EP2247761A1 - Procédé de réalisation d'un acier inoxydable durcissable par précipitation, résistant à la fatigue, à rigidité et à résistance élevées - Google Patents

Procédé de réalisation d'un acier inoxydable durcissable par précipitation, résistant à la fatigue, à rigidité et à résistance élevées

Info

Publication number
EP2247761A1
EP2247761A1 EP09713773A EP09713773A EP2247761A1 EP 2247761 A1 EP2247761 A1 EP 2247761A1 EP 09713773 A EP09713773 A EP 09713773A EP 09713773 A EP09713773 A EP 09713773A EP 2247761 A1 EP2247761 A1 EP 2247761A1
Authority
EP
European Patent Office
Prior art keywords
max
alloy
calcium
inclusions
melting
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.)
Granted
Application number
EP09713773A
Other languages
German (de)
English (en)
Other versions
EP2247761B1 (fr
Inventor
Robert Wayne Krieble
William Joseph Martin
Thomas Constantine Zogas
David Elmer Wert
Paul Michael Novotny
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.)
CRS Holdings LLC
Original Assignee
CRS Holdings LLC
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
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=40637897&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2247761(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by CRS Holdings LLC filed Critical CRS Holdings LLC
Publication of EP2247761A1 publication Critical patent/EP2247761A1/fr
Application granted granted Critical
Publication of EP2247761B1 publication Critical patent/EP2247761B1/fr
Revoked legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/06—Deoxidising, e.g. killing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/064—Dephosphorising; Desulfurising
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/10—Handling in a vacuum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/005—Manufacture of stainless steel

Definitions

  • This invention relates to precipitation-hardenable stainless steel alloys and in particular to a method of making such alloys to reduce the size and distribution of inclusions that adversely affect the fatigue resistance and fracture toughness provided by such alloys.
  • US Patent No. 5,681,528 and US Patent No. 5,855,844 describe high-strength, notch- ductile, precipitation-hardening stainless steels. Those alloys are used for structural applications in the aerospace industry and in many additional non-aerospace uses. Testing of the known alloys by the aerospace industry has indicated that the fatigue life provided by the alloys, while considered to be acceptable, leaves something to be desired. Fatigue life is a very important parameter for the design of aerospace structural members. Improved fatigue life would allow for either product weight savings or longer design service life for structural components. It is desired to provide improved fatigue-strength relative to the known alloys, while still maintaining the excellent combination of strength, toughness, and corrosion resistance that the known alloys provide.
  • the abovementioned fatigue testing has demonstrated that the majority of fatigue failures initiate at large second phase inclusions, which are present in the material as a result of the alloy composition and processing.
  • the alloy according to the present invention is designed to provide strength and toughness that are equivalent to the known alloy, but without the resultant large second phase inclusions that adversely affect the fatigue resistance of the known alloy.
  • the alloy according to this invention is a precipitation hardening Cr-Ni-Ti-- Mo martensitic stainless steel alloy that provides a unique combination of corrosion resistance, fatigue resistance, strength, and toughness.
  • compositional ranges of the precipitation hardening, martensitic stainless steel of the present invention are as follows, in weight percent:
  • the balance of the alloy is essentially iron except for the usual impurities found in commercial grades of such steels and minor amounts of additional elements which may vary from a few thousandths of a percent up to larger amounts that do not objectionably detract from the desired combination of properties provided by this alloy.
  • the alloy according to this invention is further characterized by a plurality of non-strengthening, calcium-based inclusions that are sparsely dispersed in the matrix steel.
  • the method further includes the step of adding calcium to the molten alloy in an amount sufficient to combine with available sulfur and oxygen in the molten alloy to form calcium base inclusions that are removable from said alloy.
  • the method also includes the steps of processing the alloy to remove at least a portion of the inclusions from the alloy and then solidifying the refined alloy, whereby the solidified alloy contains a sparse dispersion of such inclusions in the alloy matrix.
  • the unique combination of strength, notch toughness, and stress-corrosion cracking resistance is achieved by balancing the elements chromium, nickel, titanium, and molybdenum. At least about 10%, better yet at least about 10.5%, and preferably at least about 11.0% chromium is present in the alloy to provide corrosion resistance commensurate with that of a conventional stainless steel under oxidizing conditions. At least about 10.5%, better yet at least about 10.75%, and preferably at least about 10.85% nickel is present in the alloy because it benefits the notch toughness of the alloy. At least about 1.5% titanium is present in the alloy to benefit the strength of the alloy through the precipitation of a nickel-titanium-rich phase during aging.
  • At least about 0.25%, better yet at least about 0.75%, and preferably at least about 0.9% molybdenum is also present in the alloy because it contributes to the alloy's notch toughness. Molybdenum also benefits the alloy's corrosion resistance in reducing media and in environments which promote pitting attack and stress-corrosion cracking.
  • chromium is limited to not more than about 13%, better yet to not more than about 12.5%, and preferably to not more than about 12.0% and nickel is limited to not more than about 11.6% and preferably to not more than about 11.25%.
  • Titanium is restricted to not more than about 1.8% and preferably to not more than about 1.7% and molybdenum is restricted to not more than about 1.5%, better yet to not more than about 1.25%, and preferably to not more than about 1.1%.
  • Sulfur in this alloy tends to combine with manganese and/or titanium to form manganese sulfides (MnS) and/or titanium sulfides (TiS) which adversely affect the fracture toughness, notch toughness, and notch tensile strength of the alloy.
  • MnS manganese sulfides
  • TiS titanium sulfides
  • a product form of this alloy having a large cross-section, i.e., >0.7 in 2 (>4 cm 2 ) does not undergo sufficient thermomechanical processing to homogenize the alloy and neutralize the adverse effect of the sulfide inclusions.
  • a small addition of calcium is preferably made to the alloy to benefit the fatigue strength of the alloy by combining with sulfur to facilitate the removal of sulfur from the alloy.
  • rare earth additions are not used in the present alloy so as to avoid the presence of the rare earth inclusions.
  • Rare earth metals including cerium, lanthanum, yttrium, etc. are restricted such that the combined amounts of such elements are not more than about 0.001%.
  • the alloy contains not more than about 0.0008%, and better yet not more than 0.0007% of such elements.
  • the elimination of the rare earth treatment would have been expected to adversely affect the fracture toughness of the alloy, especially in larger section sizes.
  • the use of the calcium treatment instead of the rare earth treatment not only benefits the fatigue strength of the alloy, but does not adversely affect the combination of toughness and fracture toughness provided by this alloy. Therefore, it is believed that the alloy according to the present invention provides strength and toughness equivalent to the known alloys.
  • Additional elements such as boron, aluminum, niobium, manganese, and silicon may be present in controlled amounts to benefit other desirable properties provided by this alloy. More specifically, up to about 0.010% boron, better yet up to about 0.005% boron, and preferably up to about 0.0035% boron can be present in the alloy to benefit the hot workability of the alloy. In order to provide the desired effect, at least about 0.001% and preferably at least about 0.0015% boron is present in the alloy.
  • Aluminum and/or niobium can be present in the alloy to benefit the yield and ultimate tensile strengths. More particularly, up to about 0.25%, better yet up to about 0.10%, still better up to about 0.050%, and preferably up to about 0.025% aluminum can be present in the alloy. Also, up to about 0.3%, better yet up to about 0.10%, still better up to about 0.050%, and preferably up to about 0.025% niobium can be present in the alloy. Although higher yield and ultimate tensile strengths are obtainable when aluminum and/or niobium are present in this alloy, the increased strength is developed at the expense of notch toughness. Therefore, when optimum notch toughness is desired, aluminum and niobium are restricted to the usual residual levels.
  • Up to about 1.0%, better yet up to about 0.5%, still better up to about 0.25%, and preferably up to about 0.10% manganese and/or up to about 0.75%, better yet up to about 0.5%, still better up to about 0.25%, and preferably up to about 0.10% silicon can be present in the alloy as residuals from scrap sources or deoxidizing additions. Such additions are beneficial when the alloy is not vacuum melted.
  • Manganese and/or silicon are preferably kept at low levels because of their deleterious effects on toughness, corrosion resistance, and the austenite-martensite phase balance in the matrix material.
  • the balance of the alloy is essentially iron apart from the usual impurities found in commercial grades of alloys intended for similar service or use.
  • the levels of such elements are controlled so as not to adversely affect the desired properties.
  • Phosphorus is maintained at a low level because of its deleterious effect on toughness and corrosion resistance. Accordingly, not more than about 0.040%, better yet not more than about 0.015%, and preferably not more than about 0.010% phosphorus is present in the alloy. Not more than about 0.020%, better yet not more than about 0.010%, and preferably not more than about 0.005% sulfur is present in the alloy. Larger amounts of sulfur promote the formation of titanium-rich non-metallic inclusions which, like carbon and nitrogen, inhibit the desired strengthening effect of the titanium and serve as crack-initiation sites that adversely affect the fracture toughness and fatigue resistance provided by the alloy. Also, greater amounts of sulfur deleteriously affect the hot workability and corrosion resistance of this alloy and impair its toughness, particularly in a transverse direction.
  • Oxygen is limited to not more than about 25 parts per million (ppm). Tramp elements such as lead, bismuth, antimony, arsenic, tellurium, selenium, tin, germanium, and gallium are limited to about 0.003% max. each, better yet to not more than about 0.002% each, and preferably to not more than about 0.001% each.
  • the alloy contains not more than about 0.95%, better yet not more than about 0.75%, still better, not more than about 0.50%, and preferably not more than about 0.25% copper.
  • the method according to the present invention is preferably carried out by vacuum induction melting (VIM) the constituent elements as described above.
  • VIM vacuum induction melting
  • VAR vacuum arc remelting
  • the preferred method of providing calcium in this alloy is through the addition of a nickel-calcium compound during VIM.
  • the nickel-calcium compound such as the Ni-Cal® alloy sold by Chemalloy Co. Inc., is added in an amount effective to combine with available phosphorus, sulfur, and oxygen.
  • Other techniques for adding calcium may also be used.
  • capsules of elemental calcium or calcium master alloys can be added to the melt. It is believed that a slag containing calcium or a calcium compound may also be used.
  • any residual calcium-based inclusions are sparsely dispersed in the alloy matrix material upon solidification. It is expected that after VAR the alloy contains less than about 0.001% calcium and not more than about 0.001% sulfur.
  • the inclusions are generally smaller in major cross-sectional size than the rare-earth-based inclusions and Ti-rich non-metallic inclusions that are present in the known alloys. It is also believed that the size distribution of the calcium-based inclusions is about 0.5 ⁇ m to about 3.00 ⁇ m in major cross-sectional dimension, when such inclusions are present.
  • the very small size and sparse dispersion of Ca-based inclusions benefits the strength, toughness, and fatigue resistance provided by the alloy.
  • This alloy can be made using powder metallurgy techniques, if desired. Although the alloy of the present invention can be hot or cold worked, cold working enhances the mechanical strength of the alloy.
  • the precipitation hardening alloy of the present invention is solution annealed and then age hardened to develop the desired high strength and hardness.
  • the solution annealing temperature should be high enough to dissolve essentially all of the undesired precipitates into the alloy matrix material. However, if the solution annealing temperature is too high, it will impair the fracture toughness of the alloy by promoting excessive grain growth.
  • the alloy of the present invention is solution annealed at about 170O 0 F-1900 0 F (927°C-1038°C) for about 1 hour and then quenched.
  • this alloy can also be subjected to a deep chill treatment after it is quenched, to further develop the high strength of the alloy.
  • the deep chill treatment cools the alloy to a temperature sufficiently below the martensite finish temperature to ensure the completion of the martensite transformation.
  • a deep chill treatment consists of cooling the alloy to below about -100 0 F (-73 0 C) for about 1 to 8 hours.
  • the need for a deep chill treatment will be affected, at least in part, by the martensite finish (MF) temperature of the alloy. If the M F temperature is sufficiently high, the transformation to a martensitic structure will proceed without the need for a deep chill treatment.
  • the need for a deep chill treatment may also depend on the cross-sectional size of the piece being manufactured.
  • the length of time that the piece is chilled may need to be increased for large pieces in order to ensure that the transformation to martensite is completed. For example, it has been found that in a piece having a large cross-sectional area as described above, a deep chill treatment lasting about 8 hours is preferred for developing the high strength that is characteristic of this alloy.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Heat Treatment Of Steel (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Powder Metallurgy (AREA)
  • Heat Treatment Of Articles (AREA)

Abstract

L’invention concerne un procédé de réalisation d’un alliage en acier inoxydable durcissable par précipitation. Le procédé comprend l’étape consistant à faire fondre un alliage en acier martensitique ayant la composition suivante en pourcentage en poids : environ 0,03 max. de carbone, 1,0 max de manganèse, 0,75 max. de silicium, 0,040 max de phosphore, 0,020 max de soufre, 10-13 de chrome, 10,5-11,6 de nickel, 1,5-1,8 de titane, 0,25-1,5 de molybdène, 0,95 max de cuivre, 0,25 max de cuivre, 0,25 max d’aluminium, 0,3 max de niobium, 0,010 max de bore, 0,030 max d’azote, le reste étant constitué de fer et d’impuretés habituelles. Le procédé comprend également l’étape consistant à ajouter du calcium à l’alliage pendant qu’il est fondu. Le calcium se combine au soufre et à l’oxygène disponibles pour former des inclusions à base de calcium choisies dans le groupe constitué de sulfures de calcium, d’oxydes de calcium, d’oxysulfures de calcium, et de combinaisons de ceux-ci. Dans une autre étape, l’alliage est traité pour éliminer au moins une partie des inclusions de la base de calcium. L’alliage est ensuite solidifié. Du fait de ce procédé, l’alliage a une matrice contenant une dispersion éparse desdites inclusions à base de calcium et sensiblement aucune inclusion à base de terre rare.
EP09713773A 2008-02-29 2009-02-27 Procédé de réalisation d'un acier inoxydable durcissable par précipitation, résistant à la fatigue, à rigidité et à résistance élevées Revoked EP2247761B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US3259808P 2008-02-29 2008-02-29
PCT/US2009/035548 WO2009108892A1 (fr) 2008-02-29 2009-02-27 Procédé de réalisation d’un acier inoxydable durcissable par précipitation, résistant à la fatigue, à rigidité et à résistance élevées

Publications (2)

Publication Number Publication Date
EP2247761A1 true EP2247761A1 (fr) 2010-11-10
EP2247761B1 EP2247761B1 (fr) 2012-12-19

Family

ID=40637897

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09713773A Revoked EP2247761B1 (fr) 2008-02-29 2009-02-27 Procédé de réalisation d'un acier inoxydable durcissable par précipitation, résistant à la fatigue, à rigidité et à résistance élevées

Country Status (9)

Country Link
US (2) US20090283182A1 (fr)
EP (1) EP2247761B1 (fr)
KR (1) KR20100135242A (fr)
CN (1) CN102016082A (fr)
CA (1) CA2718576C (fr)
ES (1) ES2401753T3 (fr)
IL (1) IL208088A0 (fr)
TW (1) TW201002831A (fr)
WO (1) WO2009108892A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201408782A (zh) * 2012-08-31 2014-03-01 Metal Ind Res & Dev Ct 深冷處理方法及其外殼的製造方法
JP6113456B2 (ja) * 2012-10-17 2017-04-12 三菱日立パワーシステムズ株式会社 析出硬化型マルテンサイト系ステンレス鋼とそれを用いた蒸気タービン長翼
US20140161658A1 (en) * 2012-12-06 2014-06-12 Crs Holdings, Inc. High Strength Precipitation Hardenable Stainless Steel
JP6005234B1 (ja) * 2015-09-29 2016-10-12 日新製鋼株式会社 疲労特性に優れた高強度ステンレス鋼板およびその製造方法
SE539763C2 (en) * 2016-06-16 2017-11-21 Uddeholms Ab Steel suitable for plastic molding tools
WO2021173976A1 (fr) * 2020-02-26 2021-09-02 Crs Holdings, Inc. Acier inoxydable durcissable par précipitation à haute résistance, à ténacité élevée à la fracture
CN114058767B (zh) * 2021-11-15 2022-09-09 东北大学 一种细化超级不锈钢中稀土夹杂物的方法

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Publication number Priority date Publication date Assignee Title
US4043798A (en) * 1974-09-20 1977-08-23 Sumitomo Metal Industries Limited Process for producing steel having improved low temperature impact characteristics
US5855844A (en) * 1995-09-25 1999-01-05 Crs Holdings, Inc. High-strength, notch-ductile precipitation-hardening stainless steel alloy and method of making
US5681528A (en) * 1995-09-25 1997-10-28 Crs Holdings, Inc. High-strength, notch-ductile precipitation-hardening stainless steel alloy
US5866066A (en) * 1996-09-09 1999-02-02 Crs Holdings, Inc. Age hardenable alloy with a unique combination of very high strength and good toughness
US5922148A (en) * 1997-02-25 1999-07-13 Howmet Research Corporation Ultra low sulfur superalloy castings and method of making
DE60202598T2 (de) * 2001-03-27 2006-03-23 CRS Holdings, Inc., Wilmington Ultra-hochfester ausscheidungshärtbarer rostfreier stahl und daraus hergestellter länglicher band

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Title
See references of WO2009108892A1 *

Also Published As

Publication number Publication date
WO2009108892A1 (fr) 2009-09-03
IL208088A0 (en) 2010-12-30
KR20100135242A (ko) 2010-12-24
TW201002831A (en) 2010-01-16
CA2718576C (fr) 2013-02-12
CN102016082A (zh) 2011-04-13
CA2718576A1 (fr) 2009-09-03
ES2401753T3 (es) 2013-04-24
EP2247761B1 (fr) 2012-12-19
US20090283182A1 (en) 2009-11-19
US20120055288A1 (en) 2012-03-08

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