greater than or equal to 900°C.
  • the invention also relates to a method for designing such an alloy.
  • the invention relates to an austenitic alloy as described in claim 1.
  • the invention also relates to a method of designing a high chromium nickel-based austenitic alloy as described in claim 4.
  • the method includes a step of choosing the mass percentages of chromium (x Cr ), iron (x Fe ), carbon (x C ), titanium (x Ti ), niobium (x Nb ), silicon (x Si ) and manganese (x Mn ) so that the alloy has a molar fraction (f MX ) of secondary carbo-nitrides rich in niobium and/or titanium greater than 0.1%, after the service temperature has been applied to it.
  • the invention finally relates to a method for validating a nickel-based austenitic alloy with a high chromium content as described in claim 7.
  • the validation method comprises a step of verifying that the molar fraction (f MX ) of secondary carbo-nitrides rich in niobium and/or titanium in the alloy is greater than 0.1%, after the service temperature has been applied to said alloy.
  • FIG. 1 There figure 1 presents the mass loss observed during the cyclic oxidation of some tested alloys.
  • the invention relates to an austenitic alloy based on nickel, chromium and iron intended to be used at a service temperature between 900°C and 1150°C.
  • austenitic alloy according to the invention could be used at service temperatures below 900°C, but would not present, in these temperature ranges, any significant advantage compared to a standard alloy containing less than 40% chromium.
  • the alloy according to the invention based on nickel, comprises a high chromium content in order to ensure good resistance to corrosion, carburization and coking, thanks to the development of a protective chromium oxide on the surface of said alloy, under the conditions of use.
  • the chromium content according to the invention is further defined in a relatively narrow range. A minimum of 40% chromium is required, as mentioned above, for good environmental resistance.
  • the maximum mass percentage of chromium is limited to 45% to limit the integration of alphagenic elements tending to destabilize the austenitic structure of the alloy and to limit the formation of a' phase rich in Cr, a consequence of which is the loss of ductility after aging.
  • the iron content is also chosen within a restricted range.
  • the minimum mass percentage of iron is set at a value strictly greater than 10% so as to promote the formation of secondary carbo-nitrides of type MX rich in Nb and/or Ti at the service temperature: M is therefore mainly niobium and/or titanium, and X is composed of carbon and nitrogen.
  • Niobium, titanium and carbon are compounds included in the alloy and described below. Nitrogen is introduced into the alloy during production, due to its presence in the raw materials and/or in the ambient atmosphere.
  • Secondary carbo-nitrides are carbo-nitrides which precipitate in service, as opposed to primary carbides which are present in the structure of the as-cast alloy.
  • the minimum iron content is even 10.5%, or even 10.8%.
  • the quantity of iron is less than or equal to 14% to limit the integration of alphagenic elements tending to destabilize the austenitic structure of alloying and the formation of Cr-rich a' phase.
  • the amount of iron can advantageously be less than or equal to 12%.
  • the mass percentage of carbon is set at a minimum of 0.4% to allow the formation in the alloy of a significant molar fraction of secondary carbo-nitrides of type MX, said carbo-nitrides reinforcing the creep resistance of the alloy.
  • the maximum percentage is set at 0.6% in order to maintain sufficient ductility for the use of the material, said reinforcement by carbo-nitrides also having the effect of reducing ductility.
  • Titanium has a strong impact on the formation of finer and uniformly distributed secondary carbo-nitrides in the alloy: it is particularly effective at low contents, called micro additions. It is included in the alloy in a mass percentage ranging from 0.05% to 0.2%.
  • Niobium in proportions ranging from 0.5% to 1.5%, is added to the alloy. This compound is essential for the formation of secondary carbo-nitrides of type MX.
  • the lower limit of the range is particularly important since it ensures the triggering of precipitation of secondary carbo-nitrides of type MX in service: in fact, the applicant has observed that at a content of less than 0.5%, precipitation was not triggered.
  • the upper limit is essentially dictated by economic reasons, niobium being a relatively expensive compound.
  • the addition of at least one reactive element, selected from rare earths (such as yttrium, cerium, etc.) or hafnium, is beneficial to the growth and adhesion of the chromium oxide layer to the surface of the alloy.
  • the total amount of reactive elements is set at a minimum of 0.002%. A total quantity greater than 0.1% does not bring any additional effect while it implies a strong impact on the cost; it can even be detrimental to the mechanical properties.
  • the total content of reactive element(s) is limited to 0.05%.
  • the alloy may optionally contain silicon, to promote flow during casting of the alloy and to reinforce its resistance to corrosion.
  • the quantity of silicon is nevertheless limited to 1% to avoid negatively impacting the creep resistance of the alloy and the adhesion of the chromium oxide layer. This limit also helps to preserve good ductility after aging.
  • the alloy may also contain manganese, but in a mass percentage of less than 0.5% to avoid or limit the formation of manganese and chromium spinel oxide which has very rapid formation kinetics but is less stable and protective than chromium oxide.
  • the alloy comprises Ni, in a percentage complementing the composition of the alloy, so that the sum of the mass percentages of the compounds reaches 100%.
  • the role of nickel in the alloy is to maintain a refractory alloy with an austenitic structure.
  • the amount of nickel does not exceed 50%, in line with economic reasons, nickel being a major contributor to costs.
  • the alloy can also include at very low levels other classic elements of steels that are found in particular in the raw materials or in the manufacturing stages. At very low levels, these elements have little impact or particular need. We thus find at contents strictly less than 0.5% of elements such as molybdenum or copper.
  • the alloy may possibly be polluted by trace impurities whose content is of the order of one particle per million (ppm), and strictly less than one hundred particles per million, such as phosphorus, sulfur, lead, tin, zirconium, tungsten, etc.
  • the service temperature is the temperature to which the alloy is intended to be subjected, during its use: for example, for an alloy forming a steam cracking furnace tube, the service temperature may be between 900°C and 1150°C.
  • the applicant was able to determine that, in an austenitic alloy with a high chromium content, the creep resistance, at the service temperature, increases with the increase of the molar fraction of secondary carbonitrides of type MX rich in Nb and/or Ti in the alloy brought to said temperature.
  • a characteristic of the austenitic alloy according to the invention is that it has at least 0.1% (in mole percentage) of these secondary carbo-nitrides of type MX, after the service temperature has been applied to it for a few hours, typically for 10 hours or more.
  • the fact that the austenitic alloy comprises a minimum mole fraction of secondary carbo-nitrides of type MX rich in Nb and/or Ti makes it possible to ensure that the austenitic alloy with a high chromium content has excellent creep resistance, in addition to excellent resistance to the environment (corrosion) linked to the high percentage of chromium.
  • the presence of a minimum molar fraction of secondary carbonitrides of type MX in the alloy after the service temperature has been applied to it may be verified experimentally on a sample (for example by scanning or transmission electron microscopy analysis) or alternatively, as proposed below, anticipated during the design of the alloy or verified from the composition of said alloy measured by spark spectrometry.
  • f MX is the molar fraction of secondary carbonitrides of type MX
  • x Si , x Cr , x Fe , x Ti , x Nb , x C , x Mn are the mass percentages of Si, Cr, Fe, Ti, Nb, C and Mn respectively in the alloy.
  • f MX carbo-nitrides Since the molar fraction f MX of MX carbo-nitrides varies very little between 900°C and 1150°C in the range of alloys studied, the evaluation of f MX for a single temperature (here 1100°C) is sufficient to discriminate between compositions offering good creep resistance and those offering poor creep resistance.
  • the mass percentages x Si , x Cr , x Fe , x Ti , x Nb , x C , x Mn , respectively of Si, Cr, Fe, Ti, Nb, C and Mn in the alloy, can thus be chosen so that the alloy has at least 0.1% (in molar percentage) of secondary carbonitrides of type MX, after the service temperature Ts has been applied to it for a few hours.
  • the above-mentioned mass percentages can be chosen so as to respect the relation R2 below: (R2) 1,4022 ⁇ 1,2994 ⁇ 10 ⁇ 4 ⁇ x If 2 + 1,8791 ⁇ 10 ⁇ 3 ⁇ x If + 5,5337 ⁇ 10 ⁇ 7 ⁇ x Cr 4 ⁇ 8,8976 ⁇ 10 ⁇ 5 ⁇ x Cr 3 + 5,3453 ⁇ 10 ⁇ 3 ⁇ x Cr 2 ⁇ 1.42 ⁇ 10 ⁇ 1 ⁇ x Cr ⁇ 4,5781 ⁇ 10 ⁇ 6 ⁇ x Fe 2 + 4,5556 ⁇ 10 ⁇ 4 ⁇ x Fe + 1,5347 ⁇ x You 4 ⁇ 1,1578 ⁇ x You 3 + 2,6301 ⁇ 10 ⁇ 1 ⁇ x You 2 + 1,3352 ⁇ 10 ⁇ 2 ⁇ x You + 7.9375 ⁇ 10 ⁇ 4 ⁇ x Nb 4 ⁇ 2,06378 ⁇ 10 ⁇ 3 ⁇ x Nb 3 + 1,9558 ⁇ 10
  • Compliance with the R2 relationship ensures that the molar fraction of secondary carbonitrides of type MX will be formed at the service temperature, thus guaranteeing good creep resistance of the alloy, in addition to its qualities in ductility and corrosion resistance.
  • the alloy referenced “Ref” is a commercial alloy (Manaurite ® XTM) usually used for steam cracking furnaces in the petrochemical industry. Its chromium content (35%) limits its resistance to the environment and in particular its performance in cyclic oxidation. On the other hand, it has very good creep and ductility properties.
  • the alloy according to the present invention therefore aims to obtain an equivalent or even higher level in terms of creep resistance and ductility, and to improve the resistance to cyclic oxidation, compared to this reference alloy.
  • Alloys 1 to 4 are tested alloys not respecting the composition of the alloy according to the invention and/or not respecting the molar fraction f MX of secondary carbon-nitrides of type MX targeted according to the invention.
  • Alloy 5 is an example of an alloy in accordance with the present invention.
  • Examples of alloys 1 to 5 have a high chromium content (greater than 40%). Their high resistance to the environment (corrosion, carburization, coking) has been verified and gives a higher level of performance to said alloys compared to the reference alloy Ref.
  • FIG. 1 shows the mass loss due to flaking of the chromium oxide layer during the cyclic oxidation of alloys 2, 3, 4 and 5 and compares them to the mass loss observed during the cyclic oxidation of the reference alloy Ref.
  • the graph shows the number of cycles on the abscissa, one cycle corresponding to 45 min at 1150°C and 15 min at room temperature. It can be seen that the high chromium content in a refractory alloy is not a sufficient condition for its resistance to cyclic oxidation. Indeed, alloy 2, despite its high chromium content, exhibits more pronounced flaking during cyclic oxidation than the reference alloy Ref. This poor resistance to cyclic oxidation is explained by its relatively high silicon content, reducing the adhesion of the chromium oxide layer to the surface of the alloy and promoting its flaking.
  • Alloy 4 has a significantly higher resistance to chipping than the reference alloy Ref.
  • the low silicon content of alloy 4 contributes to this improvement.
  • alloy 5 as well as alloy 3 show very good resistance to cyclic oxidation.
  • the presence of one or more reactive element(s) also in a limited content range further improves the performance.
  • the creep resistance of the alloys presented in Table 1 was evaluated from creep tests at 1100°C, under a stress of 12.87 MPa, the tests being carried out on samples taken from parts produced in the different alloys.
  • alloys 1, 3, 4 and 5 having a molar fraction f MX greater than the criterion set in the present invention of 0.1% (relation R2), show better creep behavior than alloy 2 (time to rupture t R of 36 hours), for which the molar fraction f MX is less than 0.1%. Alloy 4 nevertheless has lower creep resistance (time to rupture t R of 111 hours), which is explained by the fact that the value of f MX is low even if it is greater than 0.1.
  • alloy 5 according to the invention has a creep resistance (time to rupture t R of 281 hours) greater than that of alloys 1 to 4 and very close to the targeted creep resistance of alloy Ref.
  • Table 3 shows further creep tests carried out at 1100°C or 950°C, for different applied stresses, which confirm that alloy 5 has good creep resistance generally equivalent to that targeted for the reference alloy Ref, and that alloy 2 has poor creep resistance.
  • alloy 3 The large loss of ductility after aging observed in alloy 3 is related to its excessively high silicon content. This silicon content leads, after annealing, to an increase in the molar fraction of phase G rich in silicon and niobium in the alloy. Alloy 4 has good performance in terms of ductility after aging, but does not have the required level of performance in resistance to cyclic oxidation (no better than alloy Ref) and creep, as previously indicated.
  • Alloy 5, in accordance with the present invention retains a good level of ductility after aging, comparable to the target level obtained on the reference alloy.
  • the high-chromium austenitic alloy according to the invention therefore comprises the compounds Ni, Cr, Fe, C, Si, Ti, Nb, Mn and reactive element(s), according to mass percentages included in the stated ranges, and further comprises a molar fraction of secondary carbonitrides of type MX rich in Nb and/or Ti greater than 0.1%, after the service temperature has been applied to it.
  • the invention also relates to a method for designing a high chromium austenitic alloy (therefore environmentally resistant) intended to be used at a service temperature between 900°C and 1150°C, and having excellent resistance to creep, cyclic oxidation and a good level of ductility after aging.
  • the design process includes choosing the mass percentages x Si , x Cr , x Fe , x Ti , x Nb , x C , x Mn , respectively of Si, Cr, Fe, Ti, Nb, C and Mn in the alloy, so that the alloy has at least 0.1% (in molar percentage) of secondary carbonitrides of type MX rich in Nb and/or Ti, after the service temperature Ts has been applied to it for a few hours.
  • Compliance with the relationship (R2) ensures that the molar fraction f MX of secondary carbon-nitrides of type MX will be formed at the service temperature, thus guaranteeing good creep resistance of the alloy, in addition to its qualities in ductility and resistance to corrosion.
  • the invention further relates to a method for validating the compatibility of a high-chromium austenitic alloy, with a service temperature Ts between 900°C and 1150°C.
  • compatible alloy is meant an alloy having excellent resistance to corrosion, cyclic oxidation and creep, while retaining a good level of ductility.
  • the validation method comprises a step of verifying that the molar fraction f MX of secondary carbo-nitrides rich in niobium and/or titanium in the alloy is greater than 0.1%, after the service temperature has been applied to said alloy.
  • This mole fraction can be measured on samples formed from the alloy to be verified, for example by scanning or transmission electron microscopy analysis; or alternatively, the mole fraction f MX can be verified using the relation R2, from the composition of said alloy measured by spark spectrometry. If the inequality is respected for the relation R2, the alloy is compatible with the service temperature range from 900°C to 1150°C. If the inequality is not respected, the alloy is identified as not compatible with this service temperature range.
  • the austenitic alloys according to the invention can find applications in the field of petrochemistry (steam cracking furnaces) or in any other high-temperature application.
  • temperature typically greater than or equal to 900°C, combining issues of resistance to the environment and creep.

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Claims (7)

  1. Austenitische Legierung auf Basis von Nickel und mit hohem Chromgehalt, die dazu bestimmt ist, bei einer gegebenen Betriebstemperatur zwischen 900 °C und 1150 °C verwendet zu werden,
    die Legierung umfassend die folgenden Verbindungen in Massenprozent:
    - Chrom zwischen 40 % und 45 %,
    - Eisen zwischen 10 % und 14 %,
    - Kohlenstoff zwischen 0,4 % und 0,6 %,
    - Titan zwischen 0,05 und 0,2 %,
    - Niob zwischen 0,5 % und 1,5 %,
    - mindestens ein reaktives Element, das aus seltenen Erden oder Hafnium ausgewählt ist, zwischen 0,002 % und 0,1 %,
    - Silizium zwischen 0 und 1 %,
    - Mangan zwischen 0 und 0,5 %,
    - Molybdän- oder Kupfergehalte unter 0,5 %
    - Spurenverunreinigungen wie Phosphor, Schwefel, Blei, Zinn, Zirkonium oder Wolfram; wobei ihr Gehalt weniger als hundert Partikel pro Million (ppm) beträgt,
    - Nickel zum Ausgleichen der Verbindungen der Legierung, und wobei die Legierung einen Molanteil an sekundären Carbonitriden, die reich an Niob und/oder Titan sind, von mehr als 0,1 % aufweist, nachdem die Betriebstemperatur darauf angewendet wurde, die mittels eines Raster- oder Transmissionselektronenmikroskops gemessen werden.
  2. Austenitische Legierung nach dem vorstehenden Anspruch, wobei die sekundären Carbonitride von Typ MX sind, wobei das Metall M zu mehr als 80 % oder sogar zu mehr als 90 % Niob und/oder Titan ist, wobei das Element X aus Kohlenstoff und Stickstoff besteht.
  3. Austenitische Legierung nach dem vorstehenden Anspruch, wobei die Massenanteile von Chrom, Eisen, Kohlenstoff, Titan, Niob, Silizium und Mangan der folgenden Beziehung (R2) entsprechen: 1,4022 − 1,2994 × 10 − 4 × x Si 2 + 1,8791 × 10 − 3 × x Si + 5,5337 × 10 − 7 × x Cr 4 − 8,8976 × 10 − 5 × x Cr 3 + 5,3453 × 10 − 3 × x Cr 2 − 1,42 × 10 − 1 × x Cr − 4,5781 × 10 − 6 × x Fe 2 + 4,5556 × 10 − 4 × x Fe + 1,5347 × x Ti 4 − 1,1578 × x Ti 3 + 2,6301 × 10 − 1 × x Ti 2 + 1,3352 × 10 − 2 × x Ti + 7,9375 × 10 − 4 × x Nb 4 − 2,06378 × 10 − 3 × x Nb 3 + 1,9558 × 10 − 3 × x Nb 2 + 6,6442 × 10 − 3 × x Nb + 3,0959 × 10 − 1 × x C 4 − 5,1282 × 10 − 1 × x C 3 + 3,1538 × 10 − 1 × x C 2 − 8,5003 × 10 − 2 × x C − 3,3333 × 10 − 6 × x Mn 3 + 1,5 × 10 − 5 × x Mn 2 + 2,2833 × 10 − 4 × x Mn ≥ 0,1
    Figure imgb0008
  4. Verfahren zum Entwerfen einer austenitischen Legierung auf Basis von Nickel und mit hohem Chromgehalt, die dazu bestimmt ist, bei einer gegebenen Betriebstemperatur zwischen 900 °C und 1150 °C verwendet zu werden, die Legierung umfassend die folgenden Verbindungen in Massenprozent:
    - Chrom zwischen 40 % und 45 %,
    - Eisen zwischen 10 % und 14 %,
    - Kohlenstoff zwischen 0,4 % und 0,6 %,
    - Titan zwischen 0,05 und 0,2 %,
    - Niob zwischen 0,5 % und 1,5 %,
    - mindestens ein reaktives Element, das aus seltenen Erden oder Hafnium ausgewählt ist, zwischen 0,002 % und 0,1 %,
    - Silizium zwischen 0 und 1 %,
    - Mangan zwischen 0 und 0,5 %,
    - Molybdän- oder Kupfergehalte unter 0,5 % - Spurenverunreinigungen wie Phosphor, Schwefel, Blei, Zinn, Zirkonium oder Wolfram; wobei ihr Gehalt weniger als hundert Partikel pro Million (ppm) beträgt,
    - Nickel zum Ausgleichen der Verbindungen der Legierung, das Verfahren umfassend einen Schritt zum Auswählen der Massenprozentsätze von Chrom (xCr), Eisen (xFe), Kohlenstoff (xC), Titan (xTi), Niob (xNb), Silizium (xSi) und Mangan (xMn), sodass die Legierung einen Molanteil (fMX) von sekundären Carbonitriden, die reich an Niob und/oder Titan sind, von mehr als 0,1 % aufweist, nachdem die Betriebstemperatur darauf angewendet wurde, die mittels eines Raster- oder Transmissionselektronenmikroskops gemessen werden.
  5. Verfahren zum Entwerfen einer autenitischen Legierung nach dem vorstehenden Anspruch, wobei der Molanteil (fMX) von sekundären Carbonitriden, die reich an Niob und/oder Titan sind, durch Raster- oder Transmissionselektronenmikroskopie an einer Probe gemessen wird, die in der Legierung ausgebildet wird, nachdem die Betriebstemperatur darauf angewendet wurde.
  6. Verfahren zum Entwerfen einer austenitischen Legierung nach einem der zwei vorstehenden Ansprüche, wobei die Massenanteile an Chrom (xCr), Eisen (xFe), Kohlenstoff (xC), Titan (xTi), Niob (xNb), Silizium (xSi) und Mangan (xMn) der folgenden Beziehung (R2) entsprechen: 1,4022 − 1,2994 × 10 − 4 × x Si 2 + 1,8791 × 10 − 3 × x Si + 5,5337 × 10 − 7 × x Cr 4 − 8,8976 × 10 − 5 × x Cr 3 + 5,3453 × 10 − 3 × x Cr 2 − 1,42 × 10 − 1 × x Cr − 4,5781 × 10 − 6 × x Fe 2 + 4,5556 × 10 − 4 × x Fe + 1,5347 × x Ti 4 − 1,1578 × x Ti 3 + 2,6301 × 10 − 1 × x Ti 2 + 1,3352 × 10 − 2 × x Ti + 7,9375 × 10 − 4 × x Nb 4 − 2,06378 × 10 − 3 × x Nb 3 + 1,9558 × 10 − 3 × x Nb 2 + 6,6442 × 10 − 3 × x Nb + 3,0959 × 10 − 1 × x C 4 − 5,1282 × 10 − 1 × x C 3 + 3,1538 × 10 − 1 × x C 2 − 8,5003 × 10 − 2 × x C − 3,3333 × 10 − 6 × x Mn 3 + 1,5 × 10 − 5 × x Mn 2 + 2,2833 × 10 − 4 × x Mn ≥ 0,1
    Figure imgb0009
  7. Verfahren zum Validieren einer austenitischen Legierung auf Basis von Nickel und mit hohem Chromgehalt für ihre Verwendung bei einer gegebenen Betriebstemperatur zwischen 900 °C und 1150 °C, die Legierung umfassend die folgenden Verbindungen in Massenprozent:
    - Chrom zwischen 40 % und 45 %,
    - Eisen zwischen 10 % und 14 %,
    - Kohlenstoff zwischen 0,4 % und 0,6 %,
    - Titan zwischen 0,05 und 0,2 %,
    - Niob zwischen 0,5 % und 1,5 %,
    - mindestens ein reaktives Element, das aus seltenen Erden oder Hafnium ausgewählt ist, zwischen 0,002 % und 0,1 %,
    - Silizium zwischen 0 und 1 %,
    - Mangan zwischen 0 und 0,5 %,
    - Molybdän- oder Kupfergehalte unter 0,5 % - Spurenverunreinigungen wie Phosphor, Schwefel, Blei, Zinn, Zirkonium oder Wolfram; wobei ihr Gehalt weniger als hundert Partikel pro Million (ppm) beträgt,
    - Nickel zum Ausgleichen der Verbindungen der Legierung, das Validierungsverfahren umfassend einen Schritt zum Überprüfen, ob der Molanteil (fMX) an sekundären Carbonitriden, die reich an Niob und/oder Titan sind, in der Legierung größer als 0,1 % ist, nachdem die Betriebstemperatur auf die Legierung angewendet wurde, die mittels eines Raster- oder Transmissionselektronenmikroskops gemessen werden.
EP20181592.5A 2019-06-28 2020-06-23 Feuerfeste legierung auf nickelbasis und mit hohem chromgehalt, und entsprechendes entwicklungsverfahren Active EP3757238B1 (de)

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FR1907175A FR3097877B1 (fr) 2019-06-28 2019-06-28 alliage réfractaire à base de nickel et à haute teneur en chrome et procédé de conception associé

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0765948B1 (de) * 1995-09-29 1999-04-28 Kubota Corporation Hitzebeständige Ni-Cr Legierung

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2333870A1 (fr) 1975-12-02 1977-07-01 Pompey Acieries Alliage refractaire a base de nickel et de chrome possedant une resistance elevee a l'oxydation, a la carburation et au fluage a tres haute temperature
FR2939808B1 (fr) * 2008-12-16 2011-01-07 Air Liquide Alliages fer-nickel-chrome stables a haute temperature
CN109415796A (zh) * 2016-06-28 2019-03-01 新日铁住金株式会社 奥氏体合金材和奥氏体合金管

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0765948B1 (de) * 1995-09-29 1999-04-28 Kubota Corporation Hitzebeständige Ni-Cr Legierung

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FR3097877A1 (fr) 2021-01-01
EP3757238A1 (de) 2020-12-30
ES2999432T3 (en) 2025-02-25
US11499211B2 (en) 2022-11-15
US20200407829A1 (en) 2020-12-31
FR3097877B1 (fr) 2021-06-11

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