EP2947171A1 - Legierung aus austenitischem edelstahl - Google Patents

Legierung aus austenitischem edelstahl Download PDF

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Publication number
EP2947171A1
EP2947171A1 EP15168453.7A EP15168453A EP2947171A1 EP 2947171 A1 EP2947171 A1 EP 2947171A1 EP 15168453 A EP15168453 A EP 15168453A EP 2947171 A1 EP2947171 A1 EP 2947171A1
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EP
European Patent Office
Prior art keywords
stainless steel
austenitic stainless
steel alloy
alloy composition
exemplary embodiment
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.)
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Application number
EP15168453.7A
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English (en)
French (fr)
Inventor
John H. Magee
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CRS Holdings LLC
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CRS Holdings LLC
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Filing date
Publication date
Application filed by CRS Holdings LLC filed Critical CRS Holdings LLC
Publication of EP2947171A1 publication Critical patent/EP2947171A1/de
Withdrawn legal-status Critical Current

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    • 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
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
    • 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
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • 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
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • 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
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • 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
    • 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
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • 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
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • 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
    • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
    • 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
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/001—Austenite
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D7/00—Modifying the physical properties of iron or steel by deformation
    • C21D7/13—Modifying the physical properties of iron or steel by deformation by hot working
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226—Hot rolling

Definitions

  • This invention relates generally to an alloy and, in particular, to an austenitic stainless steel alloy having very high annealed strength in combination with good corrosion resistance, and capable of being hot worked from cast ingots.
  • Nitrogen (N) containing austenitic stainless steels are known for their high annealed yield strength, and corrosion properties.
  • known nitrogen-containing austenitic stainless steels do not have the annealed yield strength and corrosion resistance needed in many oil-field applications.
  • severe tearing occurs during hot working of a conventional cast ingot of known austenitic stainless steel, especially in very high chromium (Cr) and N alloys.
  • the inventive very high annealed strength, high toughness austenitic stainless steel alloy includes 0.7-1.2 wt % ofN, 10-25 wt % ofNi, 26-34 wt % ofCr, 0.1-1.0 wt % ofNb, 0.1-1.0 wt % of V, and a balance of Fe and incidental impurities.
  • the invention is an austenitic stainless steel alloy having high amounts of Cr and N, as well as an addition of nickel (Ni), niobium (Nb) and vanadium (V), to improve desirable material properties, such as corrosion resistance, annealed yield strength, and tearing resistance.
  • the austenitic stainless steel alloy according to the invention includes a base composition of N, Cr, Ni, Nb, V, as well as carbon (C), molybdenum (Mo), copper (Cu), manganese (Mn), sulfur (S), silicon (Si), boron (B), and a base metal of iron (Fe).
  • the austenitic stainless steel alloy includes a nominal composition having a proportion of.7 to 1.2 wt% ofN, 26 to 34 wt% of Cr, 10 to 25 wt% of Ni, 0.1 to 1.0 wt% Nb, 0.1 to 1.0 wt% of V, and a balance wt % of Fe to complete the composition.
  • the austenitic stainless steel alloy may include a composition having other elements and impurities with a proportion of ⁇ .08 wt % of C, ⁇ 4.0 wt% of Mo, ⁇ 4 wt% of Cu, 2.0 to 10.0 wt% of Mn, ⁇ .01 wt% of S, ⁇ 2 wt% of Si, ⁇ .006 wt% of B, as shown in Table 1.
  • Table 1 Exemplary Austenitic Stainless Steel Alloy Compositions Element Comp. A (wt %) Comp. B (wt %) Comp.
  • the austenitic stainless steel alloy composition may includes about ⁇ .08 wt % C.
  • Carbon is a strong austenite-forming element which prevents ferrite and intermetallic phases. It contributes to high strength and toughness; however, , too much carbon will results in carbides which degrade corrosion resistance. As a result, lower carbon content may be used for intergranular corrosion resistance.
  • the austenitic stainless steel alloy composition includes ⁇ .05 wt % C. In yet another exemplary embodiment of the invention, the austenitic stainless steel alloy composition includes ⁇ .03 wt % C.
  • the austenitic stainless steel alloy composition according to the invention may also include about 0.7 to about 1.2 wt % N. While the presence of N is used to achieve the austenite structure, strength, and chloride corrosion resistance, excessive nitrogen can form stable chromium nitrides that would degrade mechanical and corrosion properties. Accordingly, the N content is limited to 1.2%.
  • the austenitic stainless steel alloy composition may include about 0.75 to about 1.10 wt % N. In yet another exemplary embodiment of the invention, the austenitic stainless steel alloy composition may include about 0.8 to about 1.0 wt % N.
  • the austenitic stainless steel alloy composition according to the invention further includes about 26 to about 34 wt % Cr.
  • Cr increases the chloride corrosion resistance and nitrogen solubility of the composition. Too much Cr can result in stable intermetallic phases causing a negative effect on corrosion, toughness, and hot workability.
  • the austenitic stainless steel alloy composition may include about 28 to about 33 wt % Cr. In yet another exemplary embodiment of the invention , the austenitic stainless steel alloy composition may include about 30 to about 32 wt % Cr.
  • the austenitic stainless steel alloy composition according to the invention further includes about 10 to about 25 wt % Ni. While Ni increases the toughness of the composition and, is a key austenite forming element in a high Cr alloy, too much Ni can negatively affect nitrogen solubility and hot workability.
  • the austenitic stainless steel alloy composition may include about 12 to about 22 wt % Ni.
  • the austenitic stainless steel alloy composition may include about 14 to about 18 wt % Ni.
  • the austenitic stainless steel alloy composition according to the invention includes about ⁇ 4.0 wt % Mo. While Mo provides chloride and hydrogen sulfide corrosion resistance, the presence of Mo can form deleterious intermetallics phases which can affect corrosion, mechanical properties, and hot workability. Accordingly, the Mo content is kept lower. In another exemplary embodiment of the invention, the austenitic stainless steel alloy composition may include about 0.5 to about 3.0 wt % Mo. In another exemplary embodiment of the invention, the austenitic stainless steel alloy composition may include about 0.75 to about 1.50 wt % Mo.
  • the austenitic stainless steel alloy composition according to the invention further includes about 0.1 to about 1.0 wt % Nb.
  • Niobium improves grain refining, retardation of grain growth , and strengthening of the austenitic stainless steel alloy. Too much niobium may degrade toughness and corrosion resistance by the formation of primary carbides or nitrides.
  • the austenitic stainless steel alloy composition may include about 0.1 to about 0.5 wt % Nb.
  • the austenitic stainless steel alloy composition may include about 0.1 to about 0.3 wt % Nb.
  • Nb can be interchanged with columbium(Cb), as well as the aforementioned compositions, since it is recognized that both are the same element.
  • the austenitic stainless steel alloy composition according to the invention further includes about 0.1 to about 1.0 wt % V.
  • Vanadium may be a carbide and nitride former that contributes to the high strength and toughness of the composition, by promoting grain refinement. Too much vanadium may degrade corrosion and toughness by the formation of primary carbides or nitrides.
  • the austenitic stainless steel alloy composition may include about 0.1 to about 0.5 wt % V.
  • the austenitic stainless steel alloy composition may include about 0.1 to about 0.3 wt % V.
  • the austenitic stainless steel alloy composition also includes ⁇ 4 wt % Cu. While Cu enhances austenite formation and improves corrosion resistance, too much Cu can result in poor hot workability.
  • the austenitic stainless steel alloy composition may include ⁇ 3 wt % Cu.
  • the austenitic stainless steel alloy composition includes about 0.5 to about 7.0 wt % Cu.
  • the austenitic stainless steel alloy composition also includes about 2.0 to about 10.0 wt % Mn. Nitrogen solubility, necessary in this alloy, is increased by Mn ;. however, too much Mn can degrade corrosion resistance.
  • the austenitic stainless steel alloy composition may include about 3.0 to about 8.0 wt % Mn. In yet another exemplary embodiment of the invention, the austenitic stainless steel alloy composition includes about 4.0 to about 7.0 wt % Mn..
  • the austenitic stainless steel alloy composition may include ⁇ .01 wt % S from scrap charge, but is restricted to enhance hot workability and corrosion resistance.
  • the austenitic stainless steel alloy composition may include ⁇ .005 wt % S.
  • the austenitic stainless steel alloy composition includes ⁇ .003 wt % S.
  • the austenitic stainless steel alloy composition also includes ⁇ 2 wt % Si. Si may be is added for deoxidation, since low oxygen improves hot workability.. In another exemplary embodiment of the invention, the austenitic stainless steel alloy composition may include ⁇ 1 wt % Si.
  • the austenitic stainless steel alloy composition also includes ⁇ .006 wt % B. B may be added to improve hot workability in fully austenitic stainless steels.
  • the austenitic stainless steel alloy composition may include about .001 to about .005 wt % B.
  • the austenitic stainless steel alloy composition includes .002 to about .004 wt % B.
  • the balance of the austenitic stainless steel alloy composition according to the invention is substantially Fe.
  • the austenitic stainless steel alloy composition may also include additional elements and known impurities common in commercial grades of similar compositions.
  • additional elements and known impurities common in commercial grades of similar compositions.
  • impurities may also be present in trace amounts.
  • the austenitic stainless steel alloy according to invention was prepared using three separate heats (Examples 1-3).
  • Example 1 the austenitic stainless steel alloy composition was prepared with minimal amounts ofNb and V, while Examples 2 and 3 include approximately .2 wt % of Nb and .2 wt % of V to provide greater yield and ultimate tensile strength, an increase in hardness with an increase in grain size number, i.e. finer grain size Corrosion resistance in hydrogen sulfide (H 2 S) and chloride (Cl) environments are similar for all three examples.
  • H 2 S hydrogen sulfide
  • Cl chloride
  • Example 3 material properties of the austenitic stainless steel alloys according to invention were prepared with three separate heats (Examples 1-3).
  • Example 1 the austenitic stainless steel alloy composition was prepared with minimal amounts of Nb and V.
  • Material properties of Example 1 were observed after Example 1 was annealed, and either press forged or hot rolled.
  • Examples 2 and 3 having approximately 0.2 wt % ofNb and 0.2 wt % of V, were also annealed and either press forged or hot rolled.
  • the material properties of Examples 2 and 3 were also observed after being annealed, and either press forged or hot rolled and listed in Table 3.
  • Figure 1 shows a micrograph of the austenitic stainless steel alloy composition of Example 1, where the composition has no amount ofNb and V. The grain size of the austenitic stainless steel alloy composition is observed.
  • Figure 2 which shows a micrograph of the austenitic stainless steel alloy composition of Example 2
  • the grain size is decreased with the addition ofNb and V, regardless of whether the austenitic stainless steel alloy is press forged or hot rolled.
  • Figure 3 shows a micrograph of the austenitic stainless steel alloy composition of Example 3, which includes Cu as well as the addition of Nb and V, and, also shows a decrease in grain size from the austenitic stainless steel alloy composition of Example 1.
  • Nb and V significantly increased the annealed YS to a level higher than any currently available annealed austenitic stainless steel.
  • elements such as Ni, Cu, and Mo can be adjusted in the austenitic stainless steel alloy composition to obtain excellent corrosion resistance in chloride pitting and crevice conditions, as well as hydrogen sulfide environments.
  • ESR electroslag remelting
  • the ESR process offers an austenitic stainless steel ingot to have improved qualities from the electrode by the formation of a solidified thin slag skin between ingot and mold wall during the remelting operation.
  • the electrode is refined to reduce impurities, especially oxygen and sulfur.
  • the ESR process also reduces segregation in the ingot.
  • VAR vacuum arc remelt
  • VAR may degrade the properties by loss ofN content in the electrode.
  • the ingot may be hot worked.
  • the ingot may be press or rotary forged at a temperature of 2000-2300 degrees F to large diameter bar and annealed.
  • large diameter bars cannot be cold rolled due to their large section size and thus, final attained yield strength will be in the annealed condition, especially for optimum corrosion resistance. If hot rolling to smaller sizes then cold rolling can be performed.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
EP15168453.7A 2014-05-20 2015-05-20 Legierung aus austenitischem edelstahl Withdrawn EP2947171A1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US14/282,746 US20150337419A1 (en) 2014-05-20 2014-05-20 Austenitic Stainless Steel Alloy

Publications (1)

Publication Number Publication Date
EP2947171A1 true EP2947171A1 (de) 2015-11-25

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EP15168453.7A Withdrawn EP2947171A1 (de) 2014-05-20 2015-05-20 Legierung aus austenitischem edelstahl

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US (1) US20150337419A1 (de)
EP (1) EP2947171A1 (de)
CA (1) CA2891861A1 (de)
RU (1) RU2015118728A (de)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61227153A (ja) * 1985-03-29 1986-10-09 Sumitomo Metal Ind Ltd 高窒素含有オ−ステナイト系焼結合金およびその製造方法
DE3729577C1 (en) * 1987-09-04 1988-09-01 Thyssen Edelstahlwerke Ag Use of a steel in the construction of tankers for chemicals
JPH046216A (ja) * 1990-04-23 1992-01-10 Nippon Steel Corp 耐海水性に優れ、溶接軟化の少ない高強度オーステナイトステンレス鋼の製造方法
JPH0426740A (ja) * 1990-05-21 1992-01-29 Nippon Stainless Steel Co Ltd 高強度非磁性鋼
US5480609A (en) * 1993-05-28 1996-01-02 Creusot-Loire Industrie Austenitic stainless steel with high resistance to corrosion by chloride and sulphuric media and uses
US5494636A (en) * 1993-01-21 1996-02-27 Creusot-Loire Industrie Austenitic stainless steel having high properties
JPH08134593A (ja) * 1994-11-09 1996-05-28 Sumitomo Metal Ind Ltd 耐海水腐食性と耐硫化水素腐食性に優れた高強度オーステナイト合金
EP2058415A1 (de) * 2007-11-09 2009-05-13 General Electric Company Geschmiedete austenitische Edelstahllegierungskomponenten und Verfahren dafür

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1079582A (en) * 1965-07-28 1967-08-16 Schoeller Bleckmann Stahlwerke Corrosion -resistant steel alloy
DE4110695A1 (de) * 1991-04-03 1992-10-08 Thyssen Schweisstechnik Stahl
CN102471916B (zh) * 2009-07-23 2013-04-24 杰富意钢铁株式会社 耐腐蚀性优良的燃料电池用不锈钢及其制造方法
US9347121B2 (en) * 2011-12-20 2016-05-24 Ati Properties, Inc. High strength, corrosion resistant austenitic alloys

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61227153A (ja) * 1985-03-29 1986-10-09 Sumitomo Metal Ind Ltd 高窒素含有オ−ステナイト系焼結合金およびその製造方法
DE3729577C1 (en) * 1987-09-04 1988-09-01 Thyssen Edelstahlwerke Ag Use of a steel in the construction of tankers for chemicals
JPH046216A (ja) * 1990-04-23 1992-01-10 Nippon Steel Corp 耐海水性に優れ、溶接軟化の少ない高強度オーステナイトステンレス鋼の製造方法
JPH0426740A (ja) * 1990-05-21 1992-01-29 Nippon Stainless Steel Co Ltd 高強度非磁性鋼
US5494636A (en) * 1993-01-21 1996-02-27 Creusot-Loire Industrie Austenitic stainless steel having high properties
US5480609A (en) * 1993-05-28 1996-01-02 Creusot-Loire Industrie Austenitic stainless steel with high resistance to corrosion by chloride and sulphuric media and uses
JPH08134593A (ja) * 1994-11-09 1996-05-28 Sumitomo Metal Ind Ltd 耐海水腐食性と耐硫化水素腐食性に優れた高強度オーステナイト合金
EP2058415A1 (de) * 2007-11-09 2009-05-13 General Electric Company Geschmiedete austenitische Edelstahllegierungskomponenten und Verfahren dafür

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US20150337419A1 (en) 2015-11-26
RU2015118728A (ru) 2016-12-10
CA2891861A1 (en) 2015-11-20

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