EP1626101B1 - Acier austénitique inoxydable à haute teneur en azote - Google Patents

Acier austénitique inoxydable à haute teneur en azote Download PDF

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EP1626101B1
EP1626101B1 EP05107313.8A EP05107313A EP1626101B1 EP 1626101 B1 EP1626101 B1 EP 1626101B1 EP 05107313 A EP05107313 A EP 05107313A EP 1626101 B1 EP1626101 B1 EP 1626101B1
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stainless steel
steel
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EP1626101A1 (fr
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Tetsuya Shimizu
Shuji Hamano
Toshiharu Noda
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Daido Steel Co Ltd
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Daido Steel Co Ltd
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    • 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
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • 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
    • 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
    • C22C38/04—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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium 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
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of 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
    • C22C38/18—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
    • C22C38/52—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
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of 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
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
    • 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
    • C21D6/005—Heat treatment of ferrous alloys containing Mn
    • 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
    • C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
    • C21D8/065—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires of ferrous alloys

Definitions

  • This invention relates to a high-nitrogen austenitic stainless steel.
  • Austenitic stainless steel represented by SUS304, SUS316 and so forth are widely used as a steel excellent in corrosion resistance and workability.
  • SUS316 as an austenitic stainless steel, and SUS329 as a dual-phase stainless steel are generally used.
  • SUS836L also referred to as "super-austenitic stainless steel” having Ni and Mo contents increased therein to a considerable degree.
  • the high-nitrogen austenitic stainless steel is used for versatile applications including air shaft, ball bearing, shaft bush and mold for plastic products, and is also expectant as a biological material as disclosed in Japanese Laid-Open Patent Publication "Tokkaihei" No. 10-183303 .
  • the general austenitic stainless steels contain a considerable amount of Ni, which is possibly causative of Ni allergy problem in the field of biological materials, and is understood as one of an undesirable element to human body, whereas the high-nitrogen austenitic stainless steel, using nitrogen as a major austenitic phase stabilizing element, is successful in getting rid of most part of Ni, and is advantageous in keeping the hardness and corrosion resistance at an equivalent or higher level.
  • the austenitic stainless steel disclosed in Japanese Laid-Open Patent Publication "Tokkaihei" No. 10-183303 is, however, added with a relatively large amount of Mn in order to raise the amount of solubilization of nitrogen (the patent claims a range of Mn content as relatively wide as 2 to 26% by mass, but discloses Mn contents of as relatively high as 11 % by mass and 12% by mass in the embodiments). Adoption of such high Mn composition may result in a degraded corrosion resistance, and also in an insufficient strength.
  • EP-1 229 142 A1 discloses a high-strength, high corrosion-resistant and nonmagnetic stainless steel which is further excellent in strength and corrosion resistance and safe in the living body and also can stand against various corrosive environments.
  • This stainless steel comprises 0.15% by weight or less of C, 1.0% or less of Si, 3.0 to 12.0% of Mn, 0.030% or less of P, 0.50% or less of Ni, 15.0 to 21.0% of Cr, 0.70 to 1.50% of N, 0.020% or less of Al and 0.020% or less of O, and a remainder of Fe and inevitable impurities.
  • Tensile strengths over 1051 MPa can be attained, when at first forged or hot rolled and then solution treated. Further a pitting potential at least 1 V vs SCE can be attained.
  • Publication DE-196 07 828 A1 also discloses an austenitic steel having high strength, good toughness, corrosion resistance, tearing resistance and which is nonmagnetic.
  • the steel comprises, in weight-%, up to 0.1% C, 8-15% Mn, 13-18% Cr, 2.5-6% Mo, 0-5% Ni, 0.55-1.1 % N, and the rest Fe together with inevitable impurities. After hot working with subsequent solution treatment followed by cold working of at least 80% deformation it is attained a yield strength of at least 2500 MPa with an elongation to fracture over 8%.
  • a high-nitrogen austenitic stainless steel of this invention consists of :
  • the high-nitrogen austenitic stainless steel of this invention makes it possible to attain a good balance between the strength and corrosion resistance, by allowing a large amount of N (nitrogen) to solubilize while limiting Ni content, and by optimizing contents of the essential elements which comprise Cr, Mo, N and Mn within ranges specific to this invention.
  • N nitrogen
  • This consequently makes it possible to realize a high-nitrogen austenitic stainless steel superior to conventional one both in the corrosion resistance and strength, despite a low Ni content.
  • Cr functions to distinctively increase N solubility in the molten metal, largely contributes to the corrosion resistance and strength, and also effectively suppresses generation of nitrogen blow holes.
  • a Cr content of less than 25.0% by mass results in only an insufficient N solubility in the molten metal, and this makes it difficult to ensure satisfactory levels of corrosion resistance and strength, and makes the nitrogen blow holes more likely to occur.
  • the Cr content exceeding 35.0% by mass may destabilize the austenitic phase and may fail in keeping non-magnetism of the material due to ferrite-forming nature of Cr. It is also anticipated that ⁇ phase causative of degradation in the toughness and ductility becomes more likely to precipitate. It is therefore preferable to adjust the Cr content within a range from 25.0% by mass to 32.0% by mass, and more preferably from 25.0% by mass to 30.0% by mass.
  • Mo distinctively increases N solubility in the molten metal, but can exhibit a larger effect of improving the corrosion resistance than Cr can only with a smaller amount, and is successful in obtaining an effect of improving the strength through solid solution strengthening.
  • An amount of Mo addition of less than 0.05% by mass results in only a poor effect, whereas the amount of addition exceeding 8.0% by mass induces nitrogen blow holes and destabilizes the austenitic phase, and thereby makes it difficult to keep the non-magnetism. Formation of an embrittled phase degrades the toughness and ductility, and it becomes hazardous during the hot working. This also raises a problem of increasing insoluble Cr nitride during the solution heat treatment, and of considerably degrading the corrosion resistance.
  • the amount of Mo addition is therefore preferably adjusted to 0.05% or more and less than 5.0% by mass, and more preferably to 0.10% by mass or more and less than 2.5% by mass.
  • Mn is an austenite forming element, and contributes to stabilization of the austenitic phase and to lowering of the solid solution temperature of the Cr nitride described later. Also, Mn distinctively increases N solubility in the molten metal, it is effective in improving the strength and suppressing generation of the nitrogen blow holes. It is also effective as a deoxidation element or desulfurizing element.
  • a Mn content of less than 0.2% by mass results in only an insufficient N solubility in the molten metal, and this makes it difficult to ensure a satisfactory level of strength, and tends to cause nitrogen blow holes.
  • the Mn content exceeding 10.0% by mass degrades the corrosion resistance.
  • the Mn content is therefore preferably adjusted within a range from 0.2% by mass to 6.0% by mass, and more preferably from 0.2% by mass to 2.0% by mass, both ends inclusive.
  • Cu is an austenite forming element, and contributes to stabilization of the austenitic phase and to improvement in the corrosion resistance.
  • An amount of Cu addition of less than 0.01% by mass results in only a poor effect, and the addition exceeding 4.0% by mass raises a problem of lowering in the hot workability. This also increases residual amount of insoluble Cr nitride after the solution heat treatment, and undesirably degrades the corrosion resistance.
  • the amount of Cu addition is therefore preferably adjusted within a range from 0.02% by mass to 1.8% by mass, and still preferably from 0.05% by mass to 1.5% by mass, both ends inclusive.
  • N is an interstitial solid solution element into the austenitic phase, and is a basic additive element contributes all of improvement in the strength, stabilization of the austenitic phase, and improvement in the corrosion resistance.
  • the amount of N addition exceeding 1.5% by mass makes the nitrogen blow holes more likely to generate, allows a large amount of insoluble Cr nitride or other transition metal nitrides (e.g., nitrides of Ti, Nb, V and so forth, described later) to remain in the steel after the solution heat treatment, to thereby raise a problem of a considerable degradation in the corrosion resistance.
  • the amount of N addition is therefore preferably adjusted within a range from 0.8% by mass to 1.4% by mass, both ends inclusive.
  • Fe is a major component (i.e., 50% by mass or more) of the steel, and basically composes the residual portion of the steel other than five above-described essential additive elements, optional elements described below, and inevitable impurities.
  • ⁇ is a compositional parameter expressed by: ⁇ ⁇ W Cr + 3.3 ⁇ W Mo + 16 ⁇ W N / W Mn where W Cr is Cr content (% by mass), W Mo is Mo content (% by mass), W N is N content (% by mass) and W Mn is Mn content (% by mass).
  • W Cr Cr content (% by mass)
  • W Mo Mo content (% by mass)
  • W N N content (% by mass)
  • W Mn Mn content (% by mass).
  • the numerator of ⁇ is obtained by quantifying effects of improving the corrosion resistance by Mo and N converted on the basis of Cr equivalent.
  • N, Cr and Mo contribute to improvement in the corrosion resistance, wherein the effect of improving the corrosion resistance by N measures surprisingly 16 times as large as that of Cr. It is finally indispensable to add Mn in order to dramatically increase the amount of N solubility in the austenitic phase, but excessive addition of Mn seems to partially cancel the net improvement in the corrosion resistance ascribable to thus-increased N, because Mn functions to degrade the corrosion resistance.
  • the ⁇ value having a numerator as a result of positive contribution by N, Cr and Mo to the corrosion resistance, and having a denominator as a result of negative contribution by Mn to the corrosion resistance, can be an effective parameter for generally predicting the corrosion resistance of the finally-obtained steel.
  • the present inventors found out, after extensive investigations, that the effect of improving the corrosion resistance could distinctively be optimized, and that it was even possible to ensure a level of corrosion resistance equivalent to, or superior to that of super-austenitic stainless steel SUS836L, by balancing the amounts of addition of N, Cr, Mo and Mn so as to adjust ⁇ to 5 or above.
  • C is an interstitial solid solution element, contributes to improvement in the strength, and is effectively functions, as an austenite forming element, to suppress formation of nitrogen blow holes.
  • the amount of addition thereof exceeding 0.20% by mass lowers the N solubility, decreases Cr content in the austenite phase through formation of Cr carbide, and thereby results in degradation in the corrosion resistance.
  • C is preferably added in an amount of 0.005% by mass or more in view of making the effect of intentional addition thereof distinct.
  • the C content is preferably adjusted within a range from 0.005% by mass to 0.15% by mass, and more preferably from 0.01% by mass to 0.10% by mass, both ends inclusive.
  • Si is an effective deoxidizing element.
  • Al is known as a deoxidizing element stronger than Si in the general steels, but in the high-nitrogen steel, it is causative of formation of AIN which considerably degrades the high-temperature strength, toughness and ductility. It is therefore preferable to use Si, together with the essential element Mn, as the major deoxidizing element.
  • the deoxidizing effect of Si becomes distinct when it is added in an amount of 0.01% by mass or more.
  • the amount of Si addition exceeding 2.0% by mass makes the steel more likely to cause undesirable as crack or something during the hot working, and also degrades the toughness and ductility.
  • the amount of Si addition is therefore more preferably adjusted within a range from 0.01% by mass to 1.0% by mass, and still more preferably from 0.01% by mass to 0.5% by mass, both ends inclusive.
  • P is one of hazardous impurities, and the content exceeding 0.03% by mass results in degradation of the hot workability, and also in degradation of the toughness and ductility due to lowered strength at the grain boundary. It is therefore preferable that P is not contained as possible, and the lower limit thereof is appropriately determined taking the cost balance into account.
  • S is one of hazardous impurities, and the content exceeding 0.05% by mass results in degradation of the hot workability, and also tends to degrade the corrosion resistance due to formation of MnS. It is therefore preferable that S is not contained as possible, and the lower limit thereof is appropriately determined taking the cost balance into account. It is preferably adjusted to 0.01% by mass or less.
  • Ni is intentionally suppressed in this invention in order to reduce the cost and to avoid adverse influences such as Ni allergy when applied to human body. It is therefore preferable that Ni is not contained as possible, but a content to as much as 0.5% by mass is allowable, because an unnecessarily high level of reduction undesirably increases the cost.
  • the Ni content is preferably limited to 0.3% by mass or less, and more preferably to 0.1 % by mass or less.
  • Al is effective as a deoxidizing element, but considerably lowers the corrosion resistance through formation of AIN in the high-nitrogen steel, even under a slight excess of the Al content.
  • the Al content is limited to 0.03% by mass or less, in view of avoiding the nonconformity and of raising the amount of N solubilization into the austenite phase as possible.
  • the Al content is preferably limited to 0.025% by mass or less, and more preferably to 0.020% by mass or less.
  • the O content is limited to 0.020% by mass or less, because an excess content lowers the cleanliness of the steel, and thereby degrades the corrosion resistance.
  • the O content is preferably limited to 0.015% by mass or less, and more preferably 0.010% by mass or less.
  • W not only contributes to improvement in the corrosion resistance, but also to improvement in the strength as a solid solution strengthening element.
  • An amount of addition of less than 0.01% by mass results in only a poor effect, whereas the amount of addition exceeding 1.0% by mass degrades the toughness and ductility due to formation of an embrittled phase, and thereby induces a nonconformity which is hazardous for the hot working. This also increases insoluble Cr nitride during the solution treatment, and thereby considerably lowers the corrosion resistance.
  • the W content is preferably adjusted within a range from 0.05% by mass to 0.9% by mass, and more preferably from 0.1% by mass to 0.8% by mass, both ends inclusive.
  • Co contributes to improvement in the corrosion resistance and strength.
  • An amount of addition of less than 0.01% by mass results in only a poor effect, whereas the amount of addition exceeding 5.0% by mass increases the cost, and undesirably increases insoluble Cr nitride during the solution heat treatment, and thereby considerably lowers the corrosion resistance.
  • the Co content is preferably adjusted within a range from 0.05% by mass to 4.5% by mass, and more preferably from 0.1% by mass to 4.0% by mass, both ends inclusive.
  • either one of, or both of W and Co can be added within the above-specified ranges.
  • All of Ti, Nb, V and Ta can bind with C and N, allow carbides or carbonitrides to precipitate, and thereby contribute to improvement in the strength.
  • the precipitation can suppress growth of the austenitic grain by the pinning effect, and consequently contribute to improvement in the strength and toughness through refinement of the grain.
  • Amounts of addition of these elements of less than 0.01 % by mass result only in poor effects, whereas the amounts of addition exceeding the respective upper limits considerably degrade the corrosion resistance through formation of hazardous oxides or nitrides in the steel, and also undesirably make the strength more likely to degrade through lowering of an effective amount of N solubility.
  • the Ti content is preferably adjusted within a range from 0.02% by mass to 0.4% by mass, and more preferably from 0.03% by mass to 0.3% by mass, both ends inclusive.
  • the Nb content is preferably adjusted within a range from 0.02% by mass to 0.4% by mass, and more preferably from 0.03% by mass to 0.3% by mass, both ends inclusive.
  • the V content is preferably adjusted within a range from 0.02% by mass to 0.9% by mass, and more preferably from 0.03% by mass to 0.8% by mass, both ends inclusive.
  • the Ta content is preferably adjusted within a range from 0.02% by mass to 0.4% by mass, and more preferably from 0.03% by mass to 0.3% by mass, both ends inclusive.
  • (21) B 0.001 % by mass to 0.01 % by mass
  • B is an element effective for improving the strength and hot workability. An amount of addition of less than 0.001% by mass results in only a poor effect, whereas the content exceeding 0.01% by mass adversely affects the hot workability and also degrades the corrosion resistance.
  • the B content is preferably adjusted within a range from 0.001 % by mass to 0.008% by mass, and more preferably from 0.001 % by mass to 0.005% by mass, both ends inclusive.
  • Zr is an additive element effective for improving the strength. An amount of addition of less than 0.01% by mass results in only a limited effect, whereas the amount of addition exceeding 0.50% by mass degrades the toughness and ductility.
  • the Zr content is preferably adjusted within a range from 0.03% by mass to 0.40% by mass, and more preferably from 0.05% by mass to 0.30% by mass, both ends inclusive.
  • Both of Ca and Mg are additive elements effective for improving the hot workability. Excessive addition of the both degrades the corrosion resistance, toughness, ductility and hot workability. They are also effective in view of improving the machinability. Amounts of addition of the both less than 0.001% results in only poor effects, whereas the amounts of addition exceeding 0.01% by mass undesirably degrade the hot workability.
  • Each of the Ca and Mg contents is preferably adjusted within a range from 0.001% by mass to 0.008% by mass, and more preferably from 0.001 % by mass to 0.005% by mass, both ends inclusive.
  • Te and Se are additive elements effective for improving the machinability. Amounts of addition of the both less than the lower limits result in only poor effects, and the amounts of addition exceeding the upper limits undesirably degrade the corrosion resistance, toughness, ductility and hot workability.
  • the Te content is preferably adjusted within a range from 0.01% by mass to 0.04% by mass, both ends inclusive.
  • the Se content is preferably adjusted within a range from 0.02% by mass to 0.18% by mass, and more preferably from 0.05% by mass to 0.15% by mass, both ends inclusive.
  • the high-nitrogen austenitic stainless steel of this invention is preferably subjected to solution treatment at 1,100°C to 1,250°C, both ends inclusive (typically for 0.1 hours to 2 hours, both ends inclusive).
  • solution treatment typically for 0.1 hours to 2 hours, both ends inclusive.
  • the Cr nitride particularly having a diameter (expressed in this patent specification by a diameter of a circle having an area same as that of the projected area of the nitride grain (referred to as circle-converted diameter, hereinafter)) of 2 ⁇ m or larger remaining in the steel was found to largely affect the corrosion resistance.
  • circle-converted diameter hereinafter
  • solution heat treatment carried out within a temperature range from 1,100°C to 1,250°C does not always ensure disappearance of the Cr-base nitride of 2 ⁇ m or larger in diameter, and that the hazardous Cr-base nitride of 2 ⁇ m or larger in diameter can be suppressed to a satisfactory degree, only when an optimum solution heat treatment temperature is selected depending on steel composition within the above-described temperature range, which will be described later in Examples.
  • the steel of this invention can realize a strength of as large as 1,000 MPa on the tensile strength basis, after being subjected to the solution treatment carried out to an extent not causative of observable Cr-base nitride having a diameter of 2 ⁇ m or larger.
  • the high-nitrogen austenitic stainless steel of this invention can be worked so as to produce wire product or sheet product.
  • a more distinct level of strengthening is available by carrying out the area-reducing process at the final stage of the wire making or sheet making by cold wire drawing or cold rolling.
  • Cr-base nitride having a diameter of 2 ⁇ m or larger is observed neither in the section of a wire product 100, shown in FIG. 1 , normal to the axis thereof, nor in the section of a sheet product 150, shown in FIG. 2 , normal to the drawing direction thereof, and it is made possible to obtain the wire product or sheet product as having a mean grain size (in circle-converted diameter) of the austenitic matrix phase of 100 ⁇ m or smaller.
  • a specific attainable level of strength may be 1,500 MPa or more, or may be even 2,000 MPa or more (strengthening up to 2,500 MPa or around, for example, is attainable, with the upper limit value not specifically limited).
  • the finally-obtained grain size of the austenitic matrix phase of the wire product or sheet product is adjustable by working ratio (reduction of area for the wire product, and draft for the sheet product) in cold working which precedes the solution heat treatment.
  • the mean grain size exceeding 100 ⁇ m results in only a limited effect of improvement in the strength, whereas reduction in the mean grain size to as small as 2 ⁇ m or smaller is technically difficult, considering that re-crystallization can proceed to a certain degree during the solution heat treatment within the above-described temperature range.
  • Refinement of the structure may be more distinctive when any one or more of Ti, Nb, V and Ta, all of which being known to be effective in suppressing growth of the grain, are added within the above-described compositional ranges.
  • the high-nitrogen austenitic stainless steel of this invention is successful in achieving both of high corrosion resistance equivalent to that of SUS836L which is a super-austenitic stainless steel, and strength higher than that of SUS329J4L which is a dual-phase stainless steel, after being subjected to solution heat treatment.
  • the steel can realize a strength of as high as 1,500 MPa or more (or even as high as 2,000 MPa or more), when cold-worked in a form of wire product or sheet product after the solution heat treatment.
  • the high-nitrogen austenitic stainless steel of this invention can be processed into various forms of wire product, rod steel, sheet steel, plate product, pipe, forged product and shape steel. Specific applications will be listed below.
  • accessories such as necklace, pierce and ring; watch components such as back lid of wrist watch and band of wrist watch; spectacle components such as frame of a pair of spectacles; metal components for furniture or building interior such as door knob; cutlery and kitchen tools such as spoon, folk and ladle; metal components for home appliances; dental materials such as dental floss, artificial root and orthodontic wire; biological implant materials such as plate, bolt, nut, spring, screw, wire, electrode, artificial bone and artificial joint; and medical tools such as syringe needle, surgical knife, scalpel, saw, forceps and surgical drill.
  • the steel is applicable to general high-strength, high-corrosion-resistant materials, and preferable examples of the applications include bolt, nut, cylinder liner, shaft, hub, connecter, bearing, lathe, rail, gear, pin, screw, roll, turbine blade, mold, die, drill, valve, valve sheet, cutting edge, nozzle, gasket, ring, spring, ocean beach environmental components, industrial furnace components, chemical plant components, oil drilling components, oil refining plant components, waste incinerator components, steam turbine components, gas turbine components, nuclear reactor components (e.g., secondary cooling water piping components for pressurized water reactor), aircraft components, structural components for construction and civil engineering (e.g., bridge components such as bridge pier and suspension bridge components, electric pole and steel tower for power cable), and decorative components.
  • industrial furnace components chemical plant components, oil drilling components, oil refining plant components, waste incinerator components, steam turbine components, gas turbine components, nuclear reactor components (e.g., secondary cooling water piping components for pressurized water reactor), aircraft components, structural components for
  • the steel is also effectively applicable to high-strength, high-corrosion-resistant components which are necessarily non-magnetic, and examples of which include spring, shaft, bearing, lathe, pin, die and rail for precision electronic components; wire used for components for printed board production; mesh; biological implant electrode: MRI component; drug production components; hanger components; linear motor car components; components for semiconductor production apparatus; forceps, bearing; saw; and cutting edge.
  • high-strength, high-corrosion-resistant components which are necessarily non-magnetic, and examples of which include spring, shaft, bearing, lathe, pin, die and rail for precision electronic components; wire used for components for printed board production; mesh; biological implant electrode: MRI component; drug production components; hanger components; linear motor car components; components for semiconductor production apparatus; forceps, bearing; saw; and cutting edge.
  • Example 1 0.04 0.15 0.2 0.01 0.01 0.16 0. 21 30.0 1.00 0.15 0.20 0.008 0.01 0.002 1.38 Reference Example 2 0.03 0.20 1.5 0.02 0.01 0.05 0.20 * 24.0 6.02 1.52 0.46 0.007 0.05 0.003 1.20
  • Example 3 0.10 0.31 1.0 0.02 0.01 0.20 0.01 21.0 1.87 0.006 0.002 1.05
  • Reference Example 4 0.03 0.50 7.0 0.01 0.01 0.51 0.10 * 18.0 4.03 0.26 0.10 0.21 0.006 0.09 0.04 0.002 1.07
  • Example 5 0.02 0.11 9.0 0.02 0.01 0.32 0.30 26.0 2.50 0.98 0.48 0.005 0.06 0.002 1.33
  • Example6 0.03 0.19 2.0 0.02 0.01 0.16 0.20 25.0 1.50 0.34 0.14 0.01 0.006 0.001 1.20
  • Example7 0.05 0.16 3.0 0.01 0.01 1.50 0.08 26.0 2.01 0.13 0.004 0.003 0.
  • Each of steels having chemical compositions listed in Table 1 and Table 2 was melted under a pressurized atmosphere having a nitrogen partial pressure of 50 atm or less during melting in a pressurizable high-frequency induction furnace, and then cast to produce a 50-kg steel ingot.
  • a test piece was cut out from the bottom portion of the steel ingot, and visually observed for presence or absence of nitrogen blow holes.
  • the steel ingot was then homogenized under heating, and hot-forged to thereby produce a 24-mm-diameter round rod.
  • a rod was heated at a varied temperature from 1,100°C to 1,300°C for one hour, and water-cooled so as to accomplish the solution heat treatment.
  • Example 5 the 50-kg steel ingot was homogenized under heating, then hot-forged, and hot-rolled so as to obtain a 12.5-mm-diameter wire product, subjected to solution heat treatment under the condition determined in the above, and cold-drawn with reductions of area of 50% and 70% so as to obtain wire products of 8.8 mm in diameter and 6.8 mm in diameter, respectively.
  • These wire products were also subjected to measurements of tensile strength and mean grain size, similarly to as described in the above.
  • the 50-kg steel ingot was homogenized under heating, then hot-forged, and hot-rolled so as to obtain a 5-mm-thick sheet product, subjected to solution heat treatment under the condition determined in the above, and cold-rolling with drafts of 50% and 70% so as to obtain sheet products of 2.5 mm thick and 1.5 mm thick, respectively.
  • These sheet products were also subjected to measurements of tensile strength and mean grain size, similarly to as described in the above. Results are shown in Table 3 and Table 4.

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Claims (6)

  1. Acier inoxydable austénitique riche en azote se composant de :
    Cr : 25,0 % en masse à 35,0 % en masse ;
    Mo : 0,05 % en masse à 8,0 % en masse ;
    Mn : 0,2 % en masse à 10,0 % en masse ;
    Cu : 0,01 % en masse à 4,0 % en masse ;
    N : 0,8 % en masse à 1,5 % en masse,
    les deux extrémités étant incluses ;
    ayant une teneur en C inférieure ou égale à 0,20 % en masse, une teneur en Si inférieure ou égale à 2,0 % en masse, une teneur en P inférieure ou égale à 0,3 % en masse, une teneur en S inférieure ou égale à 0,05 % en masse, une teneur en Ni inférieure ou égale à 0,5 % en masse, une teneur en Al inférieure ou égale à 0,03 % en masse et une teneur en O inférieure ou égale à 0,020 % en masse ;
    et facultativement comprenant en outre un ou deux de :
    W : 0,01 % en masse à 1,0 % en masse ; et
    Co : 0,01 % en masse à 5,0 % en masse ;
    les deux extrémités étant incluses ;
    et facultativement comprenant en outre au moins un de :
    Ti : 0,01 % en masse à 0,5 % en masse ;
    Nb : 0,01 % en masse à 0,5 % en masse ;
    V : 0,01 % en masse à 1,0 % en masse ;
    Ta : 0,01 % en masse à 0,5 % en masse ;
    les deux extrémités étant incluses ;
    et facultativement comprenant en outre au moins un de :
    B : 0,001 % en masse à 0,01 % en masse ;
    Zr : 0,01 % en masse à 0,50 % en masse ;
    Ca : 0,001 % en masse à 0,01 % en masse ;
    Mg : 0,001 % en masse à 0,01 % en masse ;
    les deux extrémités étant incluses ;
    et facultativement comprenant en outre un ou les deux de :
    Te : 0,005 % en masse à 0,05 % en masse ; et
    Se : 0,01 % en masse à 0,20 % en masse ;
    les deux extrémités étant incluses ;
    et le reste étant Fe et des impuretés inévitables, dans lequel Fe est supérieur ou égal à 50 % en masse ;
    dans lequel les teneurs en Cr, Mo, N et Mn sont ajustées de sorte qu'un paramètre de composition η, exprimé par l'équation η ≡ W Cr + 3 , 3 ⁢ W Mo + 16 ⁢ W N / W Mn
    Figure imgb0005
    où WCr est la teneur en Cr (en % en masse), WMo est la teneur en Mo (en % en masse), WN est la teneur en N (en % en masse) et WMn est la teneur en Mn (en % en masse), ait une valeur supérieure ou égale à 5.
  2. Acier inoxydable austénitique riche en azote tel que défini selon la revendication 1, ledit acier ne comprenant pas de nitrure à base de Cr ayant un diamètre de 2 µm ou plus observé dans la structure sectionnelle après avoir été soumis à un traitement thermique en solution à 1100 °C à 1250 °C, les deux extrémités é tant incluses.
  3. Acier inoxydable austénitique riche en azote tel que défini selon la revendication 2, ledit acier ayant une contrainte de rupture supérieure ou égale à 1000 MPa après avoir été soumis à un traitement thermique en solution.
  4. Acier inoxydable austénitique riche en azote tel que défini selon l'une quelconque des revendications 1 à 2, ledit acier sous la forme d'un produit de type fil ouvré à froid ne comprenant pas de nitrure à base de Cr ayant un diamètre de 2 µm ou plus observé dans la structure sectionnelle de celui-ci qui apparait dans une section normale par rapport à l'axe du produit de type fil, et ayant une taille de grain moyenne de la phase matricielle austénitique inférieure ou égale à 100 µm.
  5. Acier inoxydable austénitique riche en azote tel que défini selon l'une quelconque des revendications 1 à 2, ledit acier sous la forme d'un produit de type fil ouvré à froid ne comprenant pas de nitrure à base de Cr ayant un diamètre de 2 µm ou plus observé dans la structure sectionnelle de celui-ci qui apparait dans une section normale par rapport au sens de tirage du produit de type feuille, et ayant une taille de grain moyenne de la phase matricielle austénitique inférieure ou égale à 100 µm.
  6. Acier inoxydable austénitique riche en azote tel que défini selon la revendication 4 ou 5, ledit acier ayant une contrainte de rupture supérieure ou égale à 1500 MPa.
EP05107313.8A 2004-08-13 2005-08-09 Acier austénitique inoxydable à haute teneur en azote Not-in-force EP1626101B1 (fr)

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