EP1188845B1 - Alliage à base de nickel pour des utilisations à haute température - Google Patents

Alliage à base de nickel pour des utilisations à haute température Download PDF

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Publication number
EP1188845B1
EP1188845B1 EP01890180A EP01890180A EP1188845B1 EP 1188845 B1 EP1188845 B1 EP 1188845B1 EP 01890180 A EP01890180 A EP 01890180A EP 01890180 A EP01890180 A EP 01890180A EP 1188845 B1 EP1188845 B1 EP 1188845B1
Authority
EP
European Patent Office
Prior art keywords
nickel
based alloy
chromium
alloy according
carbon
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.)
Expired - Lifetime
Application number
EP01890180A
Other languages
German (de)
English (en)
Other versions
EP1188845A1 (fr
Inventor
Markus Dr. Speidel
Josef Dipl-Ing. Bernauer
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.)
Voestalpine Boehler Edelstahl GmbH
Original Assignee
Boehler Edelstahl GmbH
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Filing date
Publication date
Application filed by Boehler Edelstahl GmbH filed Critical Boehler Edelstahl GmbH
Priority to AT01890180T priority Critical patent/ATE301730T1/de
Publication of EP1188845A1 publication Critical patent/EP1188845A1/fr
Application granted granted Critical
Publication of EP1188845B1 publication Critical patent/EP1188845B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • 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
    • C22C19/053—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%

Definitions

  • the invention relates to a creep-resistant corrosion-resistant nickel-based alloy for Applications in high-temperature technology.
  • a nickel-based alloy with the abbreviation NiCr 7030 accordingly DIN material number 2.4658 is considered to be heat-resistant and is used for heating conductors, Furnace components and the like used. Although such a material depending on Silicon and aluminum content has good oxidation resistance, this shows but low strength and low fatigue properties as well as high Creep values at operating temperatures of around 1000 ° C.
  • This high-temperature, oxidation-resistant, massively embroidered, warm and cold-workable nickel-based alloy consists essentially of (in Mass%) 0.001 to 0.15 carbon, 0.10 to 3.0 nitrogen, 25.0 to 30.0 chromium, more than 0.3 to 1.2 nitrogen, 0.001 to 0.01 boron, 0.01 to 0.5 yttrium, cerium, Lanthanum, hafnium and tantalum, singly or in combination, balance nickel with one Share of at least 64.0%.
  • the carbon content can indeed a Solid solution hardening can be achieved, the mainly effective elements
  • the above alloy in terms of high temperature properties are Chromium and nitrogen. Chromium and nitrogen form chromium nitrides which form the Improve creep strength, with nitrogen in addition a Solid solution solidification yields. With the alloy according to DE-C-4411228 significantly improved creep strength and heat resistance values appear reachable.
  • the object of the present invention is to overcome this deficiency eliminate and an improved nickel base alloy for To create high temperature applications.
  • the advantages achieved by the invention are essentially based on the fact that In the material at temperatures up to 1200 ° C a grain boundary sliding by stable Excretions in the grain boundary areas largely prevented and a Increased solid solution hardening can be achieved. Furthermore, the adhesive strength the chromium spinel or the like layers on the surface increases, thereby an improved high temperature corrosion resistance of the parts is given.
  • the elements of group 4,5 and 6 (except chromium), that are in essential titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), molybdenum (Mo) and tungsten (W) act as solid solution strengthening agents and have different activities with respect to the non-metallic elements Carbon and nitrogen.
  • Ta and Nb form thermally highly stable Nitrides, however, is the nitrogen affinity of the strong carbide formers Mo and W. low.
  • a degree of solid solution hardening may be due to the carbon content and the content of strong carbide formers are adjusted. Is for example the Carbon content of the alloy low, become the strong carbide-forming elements Reinforced in the crystal lattice of the mixed crystals installed and brace this.
  • Another important advantage of the alloy according to the invention is that the above-mentioned elements, in particular the elements Mo and W, shift the peritectic transformation of the II phase by substitution of Cr atoms to higher temperatures and thereby a stabilization of the II precipitates under conditions of use is effected.
  • a transformation taking place at about 1000 ° C with increasing temperature ⁇ + ⁇ ⁇ ⁇ + ⁇ corresponding to ⁇ + Cr 13 Ni 7 N 4 ⁇ ⁇ + Cr 2 N
  • Ni-Cr-N alloys which is associated with a volume change of about 1 ⁇ 10 -3 %, as shown in Table 1, by a Mo concentration of 4% by weight to a temperature of raised above 1210 ° C.
  • Carbon containing greater than 0.0015% by weight promotes the nitride and Carbonitride, but withdrawn at a content of greater than 0.6 wt .-% of Alloy too large amounts of carbide-forming elements, causing a Counteracts matrix solidification. Preference is given to carbon contents of 0.16 to 0.5% by weight.
  • the ratio nitrogen - to carbon content in the Alloy in the range of 0.5 to 5.5, preferably 1.0 to 4.0, optionally 1.0 to 3.0, will be particularly effective and stable Carbonitride precipitates formed and efficient solid solution hardening reached.
  • the material is at least 0.03 wt .-% Al and at least 0.4 wt .-% Si. Higher levels than 3.0 wt .-% Al lead to an adverse excretion behavior, stress cracks and a Coarse grain formation and contents higher than 3.0% Si deteriorate the Thermoformability of the alloy.
  • the corrosion resistance at high temperatures is increased in the the material with elements of group 3 of the periodic table, which are Scandium (Sc), yttrium (Y) lanthanum (La) and lanthanide in one concentration from 0.01 to 0.12% by weight is alloyed.
  • Sc Scandium
  • Y yttrium
  • La lanthanum
  • lanthanide in one concentration from 0.01 to 0.12% by weight is alloyed.
  • Nickel-base alloys with a composition according to the invention can with the help of pressure metallurgy, in which the liquid melt until solidification the same is kept under high pressure (eg DESU method) or powder metallurgically produced.
  • pressure metallurgy in which the liquid melt until solidification the same is kept under high pressure (eg DESU method) or powder metallurgically produced.
  • a deformation of the cast or sintered block is usually after one Homogenization of the material at 1250 ° C with a forming at 1200 ° C.
  • grain sizes of 35 to 80 microns and nitride precipitates with a Diameter of 1 to 5 microns created in the material.
  • the transition temperature of the II phase by a Presence of elements of group 4,5 and 6 increased.
  • Tab. 1 are the determined dissolution and formation temperatures, the composition the II phase and that of the - mixed crystal for a Mo-free Ni-Cr-N alloy and for those with a Mo content of 4 and 8 wt% and one with 4 wt% W specified.
  • concentrations of 8 wt .-% Mo and 0.7 wt .-% N are For example, both temperature values for a ⁇ ⁇ ⁇ conversion above 1300 ° C.
  • the II phase has a reduced chromium content of 45 wt .-% at a molybdenum concentration of 11 wt .-% on.
  • the ⁇ -mixed crystal has increased chromium values of 29% by weight and a molybdenum content of 6.5% by weight at a reduced nickel concentration. Influence of the molybdenum and tungsten content on the interval of the ⁇ + Cr 2 N transformation temperature ⁇ T (dilatometer investigations) Chemical composition [wt.
  • Table 2 shows the chemical composition of the invention Alloys (Legs 1 to 5) and comparative alloys (Legs 6 to 9).
  • the resistance to high temperature corrosion was improved by about 16% (Alloy 3 by more than 22%) in the alloys of the present invention over those of the prior art.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Contacts (AREA)
  • Chemically Coating (AREA)
  • Heat Treatment Of Steel (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Soft Magnetic Materials (AREA)

Claims (8)

  1. Alliage à base de nickel résistant au fluage et à la corrosion destiné à être mis en oeuvre à hautes températures, contenant,
       0,0015 à 0,60 % en poids de carbone (C)
       0,20 à 0,90 % en poids d'azote (N)
       22,0 à 32,0 % en poids de chrome (Cr)
       5,0 à 20,0 % en poids d'éléments des groupes 4, 5 et 6 de la classification périodique, à l'exception du chrome (Cr), contenant du tungstène (W), dans lequel la concentration cumulée Mo + W/2 = 3,0 à 10,0    0,03 à 3,0 % en poids d'aluminium (Al)
       0,4 à 3,0 % en poids de silicium (Si)
       0,01 à 0,12 % en poids d'éléments du groupe 3 de la classification périodique, à l'exception des actinides
       jusqu'à 0,60 % en poids de manganèse (Mn)
       jusqu'à 14,8 % en poids de fer (Fe)
       jusqu'à 0,01 % en poids de bore (B)
       jusqu'à 10,3 % en poids de cobalt (Co)
       0,014 % maximum en poids de phosphore (P)
       0,004 % maximum en poids de soufre (S)
    pour le reste, 51,0 % en poids de nickel (Ni) ainsi que des impuretés liées au procédé d'élaboration.
  2. Alliage à base de nickel selon la revendication 1, contenant 0,16 à 0,5 % en poids de carbone (C).
  3. Alliage à base de nickel selon la revendication 1 ou 2, caractérisé en ce que le rapport azote/carbone est compris entre 0,5 et 5,5, de préférence entre 1,0 et 4,0 et le cas échéant entre 1,0 et 3,0.
  4. Alliage à base de nickel selon l'une des revendications 1 à 3, présentant une concentration pondérale cumulée de molybdène et de tungstène satisfaisant à l'équation : Mo + M/2 = 4,0 à 8,0
  5. Alliage à base de nickel selon l'une des revendications 1 à 4, contenant 25,0 à 30,0 % en poids de chrome (Cr).
  6. Alliage à base de nickel selon l'une des revendications 1 à 5, contenant 0,5 à 1,0 % en poids de silicium (Si).
  7. Alliage à base de nickel selon l'une des revendications 1 à 6, fabriqué selon un procédé de métallurgie sous pression ou de métallurgie des poudres.
  8. Alliage à base de nickel selon l'une des revendications 1 à 7, présentant une grosseur de grain de 35 à 80 µm et des précipités de nitrure de 1 à 5 µm de diamètre.
EP01890180A 2000-09-14 2001-06-08 Alliage à base de nickel pour des utilisations à haute température Expired - Lifetime EP1188845B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT01890180T ATE301730T1 (de) 2000-09-14 2001-06-08 Nickelbasislegierung für die hochtemperaturtechnik

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT15622000 2000-09-14
AT0156200A AT408665B (de) 2000-09-14 2000-09-14 Nickelbasislegierung für die hochtemperaturtechnik

Publications (2)

Publication Number Publication Date
EP1188845A1 EP1188845A1 (fr) 2002-03-20
EP1188845B1 true EP1188845B1 (fr) 2005-08-10

Family

ID=3688355

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EP01890180A Expired - Lifetime EP1188845B1 (fr) 2000-09-14 2001-06-08 Alliage à base de nickel pour des utilisations à haute température

Country Status (5)

Country Link
US (1) US6797232B2 (fr)
EP (1) EP1188845B1 (fr)
AT (2) AT408665B (fr)
CA (1) CA2355446C (fr)
DE (1) DE50107021D1 (fr)

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US7211346B2 (en) * 2002-04-03 2007-05-01 Ut-Battelle, Llc Corrosion resistant metallic bipolar plate
US7829194B2 (en) * 2003-03-31 2010-11-09 Ut-Battelle, Llc Iron-based alloy and nitridation treatment for PEM fuel cell bipolar plates
US20060110626A1 (en) * 2004-11-24 2006-05-25 Heraeus, Inc. Carbon containing sputter target alloy compositions
DE502005005347D1 (de) * 2005-10-24 2008-10-23 Siemens Ag Schweißzusatzwerkstoff, Verwendung des Schweißzusatzwerkstoffes und Verfahren zum Schweißen
EP2059620B1 (fr) * 2006-08-08 2013-01-16 Huntington Alloys Corporation Alliage de soudage et articles destinés à être utilisés pour le soudage, ensembles soudés et procédé de production d'ensembles soudés
US8858874B2 (en) * 2007-11-23 2014-10-14 Rolls-Royce Plc Ternary nickel eutectic alloy
JP2013181190A (ja) * 2012-02-29 2013-09-12 Seiko Instruments Inc 生体用Ｃｏ基合金およびステント
US9377245B2 (en) 2013-03-15 2016-06-28 Ut-Battelle, Llc Heat exchanger life extension via in-situ reconditioning
US9540714B2 (en) 2013-03-15 2017-01-10 Ut-Battelle, Llc High strength alloys for high temperature service in liquid-salt cooled energy systems
US10017842B2 (en) 2013-08-05 2018-07-10 Ut-Battelle, Llc Creep-resistant, cobalt-containing alloys for high temperature, liquid-salt heat exchanger systems
US9435011B2 (en) 2013-08-08 2016-09-06 Ut-Battelle, Llc Creep-resistant, cobalt-free alloys for high temperature, liquid-salt heat exchanger systems
US9683280B2 (en) 2014-01-10 2017-06-20 Ut-Battelle, Llc Intermediate strength alloys for high temperature service in liquid-salt cooled energy systems
US9683279B2 (en) 2014-05-15 2017-06-20 Ut-Battelle, Llc Intermediate strength alloys for high temperature service in liquid-salt cooled energy systems
US9605565B2 (en) 2014-06-18 2017-03-28 Ut-Battelle, Llc Low-cost Fe—Ni—Cr alloys for high temperature valve applications
CN105238958A (zh) * 2015-10-28 2016-01-13 无棣向上机械设计服务有限公司 镍基高温合金
EP3269472B1 (fr) * 2016-07-13 2022-09-07 Ansaldo Energia IP UK Limited Procédé de production de composants mécaniques
DE102017007106B4 (de) 2017-07-28 2020-03-26 Vdm Metals International Gmbh Hochtemperatur-Nickelbasislegierung
CN113555068B (zh) * 2021-07-13 2024-06-18 北京航空航天大学 一种计算合金化元素在镍基单晶高温合金双相界面附近层浓度的方法
DE102022211589A1 (de) 2022-11-02 2024-05-02 Siemens Energy Global GmbH & Co. KG Kobaltbasislegierung, Pulver, Verfahren und Bauteile

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Also Published As

Publication number Publication date
EP1188845A1 (fr) 2002-03-20
CA2355446A1 (fr) 2002-03-14
CA2355446C (fr) 2011-11-22
DE50107021D1 (de) 2005-09-15
US20020057984A1 (en) 2002-05-16
US6797232B2 (en) 2004-09-28
ATA15622000A (de) 2001-06-15
ATE301730T1 (de) 2005-08-15
AT408665B (de) 2002-02-25

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