EP2902523B1 - Ferritischer edelstahl - Google Patents

Ferritischer edelstahl Download PDF

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EP2902523B1
EP2902523B1 EP13842192.0A EP13842192A EP2902523B1 EP 2902523 B1 EP2902523 B1 EP 2902523B1 EP 13842192 A EP13842192 A EP 13842192A EP 2902523 B1 EP2902523 B1 EP 2902523B1
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oxidation
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French (fr)
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EP2902523A1 (de
EP2902523A4 (de
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Tetsuyuki Nakamura
Hiroki Ota
Hiroyuki Ogata
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JFE Steel Corp
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JFE Steel Corp
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    • 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
    • C21D6/002—Heat treatment of ferrous alloys containing Cr
    • 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
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • 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
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • 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
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • 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
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • 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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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
    • 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
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • 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
    • C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
    • 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
    • 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
    • C21D2211/005—Ferrite

Definitions

  • the present invention relates to ferritic stainless steel suitable for use in exhaust parts in high-temperature environments, such as exhaust pipes and catalyst cases (also known as converter cases) of automobiles and motorcycles and exhaust ducts of thermal power plants.
  • Exhaust-system components such as exhaust manifolds, exhaust pipes, converter cases, and mufflers used as automobile exhaust parts are required to have a good thermal fatigue property and good oxidation resistance (hereinafter these properties are generally referred to as a "heat resistance property").
  • Nb-Si-containing steel Cr-containing steel such as steel containing Nb and Si (for example, JFE 429EX (15-mass% Cr-0.9 mass% Si-0.4 mass% Nb) (hereinafter referred to as Nb-Si-containing steel)) is often used in usages that require such a heat resistance property.
  • Nb is known to significantly improve heat resistance property.
  • Steel containing Mo or W, that improves the heat resistance property, in addition to Nb for example, SUS444 (18 mass% Cr-2 mass% Mo-0.5 mass% Nb) has also emerged and is used in components that require a higher heat resistance property.
  • Patent Literature 1 discloses a stainless steel sheet, the heat resistance property of which has been increased by adding Ti, Cu, and B.
  • Patent Literatures 2, 3, and 4 each disclose a heat-resistant ferritic stainless steel containing Al.
  • Patent Literature 5 also discloses a ferritic stainless steel containing Al and having good oxidation resistance in the steam addition atmosphere.
  • Patent Literature 6 discloses a ferritic stainless steel having excellent oxidation resistance, secondary working brittleness resistance and weldability.
  • the ferritic stainless steel which has the following chemical composition, C:0.03 % or less, Si:0.5% or less, Mn:1.0% or less, P:0.04 % or less, S:0.01 % or less, Ni:0.6% or less, Cr:15-20%, N:0.03 % or less, Ti: 0.5% or less, B: 0.0005-0.003%, and Al: 1.5-4.0%, remainder being Fe and unavoidable impurities.
  • Patent Literature 1 has a problem in that the required continuous oxidation resistance cannot be obtained due to occurrence of breakaway oxidation in a continuous oxidation test because of addition of Cu.
  • Patent Literatures 2 and 3 have Al added to the steel but have a problem in that they do not consider the thermal fatigue property.
  • the technique described in Patent Literature 4 also has Al added to the steel but has a problem of occasionally failing to achieve required oxidation resistance due to breakaway oxidation in a continuous oxidation test, oxide scale separation in a cyclic oxidation test, and the like.
  • the technique described in Patent Literature 5 also relates to the oxidation resistance in the steam addition atmosphere associated with addition of Al; however, there is a problem in that good cyclic oxidation resistance may not obtained due to spalling of oxide scale occurring during cyclic oxidation.
  • Mo and W are expensive elements and may cause problems such as generating surface defects by deteriorating hot workability, and deteriorating workability.
  • Nb is also an expensive element and increases the recrystallization temperature of the steel, requiring a high annealing temperature. Thus there is a problem of high production cost.
  • Cu also has problems such as a deterioration in oxidation resistance and workability.
  • An object of the present invention is to provide a ferritic stainless steel that has a good thermal fatigue property and good oxidation resistance in the condition that the amounts of Mo, W, and Nb, which are expensive and deteriorate various properties, and Cu, which deteriorates oxidation resistance and workability, are minimized.
  • the inventors have conducted extensive studies on the effects of the Al content and the Ti content on the thermal fatigue property and the effects of the contents of Cr and Ni and the Al/Cr content ratio on the oxidation resistance and found optimum content ranges for Al, Ti, Cr, and Ni.
  • the present invention has been made based on this finding and further investigations and can be summarized as follows:
  • the oxidation resistance means both continuous oxidation resistance and cyclic oxidation resistance.
  • the continuous oxidation resistance is evaluated based on the weight gain by oxidation after the steel has been isothermally held at high temperature.
  • the cyclic oxidation resistance is evaluated based on the weight gain by oxidation after heating and cooling are repeated and presence or absence of spalling of oxide scale.
  • a ferritic stainless steel having a thermal fatigue property and oxidation resistance comparable or superior to Nb-Si-containing steels can be obtained while minimizing the Mo, W, Nb, and Cu contents; thus, the present invention is significantly useful for automotive exhaust parts.
  • % means % by mass.
  • Carbon (C) is an element effective for increasing the strength of steel but a deterioration in toughness and formability is significant at a C content exceeding 0.020%.
  • the C content is to be 0.020% or less.
  • the C content is preferably as low as possible and is preferably 0.015% or less and more preferably 0.010% or less.
  • the C content is 0.001% or more and more preferably 0.003% or more.
  • Si 1.0% or less and 0.5% or more
  • Silicon (Si) is an important element for improving the oxidation resistance. This effect can be obtained at a Si content of 0.1% or more.
  • the Si content is preferably 0.3% or more if higher oxidation resistance is required.
  • the Si content is in the range of 0.5 to 1.0%.
  • Mn 1.0% or less and 0.1% or more
  • Manganese (Mn) is an element that increases the strength of steel and also acts as a deoxidizer. It also has an effect of suppressing separation of oxide scale in the case where Si is added. In order to obtain such effects, the Mn content is 0.1% or more. However, excessive Mn not only significantly increases the oxidizing speed but also tends to form ⁇ phases easily at high temperature and deteriorates the heat resistance property. Accordingly, in the present invention, the Mn content is to be 1.0% or less. The Mn content is preferably in the range of 0.1 to 0.5% and more preferably in the range of 0.15 to 0.4%.
  • Phosphorus (P) is a harmful element that deteriorates the toughness and the P content is preferably as low as possible.
  • the P content is to be 0.040% or less and preferably 0.030% or less.
  • the S content is preferably as low as possible.
  • the S content is to be 0.030% or less, preferably 0.010% or less, and more preferably 0.005% or less.
  • Chromium (Cr) is an important element effective for improving corrosion resistance and oxidation resistance, which are the features of stainless steel. At a Cr content less than 10.0%, sufficient oxidation resistance cannot be obtained. On the other hand, Cr is an element that causes solid solution strengthening of steel at room temperature, hardens the steel, and deteriorates the ductility. When an Al-containing steel such as one according to the present invention contains 16.0% or more of Cr, these undesirable properties become significant and it becomes difficult to work the steel into a complicated shape, for example, an exhaust manifold. Accordingly, the Cr content is to be in the range of 10.0% or more and less than 14.0%. The Cr content is preferably in the range of 12.0 to 14.0%.
  • N Nitrogen
  • the N content is thus to be 0.020% or less.
  • the N content is preferably as low as possible and is preferably 0.015% or less and more preferably 0.012% or less.
  • Al 1.4 to 4.0%, Al%/Cr% ⁇ 0.14
  • Aluminum (Al) is an important element for improving the thermal fatigue property. Aluminum acts as a solid solution strengthening element and significantly improves the thermal fatigue property in a thermal fatigue test particularly in which the maximum temperature exceeds 700°C. This effect is obtained when the Al content is 1.4% or more.
  • Al produces oxide scale mainly composed of dense and stable Al 2 O 3 and thus improves oxidation resistance.
  • the oxide scale is mainly composed of Cr oxides and a sufficient amount of Al 2 O 3 is not produced.
  • the Al content is 1.4% or more and the Cr and Al contents satisfy Al%/Cr% ⁇ 0.14, dense and stable Al 2 O 3 is produced and good oxidation resistance is achieved.
  • Al%/Cr% is less than 0.14, that is, when the ratio of the Cr content is large with respect to the Al content, Cr oxides are formed and inhibit formation of Al 2 O 3 oxide layer and thus good oxidation resistance is not obtained.
  • Al%/Cr% is 0.14 or more, dense and stable Al 2 O 3 oxide layer are preferentially formed rather than Cr oxides and thus good oxide resistance can be obtained. Accordingly, the Al content and the Cr content must satisfy Al%/Cr% ⁇ 0.14
  • Al has an effect of improving a thermal fatigue property and oxidation resistance.
  • the Al content is to be in the range of 1.4 to 4.0%.
  • the Al content is preferably in the range of 1.5% to 3.5% and more preferably in the range of 2.0 to 3.0%.
  • Titanium (Ti) is an important element that fixes C and N and improves corrosion resistance, formability, and weld-zone intergranular corrosion resistance.
  • Ti is an important element that prevents Al, which improves the thermal fatigue property, from precipitating as AlN so that Al can keep function as a solid solution strengthening element.
  • the Ti content needs to be more than 0.15% in order to prevent formation of AlN. At a Ti content less than this, Al combines with N and forms AlN precipitates, the amount of dissolved Al is decreased, and a good thermal fatigue property is no longer obtained.
  • Ti(C,N) precipitates are coarse and do not contribute to strengthening of the steel, but fine precipitates of FeTiP in the grain boundaries strengthen the grain boundaries and improve the thermal fatigue property. Accordingly, the Ti content is to be more than 0.15%.
  • excessive Ti will deteriorate toughness of steel and adhesion of oxide scale (cyclic oxidation resistance) and thus 0.5% is the upper limit. Accordingly, the Ti content is to be in the range of more than 0.18% and 0.5% or less.
  • the Ti content is preferably in the range of 0.18 to 0.4% and more preferably in the range of 0.20 to 0.3%.
  • the Ti content is favorably in the range of 0.18 to 0.40%, and yet more favorably in the range of 0.20 to 0.30%.
  • Nickel (Ni) is an important element in the present invention. Nickel not only improves toughness of the steel but also improves oxidation resistance, in particular, cyclic oxidation resistance, of Ti-containing steel. In order to obtain such effects, the Ni content needs to be 0.05% or more. At a Ni content of less than 0.05%, the cyclic oxidation resistance is insufficient. If the cyclic oxidation resistance is insufficient, oxide scale separates every time the temperature raising and falling and oxidation proceeds, resulting in thickness reduction of the base metal. Moreover, due to spalling of oxide scale, starting points of cracks are formed and thus a good thermal fatigue property is no longer obtained.
  • Ni is an expensive element and is a strong ⁇ -phase forming element; thus, excessive Ni will cause formation of ⁇ phases at high temperatures and deteriorate the oxidation resistance. Accordingly, the upper limit is 0.5%.
  • the Ni content is preferably in the range of 0.05 to 0.50%, more preferably in the range of 0.10 to 0.30%, and yet more preferably in the range of 0.15 to 0.25%.
  • the components described above are basic chemical components of a ferritic stainless steel of the present invention.
  • the balance is Fe and unavoidable impurities.
  • at least one selected from Nb and Cu may be contained as an optional element within the range described below.
  • Nb Niobium
  • the Nb content is preferably 0.01% or more.
  • the Nb content is preferably in the range of 0.01 to 0.15%.
  • the Nb content is more preferably in the range of 0.02 to 0.12% and yet more preferably in the range of 0.05 to 0.10%.
  • Copper (Cu) is an element effective for improving a thermal fatigue property.
  • the Cu content is preferably 0.01% or more.
  • Cu content is preferably in the range of 0.01% or more and less than 0.4%.
  • the Cu content is more preferably in the range of 0.01 to 0.2% and more preferably in the range of 0.01 to 0.1%.
  • the Cu content is favorably in the range of 0.01% or more and less than 0.40%, more favorably in the range of 0.01 to 0.20%, and yet more favorably in the range of 0.01 to 0.10%.
  • At least one selected from Mo and W may be contained as an optional element within the ranges described below.
  • Molybdenum (Mo) is an element that increases the strength of steel by solid solution strengthening and then improves heat resistance.
  • the Mo content is preferably 0.02% or more to obtain this effect.
  • Mo is an expensive element and a Mo content exceeding 0.5% will deteriorate the oxidation resistance of a steel containing 1.4% or more of Al as in the present invention.
  • the Mo content is preferably in the range of 0.02 to 0.5%, more preferably in the range of 0.02 to 0.3%, and yet more preferably in the range of 0.02 to 0.1%.
  • the Mo content is favorably in the range of 0.02 to 0.50%, more favorably in the range of 0.02 to 0.30%, and yet more favorably in the range of 0.02 to 0.10%.
  • Tungsten is an element that improves the strength of steel by solid solution strengthening and then improves the heat resistance property as with Mo.
  • the W content is preferably 0.02% or more.
  • W is also an expensive element as with Mo and, at a W content exceeding 0.3%, oxide scale generated during annealing is stabilized and it becomes difficult to remove scale by pickling after cold-roll annealing.
  • the W content is preferably in the range of 0.02 to 0.3% and more preferably in the range of 0.02 to 0.1%.
  • the W content is favorably in the range of 0.02 to 0.30% and more favorably in the range of 0.02 to 0.10%.
  • At least one selected from REM, Zr, V, and Co may be contained as an optional element within the ranges described below.
  • a rare earth element is an element that improves oxidation resistance and is contained as needed in the present invention.
  • the REM content is preferably 0.001% or more to obtain the effect. However, at a REM content exceeding 0.10%, the steel becomes brittle.
  • the REM content is preferably in the range of 0.001 to 0.10%, more preferably in the range of 0.005 to 0.06%, and yet more preferably in the range of 0.01 to 0.05%.
  • the REM content is favorably in the range of 0.001 to 0.100%, more favorably in the range of 0.005 to 0.060%, and yet more favorably in the range of 0.010 to 0.050%.
  • Zirconium is an element that improves oxidation resistance and is contained in the present invention, if desired.
  • the Zr content is preferably 0.01% or more.
  • Zr intermetallic compounds precipitate and the steel becomes brittle.
  • the Zr content is preferably in the range of 0.01 to 0.5%, more preferably in the range of 0.02 to 0.1%, and yet more preferably in the range of 0.01 to 0.10%.
  • the Zr content is favorably in the range of 0.01 to 0.50% and more favorably in the range of 0.02 to 0.10%.
  • Vanadium (V) is an element that improves oxidation resistance and further is effective for improving high-temperature strength.
  • the V content is preferably 0.01% or more. At a V content exceeding 0.5%, coarse V(C,N) precipitates are formed and toughness is deteriorated. Accordingly, if V is to be contained, the V content is preferably in the range of 0.01 to 0.5%, more preferably in the range of 0.05 to 0.4%, and yet more preferably in the range of 0.10 to 0.25%.
  • the V content is favorably in the range of 0.01 to 0.50% and more favorably in the range of 0.05 to 0.40%.
  • Co Co is an element effective for improving toughness and further improves high-temperature strength.
  • the Co content is preferably 0.01% or more.
  • Co is an expensive element and the effect is saturated at a Co content exceeding 0.5%.
  • the Co content is preferably in the range of 0.01 to 0.5%, more preferably in the range of 0.02 to 0.2%, and yet more preferably in the range of 0.02 to 0.1%.
  • the Co content is favorably in the range of 0.01 to 0.50%, more favorably in the range of 0.02 to 0.20%, and yet more favorably in the range of 0.02 to 0.10%.
  • At least one selected from B, Mg, and Ca may be contained as an optional element within the ranges described below.
  • B Boron
  • the B content is preferably 0.0002% or more.
  • the B content is preferably in the range of 0.0002 to 0.0050%, more preferably in the range of 0.0002 to 0.0030%, and yet more preferably in the range of 0.0002 to 0.0010%.
  • Magnesium (Mg) is an element that improves the equiaxed crystal ratio of a slab and is effective for improving workability and toughness. Magnesium also has an effect of suppressing coarsening of Ti carbonitrides in a steel that contains Ti as in the present invention. In order to obtain this effect, the Mg content is preferably 0.0002% or more. This is because coarsened Ti carbonitrides become starting points for brittle cracking and significantly deteriorates the toughness of the steel. However, at a Mg content exceeding 0.0020%, the surface quality of the steel is degraded.
  • the Mg content is preferably in the range of 0.0002 to 0.0020%, more preferably in the range of 0.0002 to 0.0015%, and yet more preferably in the range of 0.0004 to 0.0010%.
  • Calcium (Ca) is a component effective for preventing clogging of casting nozzles caused by precipitation of Ti-based inclusions that are likely to occur during continuous casting.
  • the Ca content is preferably 0.0005% or more.
  • the Ca content needs to be 0.0030% or less to obtain satisfactory surface quality. Accordingly, if Ca is to be contained, the Ca content is preferably in the range of 0.0005 to 0.0030%, more preferably in the range of 0.0005% to 0.0020%, and yet more preferably in the range of 0.0005% to 0.0015%.
  • any appropriate common method for producing a ferritic stainless steel can be used to produce a stainless steel in the present invention without any limitation.
  • a steel is melted and refined in a known melting furnace such as a converter or an electric furnace and, optionally, subjected to secondary refining such as ladle refining or vacuum refining to prepare a steel having the aforementioned composition according to the present invention; the steel is then formed into a slab by a continuous casting method or an ingoting-slabbing method; and the slab is formed into a cold rolled-annealed sheet through steps of hot rolling, hot rolled sheet annealing, pickling, cold-rolling, finish-annealing, pickling, etc.
  • the cold rolling may be performed once, or two or more times with intermediate annealing performed in between.
  • the steps of cold rolling, finish annealing, and pickling may be repeated.
  • the hot rolled sheet annealing may be omitted.
  • skin-pass rolling may be performed after cold rolling or finish annealing.
  • a more preferable production method involves specifying some of the conditions of performing the hot-rolling step and the cold rolling step.
  • steel making it is preferable to produce a molten steel containing the aforementioned essential components and optional additive components by melting and refining with a converter, an electric furnace, or the like and by performing secondary refining by a vacuum oxygen decarburation method (VOD method) or an argon oxygen decarburization method (AOD method).
  • VOD method vacuum oxygen decarburation method
  • AOD method argon oxygen decarburization method
  • a steel material obtained by continuous casting is, for example, heated to 1000 to 1250°C and hot-rolled into a hot rolled sheet having a desired thickness.
  • the steel material can be worked into a form other than a sheet. If needed, this hot rolled sheet is subjected to batch annealing at 600 to 900°C or continuous annealing at 850°C to 1050°C and pickling, for example, to remove scale and thus a hot rolled sheet product is obtained. If needed, scale may be removed by shot blasting before pickling.
  • the hot rolled-annealed sheet obtained as above is subjected to a cold rolling step to be a cold rolled sheet.
  • cold rolling may be performed two or more times with intermediate annealing in between as needed depending on the factors related to production.
  • the total reduction in the cold rolling step in which cold rolling is performed once or two or more times is to be 60% or more and preferably 70% or more.
  • the cold rolled sheet is then subjected to continuous annealing (finish annealing) at 850 to 1000°C and pickling to obtain a cold rolled-annealed sheet.
  • finish annealing continuous annealing
  • pickling pickling
  • the sheet may be moderately rolled (skin pass rolling or the like) after pickling so as to adjust the shape and quality of the steel sheet.
  • a hot rolled sheet product or a cold rolled-annealed sheet product produced as such is subjected to bending or the like depending on the usage so as to form exhaust pipes and catalyst cases of automobiles and motorcycles, exhaust ducts of thermal power plants, and parts (for example, separators, interconnectors, and reformers) related to fuel cells.
  • the method for welding these parts is not particularly limited.
  • Common arc welding methods such as metal inert gas (MIG), metal active gas (MAG), and tungsten inert gas (TIG) welding methods, resistance welding methods such as spot welding and seam welding, and high-frequency resistance welding and high-frequency inductive welding used in such as an electric welding method can be applied.
  • MIG metal inert gas
  • MAG metal active gas
  • TOG tungsten inert gas
  • the other segment of the sheet bar was heated to 1050°C and hot-rolled into a hot rolled sheet having a thickness of 5 mm. Then annealing is performed in the temperature range of 850 to 1050°C and the scale on the surface was removed by pickling or polishing. At this stage, the presence or absence of the surface normality of the steel sheet was observed visually.
  • the steel sheet was cold-rolled to a thickness of 2 mm and finish-annealed within the temperature range of 850 to 1000°C to be a cold rolled-annealed sheet.
  • a specimen 30 mm in length and 20 mm in width was cut out from the cold rolled-annealed sheet. All six faces of the specimen were polished with a #320 emery paper and the specimen was subjected to a continuous oxidation test and a cyclic oxidation test described below.
  • Fig. 2 shows a thermal fatigue test procedure.
  • a thermal fatigue test specimen was repeatedly heated at a heating rate of 10 °C/s and cooled at a cooling rate of 10 °C/s between 100°C and 850°C and, simultaneously, strain was repeatedly applied to the specimen at a restraint ratio of 0.3 to measure the thermal fatigue lifetime.
  • the holding time at 100°C and 850°C was 2 min each.
  • the thermal fatigue lifetime was determined as follows according to the standard test method for high temperature and low-cycle fatigue testing set forth in Standard of the Society of Materials Science, Japan: , stress was calculated by dividing the load detected at 100°C by the cross-sectional area of the gauged portion of the specimen shown in Fig. 1 , and the number of cycles on which the stress decreased to 75% of the stress on the fifth cycle was defined to be the thermal fatigue lifetime. For comparison, the same testing was performed on a Nb-Si-containing steel (15 mass% Cr-0.9 mass% Si-0.4 mass% Nb).
  • the evaluation standard of the thermal fatigue test was as follows: A specimen with a thermal fatigue lifetime equal to or longer than that of the Nb-Si-containing steel specimen(940 cycles) was evaluated as pass and a specimen with a thermal fatigue life less than 940 cycles was evaluated as fail.
  • the evaluation results are shown in Tables 1-2, 1-4, and 1-6.
  • the oxidation test specimen described above was held for 400 hours in an air atmosphere heated to 1050°C in a furnace, the difference in mass of the specimen between before and after the holding was measured, and the weight gain by oxidation per unit area (g/m 2 ) was calculated. The test was performed twice on each specimen.
  • the evaluation standard of the continuous oxidation test was as follows: A specimen with an weight gain by oxidation of less than 50 g/m 2 after the continuous oxidation test was evaluated as pass and a specimen that underwent an weight gain by oxidation of 50 g/m 2 or more even once was evaluated as fail. The evaluation results are shown in Tables 1-2, 1-4, and 1-6.
  • the oxidation test specimen described above was subjected to 400 cycles of a heat treatment that included repetition of holding at 100°C ⁇ 1 min, heating to 1050°C, holding at 1050°C ⁇ 20 min and cooling to 100°C in air, and then the difference in mass of the specimen between before and after the test was measured.
  • the weight gain by oxidation per unit area (g/m 2 ) was calculated and the absence or presence of scale separating form the specimen surface (spalling of scale) was checked.
  • the heating rate and the cooling rate were 5 °C/sec and 1.5 °C/sec, respectively.
  • Example Nos. 1 to 17 and Example Nos. 31 to 75 of the present invention all had a good thermal fatigue property, good continuous oxidation resistance, and good cyclic oxidation resistance.
  • Hot rolled, annealed, and pickled steel sheets of examples of the present invention had no defects on surfaces and had good surface quality.
  • Comparative Example No. 18 had a low Ti content of 0.14% and thus failed in thermal fatigue property.
  • Comparative Example No. 19 had a low Ni content of 0.02% and failed in cyclic oxidation resistance.
  • Comparative Examples No. 20 and Nos. 76 to 80 had an Al%/Cr% value being lower than 0.14 and thus failed in oxidation resistance (both continuous and cyclic).
  • Comparative Example No. 21 had a low Al content of 0.89% and thus failed in thermal fatigue property (850°C); moreover, Comparative Example No. 21 had a low Al%/Cr% value of 0.07 and thus failed in oxidation resistance (both continuous and cyclic).
  • Comparative Example No. 22 had a high Al content of 4.12% and thus failed in thermal fatigue property.
  • Comparative Example No. 23 had a low Cr content of 9.4% and thus failed in oxidation resistance (both continuous and cyclic).
  • Comparative Example No. 24 had a high Cu content of 1.06% and thus failed in oxidation resistance (both
  • Comparative Example No. 25 had a low Al content and a low Ti content and thus failed in thermal fatigue property. Moreover, since the Cu content was as high as 1.25%, oxidation resistance (both continuous and cyclic) was evaluated as fail and since Ni was not contained, the cyclic oxidation property was evaluated as fail. Comparative Example No. 26 had a low Ti content and thus failed in thermal fatigue property. Comparative Examples No. 27 and No. 28 had a small Al%/Cr% value and thus failed in oxidation resistance (both continuous and cyclic). Comparative Example No. 29 did not contain Ni and thus failed in cyclic oxidation property.
  • a steel according to the present invention is not only suitable for use in exhaust parts of automobiles, etc., but also suitable for use in exhaust parts of thermal power plants and solid oxide-type fuel cell parts that require similar properties.

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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 Sheet Steel (AREA)
  • Heat Treatment Of Steel (AREA)

Claims (1)

  1. Ferritischer rostfreier Stahl, bestehend aus, nach Ma%, C: 0,020 % oder weniger und 0,001 % oder mehr, Si: 1,0 % oder weniger und 0,5 % oder mehr, Mn: 1,0 % oder weniger und 0,1 % oder mehr, P: 0,040 % oder weniger, S: 0,010 % oder weniger, Cr: 10,0 % oder mehr und 14,0 % oder weniger,
    N: 0,020 % oder weniger, AI: 1,4 bis 4,0 %, Ti: 0,18 % oder mehr und 0,5 % oder weniger, Ni: 0,05 bis 0,5 %, optional mindestens einem, das aus Folgendem gewählt wird: Nb 0,01 bis 0,15 %, Cu: 0,01 % oder mehr und weniger als 0,4 %, Mo: 0,02 bis 0,5 %, W: 0,02 bis 0,3 %, REM: 0,001 bis 0,10 %, Zr: 0,01 bis 0,5 %, V: 0,01 bis 0,5 %, Co: 0,01 bis 0,5 %, B: 0,0002 bis 0,0050 %, Mg: 0,0002 bis 0,0020 %, und Ca: 0,0005 bis 0,0030 %, wobei der Rest Fe und unvermeidbare Verunreinigungen sind, wobei der ferritische rostfreie Stahl folgende Formel (1) erfüllt: Al % / Cr % ≥ 0,14
    Figure imgb0003
     wobei Al % und Cr % in der Formel jeweils einen Al-Gehalt bzw. einen Cr-Gehalt (in Ma%) kennzeichnen.
EP13842192.0A 2012-09-25 2013-09-17 Ferritischer edelstahl Active EP2902523B1 (de)

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