WO1999028515A1 - Superalliage de nickel malaxable et stable a l'oxydation - Google Patents

Superalliage de nickel malaxable et stable a l'oxydation Download PDF

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Publication number
WO1999028515A1
WO1999028515A1 PCT/EP1998/006335 EP9806335W WO9928515A1 WO 1999028515 A1 WO1999028515 A1 WO 1999028515A1 EP 9806335 W EP9806335 W EP 9806335W WO 9928515 A1 WO9928515 A1 WO 9928515A1
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WO
WIPO (PCT)
Prior art keywords
max
nickel alloy
temperature range
resistance
alloys
Prior art date
Application number
PCT/EP1998/006335
Other languages
German (de)
English (en)
Inventor
Ulrich Brill
Original Assignee
Krupp Vdm Gmbh
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Krupp Vdm Gmbh filed Critical Krupp Vdm Gmbh
Priority to DE59802586T priority Critical patent/DE59802586D1/de
Priority to EP98954347A priority patent/EP1047801B1/fr
Publication of WO1999028515A1 publication Critical patent/WO1999028515A1/fr

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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
    • C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W

Definitions

  • the invention relates to a kneadable, austenitic nickel alloy for objects with high resistance to isothermal and cyclic high-temperature oxidation, high heat resistance and creep resistance up to 1200 ° C, but in particular in the temperature range from 700 to 900 ° C.
  • Components in flying and stationary gas turbines such as combustion chamber linings, guide vanes, honey combs, heat shields and plates, as well as the rotating disks and rotor blades are particularly mechanically stressed in this temperature range.
  • Good oxidation resistance and resistance to hot gas corrosion protect the material without the need for expensive coating systems.
  • Objects such as furnace components, firing racks, radiant tubes, furnace rollers, furnace muffles, retorts, support and fastening elements in furnaces for ceramic products, catalyst foils, heating conductors and diesel glow plugs, on the other hand, are often exposed to significantly higher temperatures, reaching up to 1,200 ° C. They must be characterized by good scaling resistance not only in the case of isothermal, but also in the case of cyclic oxidation, and by sufficient heat and creep resistance.
  • An austenitic alloy has become known for the first time from US Pat. No. 3,607,243 with contents in mass% to 0.1% carbon, 58-63% nickel, 21-25% chromium, 1-1.7% aluminum and optionally up to 0.1%. 5% silicon, up to 1.0% manganese, up to 0.6% titanium, up to 0.006% boron, up to 0.1% magnesium, up to 0.05% calcium, the rest iron, the phosphorus content below 0.030%, the sulfur content below 0.015%, which has a good resistance especially to cyclic oxidation at temperatures up to 1 093 ° C.
  • the heat resistance values are given as follows: 80 MPa for 982 ° C, 45 MPa for 1 093 ° C and 43 MPa for 1 149 ° C.
  • the creep rupture strength after 1,000 hours is 32 MPa for 871 ° C, 16 MPa for 982 ° C and 7 MPa for 1 093 ° C.
  • NiCr23Fe material with the German material no. 2.4851 and the UNS designation N 06601 are introduced in industrial applications.
  • This material has proven itself particularly when used in the temperature range above 1000 ° C. This is based on the formation of a protective chromium oxide-aluminum oxide layer and in particular on the low tendency of the oxide layer to flake off under changes in temperature.
  • the material has developed into an important alloy for industrial furnace construction. Typical applications are jet pipes for gas and oil-fired furnaces and transport rollers in roller hearth furnaces for the firing of ceramic products. The material is also suitable for parts in exhaust gas detoxification plants and petrochemical plants.
  • the oxidation resistance expressed by the so-called specific mass change in g / m 2 • h in air at high test temperatures, for example 1 093 ° C, as described in US Pat. No. 4,784,830, is not the only decisive factor for the service life of highly heat-resistant objects, but rather also the heat resistance and the creep rupture strength at the respective application temperatures.
  • EP-A 0 508 058 discloses the alloying of carbon contents from 0.12 to 0.30% in connection with the stable carbide formers titanium (0.01 to 1.0%), niobium (0.01 to 1.0%) and zirconium (0.01 to 0.20%) to a nickel alloy with 23 to 30% chromium, 8 to 11% iron, 1, 8 to 2.4% aluminum, 0.01 to 0.15% yttrium, 0.001 to 0.015% magnesium, 0.001 to 0.010% calcium, with maximum contents of 0.030% for nitrogen, 0.50% for silicon, 0.25% for manganese , 0.020% for phosphorus and 0.010% for sulfur. To ensure sufficient resistance to oxidation at temperatures above 1,100 ° C, chrome contents of at least 23% are prescribed.
  • the hot and creep rupture strengths achieved with this material exceed the 1% creep strength limits (R p ⁇ , 0/104) and creep rupture strengths (R m / ⁇ o 4 ) as well as the thermal strengths (Rm) and 1% yield strength (R p ⁇ , o) in the temperature range from 850 to 1 200 ° C.
  • the nickel alloy should contain 2.3 to 3.0% aluminum and 0.01 to 0.15% yttrium, additions of titanium (0.01 to 0.20%), niobium (0.01 to 0.20%) and zirconium (0.01 to 0.10%) are used for the primary excretion of carbonitrides.
  • EP-A 0 752 481 limits the magnesium content to 0.001 to 0.015% and the calcium content to 0.001 to 0.010%, while for the elements nitrogen with max. 0.020% and sulfur with max. 0.010% the upper limits are given.
  • EP-A 0 752 481 relate exclusively to the temperature range 850-1,200 ° C, while in the temperature range 700-900 ° C no increase in strength could be achieved. However, it is precisely this temperature range that materials are exposed to, particularly in stationary and flying gas turbines.
  • the tantalum carbide-strengthened nickel-chromium wrought alloy according to the invention has the addition of 7.5 to 8.5% tantalum.
  • This surprisingly leads to the excretion of primary tantalum carbides of the TaC type, which likewise separate between the liquidus and solidus temperatures during the solidification of the melt, but which result in a significantly higher strength increase compared to the primarily eliminated chromium carbides of the type Cr 7 C 3 they are smaller and more evenly distributed and have a higher thermal stability, which manifests itself in the fact that no reaction with the matrix could be observed for the operating temperature range of the new material up to 1200 ° C.
  • tantalum not set as carbide a significant increase in solid-solution strengthening, which is much higher than the solid-solution strengthening caused by chromium due to the significantly larger atomic radius of the Ta atom compared to chromium.
  • the lower limit of the claimed Ta content is determined by the transition from chromium carbide to tantalum carbide.
  • the matrix contains up to 7.5% tantalum exclusively chromium carbide, which cannot be eliminated in favor of tantalum carbide at higher tantalum contents.
  • tantalum contents of more than 8.5% no longer allow hot forming.
  • Chromium contents of at least 25% are required to ensure adequate resistance to oxidation, especially at temperatures above 1,100 ° C.
  • the upper limit should not exceed 30% to avoid problems with the hot and cold forming of the alloy.
  • yttrium in the range of 0.01 to 0.15%, the cyclic oxidation resistance in particular is sustainably improved. Levels below 0.01% have no significant influence on the adhesive strength of the oxide layers. On the other hand, yttrium contents above 0.15% can lead to restricted hot forming due to local melting.
  • Aluminum causes, in particular in the temperature range from 600 to 800 ° C, which the material passes through in use both during heating and cooling, an increase in heat resistance through the elimination of the NisAI phase ( ⁇ 1 phase). Since the elimination of this phase is associated with a drop in toughness, it is necessary to limit the aluminum content.
  • the determination of the elongation at break in the temperature range from room temperature to 1200 ° C. showed only a slight reduction in the elongation at break in the temperature range around 800 ° C., so that the aluminum content could be set at 2.3 to 3.0%.
  • the silicon content should be kept as low as possible in order to avoid the formation of low-melting phases.
  • the silicon content should be less than or equal to 0.50%, which is technically manageable today without any problems.
  • the manganese content should not exceed 0.25% in order to avoid negative effects on the oxidation resistance of the material.
  • Additions of magnesium and calcium serve to improve the hot formability and also improve the resistance to oxidation.
  • the upper limits of 0.015% for magnesium and 0.010% for calcium should not be exceeded, since levels of magnesium and calcium above these limits promote the occurrence of low-melting phases and thus in turn deteriorate the hot formability.
  • the nickel alloy according to the invention is largely free of iron, which may be represented up to a maximum of 1%.
  • Table 1 contains analyzes of four prior art alloys A, B, C, D, and three alloys E, F, and G that fall under the invention.
  • Fig. 3 shows the R p0 , ⁇ -strain limits for 700 ° C for the alloys
  • Fig. 4 shows the R p0 , ⁇ time expansion limits for 800 ° C for the alloys
  • Fig. 5 shows the R p0 , ⁇ -time expansion limits for 900 ° C for the alloys
  • FIGS. 3 to 5 show the 0.1% strain limits for the alloys B - D and for the alloys E - G according to the invention for 700 ° C., 800 ° C. and 900 ° C. for test times of up to 1,000 hours. At all test temperatures, the alloys E-G according to the invention proved to be clearly superior to the alloys B-D representing the prior art.
  • FIGS. 6 to 8 show the development over time of the specific mass change in cyclic oxidation tests in air at 1,000 ° C., 1,100 ° C. and 1,200 ° C. up to test times of approximately 1,100 hours.
  • the alloy F according to the invention exhibits the smallest change in mass at the end of the test and is therefore to be classified as the most resistant to oxidation.
  • the specific mass change of the alloy F according to the invention is at a very low level at 1,000 ° C., but higher than that of the comparative alloys B and C, but shows the desired parabolic behavior of the mass change over time. Since the higher test temperatures of 1 100 ° C and 1 200 ° C represent the highest stress conditions, it can be said that the alloy F according to the invention has the best oxidation behavior over the entire temperature range up to 1 200 ° C.
  • the austenitic, tantalum carbide-hardened nickel-chromium alloy according to the invention is therefore particularly suitable for: because of its superior mechanical properties at temperatures up to 900 ° C. and its good cyclic oxidation resistance up to 1200 ° C.
  • the objects mentioned can be easily manufactured from the material according to the invention, since it is not only readily thermoformable, but also for cold-forming processes, such as Cold rolling to thin dimensions, folding, deep drawing, flanging and stretch drawing, which has the necessary forming capacity.
  • the material can also be welded without problems using the techniques available today.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)

Abstract

L'invention concerne un superalliage de nickel malaxable austénitique destiné à des objets ayant une grande stabilité vis-à-vis de l'oxydation haute température isotherme et cyclique et une grande résistance au fluage pour une durée déterminée jusqu'à 1200 °C, notamment dans la plage comprise entre 700 et 900 °C. Ce superalliage est composé de 0,20 à 0,40 % en poids de carbone; 25 à 30 % en poids de chrome 7,5 à 8,5 % en poids de tantale; 2,3 à 3,0 % en poids d'aluminium; 0,01 à 0,15 % en poids d'yttrium; 0,01 à 0,20 % en poids de titane; 0,01 à 0,20 % en poids de niobium; 0,01 à 0,15 % en poids de circonium; 0,001 à 0,015 % en poids de magnésium; 0,001 à 0,010 % en poids de calcium; max. 0,030 % en poids d'azote; max. 0,50 % en poids de silicium; max. 0,25 % en poids de manganèse; max. 0,020 % en poids de phosphore; max. 0,010 % en poids de soufre. Le reste comprend du nickel, y compris des impuretés inévitables dues à l'élaboration.
PCT/EP1998/006335 1997-12-03 1998-10-05 Superalliage de nickel malaxable et stable a l'oxydation WO1999028515A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE59802586T DE59802586D1 (de) 1997-12-03 1998-10-05 Hochwarmfeste, oxidationsbeständige knetbare nickellegierung
EP98954347A EP1047801B1 (fr) 1997-12-03 1998-10-05 Superalliage de nickel malaxable et stable a l'oxydation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19753539A DE19753539C2 (de) 1997-12-03 1997-12-03 Hochwarmfeste, oxidationsbeständige knetbare Nickellegierung
DE19753539.9 1997-12-03

Publications (1)

Publication Number Publication Date
WO1999028515A1 true WO1999028515A1 (fr) 1999-06-10

Family

ID=7850555

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1998/006335 WO1999028515A1 (fr) 1997-12-03 1998-10-05 Superalliage de nickel malaxable et stable a l'oxydation

Country Status (4)

Country Link
EP (1) EP1047801B1 (fr)
DE (2) DE19753539C2 (fr)
WO (1) WO1999028515A1 (fr)
ZA (1) ZA9810883B (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0456119A1 (fr) * 1990-05-07 1991-11-13 PM HOCHTEMPERATUR-METALL GmbH Superalliage à base de nickel
EP0508058A1 (fr) * 1991-04-11 1992-10-14 Krupp VDM GmbH Alliage austénitique nickel-chrome-fer
EP0752481A1 (fr) * 1995-07-04 1997-01-08 Krupp VDM GmbH Alliage de nickel malléable

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4312682A (en) * 1979-12-21 1982-01-26 Cabot Corporation Method of heat treating nickel-base alloys for use as ceramic kiln hardware and product
US4439248A (en) * 1982-02-02 1984-03-27 Cabot Corporation Method of heat treating NICRALY alloys for use as ceramic kiln and furnace hardware
US4891183A (en) * 1986-12-03 1990-01-02 Chrysler Motors Corporation Method of preparing alloy compositions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0456119A1 (fr) * 1990-05-07 1991-11-13 PM HOCHTEMPERATUR-METALL GmbH Superalliage à base de nickel
EP0508058A1 (fr) * 1991-04-11 1992-10-14 Krupp VDM GmbH Alliage austénitique nickel-chrome-fer
EP0752481A1 (fr) * 1995-07-04 1997-01-08 Krupp VDM GmbH Alliage de nickel malléable

Also Published As

Publication number Publication date
DE19753539A1 (de) 1999-06-17
DE59802586D1 (de) 2002-01-31
ZA9810883B (en) 1999-05-18
EP1047801B1 (fr) 2001-12-19
DE19753539C2 (de) 2000-06-21
EP1047801A1 (fr) 2000-11-02

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