EP2371977B1 - Alliage de cobalt et son procédé de fabrication - Google Patents

Alliage de cobalt et son procédé de fabrication Download PDF

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Publication number
EP2371977B1
EP2371977B1 EP11158754.9A EP11158754A EP2371977B1 EP 2371977 B1 EP2371977 B1 EP 2371977B1 EP 11158754 A EP11158754 A EP 11158754A EP 2371977 B1 EP2371977 B1 EP 2371977B1
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EP
European Patent Office
Prior art keywords
alloy
cobalt
carbides
accordance
weight
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EP11158754.9A
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German (de)
English (en)
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EP2371977A1 (fr
Inventor
Jozef H.G. Mattheij
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.)
Sulzer Turbo Services Venlo BV
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Sulzer Turbo Services Venlo BV
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Priority to EP11158754.9A priority Critical patent/EP2371977B1/fr
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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
    • C22C19/07—Alloys based on nickel or cobalt based on cobalt
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49316—Impeller making
    • Y10T29/49318—Repairing or disassembling

Definitions

  • the invention relates to a cobalt alloy according to the preamble of the independent claim of this category and to a method for producing such a cobalt alloy.
  • Cobalt alloys or cobalt-based alloys, commonly associated with the so-called superalloys, are now commonly used for high temperature applications, and particularly in corrosive environments. They are characterized by a high (warm) strength and also offer a high creep resistance and a good resistance to galling, abrasion and Reibverschleiss in general.
  • cobalt-based alloys are also used for parts of gas turbines that may typically be exposed to temperatures of up to over 1000 ° C under severe oxidizing conditions during operation.
  • One example is the turbine blades, especially those in the hottest part of the turbine.
  • cobalt alloys as a welding or coating material both for the production but also for the repair of turbine blades.
  • cobalt-based alloys contain the following components: In addition to the cobalt element cobalt, nickel is often added, mainly to stabilize the austenitic structure. This refers to the structure that corresponds to the cubic face-centered (fcc: face centered cubic) structure of the Austentit.
  • chromium is added especially for the purpose of improving the corrosion resistance. It is also known to add carbon to the alloy which serves to form carbides which increase strength, hardness and wear resistance. In addition to chromium, other metals such as tungsten, tantalum, hafnium, molybdenum or zirconium are added to form carbides.
  • a directionally solidified cobalt-based alloy in which tantalum carbides are precipitated in a fibrous structure.
  • the tantalum carbides are incorporated as a directed fibrous phase, that is, the individual tantalum carbides are each formed as a longitudinally extended fiber, these fibers are aligned substantially parallel to each other along a preferred direction.
  • alloys that can be used for tools. These alloys consist of 10 to 40% tungsten and / or molybdenum, 0.5 to 4% carbon and at least one reactive metal from the group chromium, vanadium, niobium, tantalum. Silicon or manganese. The remainder of the alloy consists of a mixture of iron and cobalt. The alloys do not contain nickel.
  • the JP-A-09 206986 describes a valve for an engine made of an alloy.
  • the alloy contains chromium, tungsten, silicon, carbon, molybdenum, nickel, niobium and cobalt. No statement is made on the atomic ratio of carbide-forming metal (niobium) to carbon.
  • the CH-A-504 926 describes armor made using alloy welding wires.
  • the alloys include carbon, silicon, manganese, chromium, tungsten, molybdenum, copper, iron, nickel and cobalt. No statement is made on the atomic ratio of carbide-forming metal (niobium) to carbon.
  • a cobalt alloy consisting of at least 30 weight percent cobalt, nickel, namely at most 20 weight percent nickel, 5 to 30 weight percent chromium, 0.4 to 2.5 weight percent carbon and at least one carbide-forming metal that forms carbides with the carbon, wherein the atomic ratio in the Alloy from the carbide-forming metal to which carbon is at least 0.8, said alloy optionally further comprising one or more of molybdenum, tungsten, aluminum, titanium, niobium, iron, silicon, manganese, vanadium, boron, zirconium and impurities.
  • the carbides are present as stable carbides in the form of a finely divided phase without preferential direction in the alloy.
  • this cobalt alloy has a significantly higher high-temperature stability, in particular with regard to the carbides.
  • cobalt-base alloys which are characterized by directional solidification, in which the carbides are precipitated in a directional fiber structure
  • the cobalt alloy according to the invention can be described as an equiaxial alloy.
  • the individual carbides have no significant preferred direction, so they are not fibrous for example, but rather comparable grains.
  • These carbides are fine and distributed substantially uniformly over the cobalt matrix, that is, the carbides form a finely divided phase.
  • a preferred direction as in the directionally solidified cobalt alloys does not exist in the inventive cobalt alloy.
  • the components designated as optional, which may be part of the cobalt alloy according to the invention, are elements which are usually used as additives in superalloys, in particular in cobalt-base alloys.
  • the carbides are at least predominantly of the MC type.
  • the atomic ratio of metal to carbon in the respective carbide is one to one, so each carbon atom is connected to exactly one metal atom to form a carbide.
  • a method for producing such a cobalt alloy is further proposed in which the components of the alloy are transferred by heat input into a melt and then to produce the finely divided carbides a cooling at a cooling rate of at least one degree per second, in particular at least ten degrees per second. This rapid cooling produces the finely divided carbide phase.
  • the desired structure of the carbide phase can be realized, namely the fine distribution of the carbides and the avoidance of a preferred direction as present in the directionally solidified alloys is.
  • the invention proposes a cobalt alloy which contains carbides and which is characterized in particular in that the carbides are in the form of a finely divided phase without preferential direction in the alloy.
  • the carbides do not form fibers aligned along a preferential direction, as in the directionally solidified cobalt alloys, but the individual carbides are formed like grains, their excretion is equiaxial and they are finely dispersed the cobalt matrix.
  • the atomic ratio of the metal M to carbon C in the carbide is one to one.
  • the alloy according to the invention consists of at least 30% by weight (wt.%) Of cobalt (Co) serving as the base material and balancing material of the alloy, at most 20% by weight of nickel (Ni), 5 to 30% by weight of chromium (Cr). , 0.4 to 2.5 wt.% Carbon (C) and at least one carbide-forming metal that forms carbides with the carbon.
  • the atomic ratio of the carbide-forming metal or the carbide-forming metals M and the carbon C is at least 0.8, that is, of the atomic ratio per carbon atom C at least 0.8 metal atom M is present. This ensures, among other things, that predominantly MC type carbides are eliminated.
  • the alloy may further include one or more of the following elements commonly used in cobalt base alloys: molybdenum, tungsten, aluminum, titanium, niobium, iron, silicon, manganese, vanadium, boron, zirconium, and impurities
  • At least the predominant part of the carbides is in each case smaller than five micrometers, preferably smaller or approximately equal to one micrometer.
  • the carbide-forming metal comprises at least one metal selected from the group consisting of tantalum (Ta), hafnium (Hf), zirconium (Zr) and niobium (Nb). Tantalum is particularly preferred.
  • Ta tantalum
  • Hf hafnium
  • Zr zirconium
  • Nb niobium
  • Tantalum is particularly preferred.
  • the fact that some elements, such as zirconium or niobium, are mentioned both as carbide formers and as optional components of the alloy, is to be understood to include a first part that serves as a carbide former and a second part that does not form carbides, but rather a carbide can fulfill other function in the alloy.
  • tantalum as the carbide-forming metal
  • the tantalum it being possible for the tantalum to be replaced completely or partially and at about the atomic ratio one to one by hafnium and / or zirconium.
  • "Atomic ratio one to one" means that a number of tantalum atoms by an equal number of hafnium atoms or an equal number of zirconium atoms, or a the same number of a mixture of hafnium and zirconium atoms can be replaced.
  • the components of the alloy are transferred into a melt by introduction of heat and then rapid cooling takes place to produce the finely divided carbides with a cooling rate of at least one degree per second, in particular at least ten degrees per second.
  • the heat input takes place by laser welding, because in this process the required cooling rate is relatively easy to implement.
  • the cobalt alloy according to the invention and the method according to the invention can be used in particular for welding or coating, in particular by means of laser welding.
  • the starting material for the alloy is provided in the form of a powder mixture.
  • the starting material contains (apart from impurities) 10% by weight of nickel, 20% by weight of chromium, 20% by weight of tantalum, 1.2% by weight of carbon.
  • the rest is cobalt.
  • the tantalum may be wholly or partially replaced at about the atomic ratio one to one by hafnium and / or zirconium.
  • This powder is then applied to a substrate in a laser welding process known per se. With the laser beam, a molten bath is locally generated on the substrate, in which the powder is introduced. During the subsequent cooling, which takes place with at least one degree per second, the cobalt alloy according to the invention then forms with the finely distributed carbide phase.
  • the powder thus serves as a weld filler in a laser welding process.
  • Fig. 1 shows an enlarged view of a layer of the embodiment of an inventive alloy.
  • the lighter spots or points form the carbide phase, which in the Republicsgemäss black or darker matrix is embedded.
  • the individual carbides are formed like grains, their excretion takes place equiaxially, ie without preferential direction, and they are finely and evenly distributed over the cobalt matrix.
  • the majority of the carbides have an extension that is less than or equal to one micrometer.
  • the in Fig. 1 Alloy held at 1000 ° C for a thousand hours.
  • Fig. 1 shows the cobalt alloy after this annealing treatment.
  • the cobalt alloy according to the invention is suitable both as a welding material, for example for the production of welds or for repairing workpieces or for build-up welding, for example for the production of components, as well as a coating material, for example to provide a protective layer against (hot) corrosion or corrosion on a substrate Apply wear.
  • the cobalt alloy according to the invention or the process according to the invention for producing or repairing parts of a gas turbine is particularly suitable for producing and repairing turbine blades.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)

Claims (7)

  1. Alliage de cobalt consistant en au moins 30 % en poids de cobalt, 0 à 20 % en poids de nickel, 5 à 30 % en poids de chrome, 0,4 à 2,5 % en poids de carbone et au moins un métal formant carbure, qui forme un carbure avec le carbone, dans lequel le rapport atomique de l'alliage du métal formant carbure sur le carbone est d'au moins 0,8, dans lequel l'alliage peut contenir des impuretés, et les carbures sont présents dans l'alliage sous la forme d'une phase finement dispersée sans direction privilégiée caractérisé par
    10 % en poids de nickel, 20 % en poids de chrome, 20 % en poids de tantale, comme le métal formant carbure, 1,2 % en poids de carbone et le reste de cobalt, dans lequel le tantale peut être remplacé en totalité ou en partie, et selon un rapport atomique d'un pour un, par de l'hafnium et/ou du zirconium.
  2. Alliage de cobalt selon la revendication 1, dans lequel les carbures sont de manière prépondérante du type MC.
  3. Alliage de cobalt selon l'une quelconque des revendications précédentes, dans lequel au moins la majeure partie des carbures est respectivement inférieure à cinq microns, de préférence inférieure ou égale à un micron.
  4. Procédé de production d'un alliage de cobalt selon l'une quelconque des revendications 1 à 3, dans lequel les composants de l'alliage sont convertis par apport de chaleur en une masse fondue, et un refroidissement intervient ensuite pour produire les carbures finement dispersés, à une vitesse de refroidissement d'au moins un degré par seconde, en particulier d'au moins dix degrés par seconde.
  5. Procédé selon la revendication 4, dans lequel l'apport de chaleur survient par soudage laser.
  6. Utilisation d'un alliage de cobalt selon l'une quelconque des revendications 1 à 3 ou d'un procédé selon l'une quelconque des revendications 4 ou 5, pour souder ou revêtir, en particulier via un soudage laser.
  7. Utilisation d'un alliage de cobalt selon l'une quelconque des revendications 1 à 3 ou d'un procédé selon l'une quelconque des revendications 4 ou 5, pour fabriquer ou réparer des pièces d'une turbine à gaz, en particulier des pales de turbine.
EP11158754.9A 2010-03-19 2011-03-18 Alliage de cobalt et son procédé de fabrication Active EP2371977B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP11158754.9A EP2371977B1 (fr) 2010-03-19 2011-03-18 Alliage de cobalt et son procédé de fabrication

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP10157037 2010-03-19
EP11158754.9A EP2371977B1 (fr) 2010-03-19 2011-03-18 Alliage de cobalt et son procédé de fabrication

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EP2371977A1 EP2371977A1 (fr) 2011-10-05
EP2371977B1 true EP2371977B1 (fr) 2016-03-16

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CN107663605A (zh) * 2016-07-29 2018-02-06 泰州市艾瑞克新型材料有限公司 单晶涡轮叶片锯齿冠阻尼面耐磨涂层及其制备工艺
CN106636761B (zh) * 2016-12-26 2018-06-19 重庆派馨特机电有限公司 一种耐磨搅拌头用激光熔敷合金粉
CN111918976B (zh) * 2019-03-07 2022-05-17 三菱重工业株式会社 钴基合金制造物
CN109898082A (zh) * 2019-04-15 2019-06-18 东南大学 一种铁基非晶纳米晶激光熔覆复合涂层及制备和测试方法
US11155904B2 (en) * 2019-07-11 2021-10-26 L.E. Jones Company Cobalt-rich wear resistant alloy and method of making and use thereof

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FR2239537B1 (fr) * 1973-07-30 1976-11-12 Onera (Off Nat Aerospatiale)
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US4481034A (en) * 1982-05-24 1984-11-06 Massachusetts Institute Of Technology Process for producing high hafnium carbide containing alloys
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SPIEKERMANN P: "LEGIERUNGEN - EIN BESONDERES PATENTRECHTLICHES PROBLEM? - LEGIERUNGSPRUEFUNG IM EUROPAEISCHEN PATENTAMT -", MITTEILUNGEN DER DEUTSCHEN PATENTANWAELTE, HEYMANN, KOLN, DE, 1 January 1993 (1993-01-01), pages 178 - 190, XP000961882, ISSN: 0026-6884 *

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US20110225823A1 (en) 2011-09-22

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