EP1602740B1 - Martensitischer rostfreier Stahl - Google Patents

Martensitischer rostfreier Stahl Download PDF

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Publication number
EP1602740B1
EP1602740B1 EP05104370A EP05104370A EP1602740B1 EP 1602740 B1 EP1602740 B1 EP 1602740B1 EP 05104370 A EP05104370 A EP 05104370A EP 05104370 A EP05104370 A EP 05104370A EP 1602740 B1 EP1602740 B1 EP 1602740B1
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amount
addition
stainless steel
toughness
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French (fr)
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EP1602740A1 (de
Inventor
Shuji c/o Daido Tokushuko K.K. Gijutsu K. Hamano
Tetsuya c/o Daido Tokushuko K.K. Gjutsu K Shimizu
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Daido Steel Co Ltd
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Daido Steel Co Ltd
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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
    • C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
    • 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
    • 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
    • C21D9/0093—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for screws; for bolts
    • 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
    • C22C38/40—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
    • C22C38/54—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
    • C22C38/60—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
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/008—Martensite

Definitions

  • This invention relates to a high-hardness martensitic stainless steel excellent in corrosion resistance.
  • Martensitic stainless steel such as SUS420J2 and SUS440C have generally been used in fields in need of certain levels of corrosion resistance, hardness and wear resistance, including cylinder liner, shaft, bearing, gear, pin, bolt, screw, roll, turbine blade, mold, die, valve, valve seat, cutting tool, nozzle, and so on.
  • the martensitic stainless steel which contains a large amount of C in view of ensuring a necessary level of hardness, is inferior to austenitic stainless steel represented by SUS304 and SUS316 in corrosion resistance, and cannot be used under outdoor environments where water drops or aqueous solution may adhere.
  • This is partially solved by providing surface treatment such as plating, but a problem arises in that any scratch or peeling-off of the plated film may allow corrosion to proceed.
  • the martensitic stainless steel is extremely low in the cold workability due to eutectic carbide produced therein.
  • the austenitic stainless steel represented by SUS304 and SUS316 are excellent in the corrosion resistance but far inferior to the martensitic stainless steel in the hardness, showing only a hardness of as small as HRC40 or around after cold working.
  • Publication US-6086686 discloses particularly a martensitic stainless steel containing 0.6% by weight or less of C, 10% to 14% by weight of Cr, 0.1 % to 0,8% by weight of Mn, 0.1% to 1.0% by weight of Si less than 0.2% by weight of N, 0.5% by weight or less of Mo, 0.2% by weight or less of V, and Fe and inevitable components as the balance, wherein the relationship between the content of C and that of Cr satisfies C% ⁇ -0.05 Cr%+1.41.
  • a martensitic stainless steel of this invention consists essentially of, in % by mass, C 0.20-0.50%; Si 0.05% or more and less than 0.20%, Mn 0.05-2.0%, P 0.03% or less; S 0.03% or less; Cu 0.05-3.0%; Ni 0.05-3.0%; Cr 13.0-20.0%; Mo 0.2-4.0%; V 0.01-1.0%; Al: 0.030% or less; Ti less than 0.020%; O 0.020% or less; N 0.30-0.80%; any one or more of steel components which consist of B 0.001-0.01%, Mg 0.001-0.01%, Ca 0.001-0.01 %, and Zr 0.020-0.20%; and further any one or more of steel components which consist of Co 0.05-4.0%, W 0.020-0.20%, Ta 0.020-0.20%, and Nb 0.010-0.20%; and the balance of Fe and inevitable impurities.
  • This invention makes it possible for a martensitic stainless steel to ensure a necessary level of temper hardness, to improve corrosion resistance and cold workability, and to ensure a necessary level of toughness, by further reducing the Si, Al and Ti contents, and by adding V.
  • the following paragraphs will describe reasons for the compositional limitations.
  • C is an interstitial element, and contributes to improvement in the strength, and improvement in the temper hardness through bonding with Cr, Mo, W, V, Nb and Ta, described later. Addition in an amount of 0.15% or more is necessary in view of obtaining these effects. An amount of addition of 0.20% or more is more preferable. On the other hand, any excessive addition lowers amount of solubility of N, and lowers amount of solubility of Cr in the matrix due to formation of Cr carbide, and results in lowering in the oxidation resistance. Formation of coarse primary carbide not only degrades the cold workability and toughness after solution treatment, but also increases amount of residual austenite to thereby degrade the temper hardness. The amount of addition is therefore limited to 0.50% or less, and more preferably 0.45% or less.
  • Si is a deoxidizer element, and is effective for suppressing Al possibly produces AlN which is causative of an extreme lowering in the toughness and ductility.
  • Addition in an amount of 0.05% or more is necessary in view of obtaining these effects, and more preferably 0.08% or more. Whereas, any excessive addition not only adversely affects the forging but also extremely lowers the toughness and ductility, so that the amount of addition is therefore limited to less than 0.20%, and more preferably 0.18% or less.
  • Mn is an element effective for increasing amount of solubility of N, and is also effective as a deoxidizing and desulfurizing element. Addition in an amount of 0.05% or more, and more preferably 0.08% or more, is necessary in view of obtaining these effects. Whereas, any excessive addition not only increases amount of residual austenite to thereby degrade the temper hardness but also degrades corrosion resistance. The amount of addition is therefore limited to 2.0% or less, and more preferably 1.0% or less.
  • P is an element lowers the hot workability, grain boundary strength, toughness and ductility, and is preferably suppressed to a lower level.
  • the amount of addition is limited to 0.03% or less, and more preferably 0.025% or less. It is to be, however, noted that any effort of excessively lowering the content will raise the cost.
  • S is an element degrades the corrosion resistance, toughness and ductility during cold working, and also degrades the hot workability, and is preferably suppressed to a lower level.
  • the amount of addition of S is set to 0.03% or less, and preferably 0.025% or less. It is to be, however, noted that any effort of excessively lowering the content will raise the cost.
  • Cu is an element capable of improving not only the toughness during cold working, but also the corrosion resistance.
  • the addition in an amount of 0.05% or more, and more preferably 0.08% or more, is necessary in view of obtaining these effects. Whereas, any excessive addition increases amount of residual austenite, and this not only results in lowered temper hardness but also in degraded hot workability.
  • the amount of addition is therefore limited to less than 3.0% or less, and more preferably 1.0% or less.
  • Ni is a potent austenite stabilizing element, and is therefore effective for suppressing nitrogen blow. It also contributes to improvements in the corrosion resistance and toughness. Addition in an amount of 0.05% or more, and more preferably 0.08% or more, is necessary in view of obtaining these effects. Whereas, any excessive addition increases the hardness after annealing, to thereby results in degraded cold workability. It extremely lowers not only the corrosion resistance, toughness and ductility due to increase in the insolubilized Cr nitride during hardening, but also lowers the temper hardness due to increase in amount of residual austenite. The amount of addition is therefore limited to 3.0% or less, and more preferably 1.0% or less.
  • Cr is an element capable of increasing amount of solubility of N, and can therefore contribute to increase not only in the strength, but also in the oxidation resistance and corrosion resistance. It also contributes to increase in the hardness through bonding with C and N during tempering. Addition in an amount of 13.0% or more is necessary in view of obtaining these effects. The content is more preferably 13.5% or more, and still more preferably 14.0% or more. Whereas, any excessive addition increases amount of residual austenite and thereby lowers the temper hardness. The amount of addition is therefore limited to 20.0% or less, and more preferably 18.0% or less.
  • Mo increases amount of solubility of N to thereby improve the corrosion resistance, and improves the hardness as a solid solution hardening element. It also contributes to improvement in the hardness through bonding with C and N during tempering. Addition in an amount of 0.2% or more, and more preferably 0.4% or more, is necessary in view of obtaining these effects. Whereas, any excessive addition will make it difficult to ensure an austenitic phase effective for suppressing nitrogen blow, and will also result in degradation of the toughness and ductility due to increase in insolubilized Cr nitride during hardening. The amount of addition is therefore limited to 4.0% or less, and more preferably 3.5% or less.
  • V contributes to refinement of the grains through bonding with C and N, and contributes also to improvement in the toughness as a solute element. Addition in an amount of 0.01% or more, and more preferably 0.02% or more, is necessary in view of obtaining these effects. Whereas, any excessive addition allows large amounts of oxide and nitride to remain in the steel, to thereby degrade the toughness. The amount of addition is therefore limited to 1.0% or less, and more preferably 0.8% or less.
  • Al is an element effective as a deoxidizing element, similarly to Si and Mn. Addition in an amount of 0.001% or more is preferable in view of obtaining the effect.
  • This invention is, however, aimed at increasing amount of solubility of N, and any excessive addition of Al is undesirable because it will extremely degrade the toughness and ductility due to formation of AlN.
  • the amount of addition is therefore necessarily limited to 0.030% or less, and more preferably 0.025% or less in view of securing a desirable level of toughness.
  • Ti allows large amounts of oxide and nitride to remain in the steel, to thereby extremely degrade the corrosion resistance and toughness. Addition in an amount of less than 0.020%, and more preferably 0.018% or less, is necessary in view of ensuring a desirable level of toughness.
  • O is preferably suppressed to a lower level because it allows a large amount of oxide to remain in the steel, to thereby extremely degrade the corrosion resistance and toughness.
  • the amount of addition is therefore limited to 0.020% or less, and more preferably 0.015% or less.
  • N is an interstitial element, and one of most important elements in this invention because it can extremely improve the hardness and corrosion resistance of the martensitic stainless steel, and can further improve the hardness through formation of fine Cr nitride during tempering.
  • Addition in an amount of 0.30% or more, and preferably 0.32% or more, is necessary in view of obtaining these effects. Whereas, any excessive addition induces generation of nitrogen blow, and allows insolubilized Cr nitride to remain during hardening, to thereby extremely degrade the corrosion resistance, toughness and ductility.
  • the amount of addition is therefore limited to 0.80% or less, and more preferably 0.70% or less.
  • the martensitic stainless steel of this invention further contains any one or more of steel components which consist of Co: 0.05-4.0%, W: 0.020-0.20%, Ta: 0.020-0.20%, and Nb: 0.010-0.20%.
  • steel components consist of Co: 0.05-4.0%, W: 0.020-0.20%, Ta: 0.020-0.20%, and Nb: 0.010-0.20%.
  • Co is a potent austenite stabilizing element, and is therefore effective for suppressing nitrogen blow. It also contributes to improvement in the corrosion resistance. It is also effective for ensuring a desirable level of hardness after hardening, because it can raise the Ms point to thereby reduce amount of residual austenite. Addition in an amount of 0.05% or more is preferable, and 0.07% or more is more preferable in view of obtaining these effects. Whereas, any excessive addition not only results in increase in the cost, but also in degradation in the corrosion resistance, toughness and ductility, due to increase in the insolubilized Cr nitride during hardening. It is therefore preferable to limit the amount of addition to 4.0% or less, and more preferably 2.0% or less.
  • W contributes to improvement in the hardness as a solid solution hardening element, or through bonding with C and N during tempering. Addition in an amount of 0.020% or more, and more preferably 0.040% or more, is preferable in view of obtaining the effect. Whereas, any excessive addition may degrade the toughness and ductility. It is therefore preferable to limit the amount of addition to 0.20% or less, and more preferably 0.15% or less.
  • Ta (tantalum): 0.020-0.20%
  • Ta contributes to refinement of the grain through bonding with C and N. Addition in an amount of 0.020% or more, and more preferably 0.040% or more, is preferable in view of obtaining this effect. Whereas, any excessive addition may allow large amounts of oxide and nitride to remain in the steel, similarly to Ti, to thereby degrade the toughness. It is therefore preferable to limit the amount of addition to 0.20% or less, and more preferably 0.15% or less.
  • Nb contributes to refinement of the grain through bonding with C and N. Addition in an amount of 0.010% or more, and more preferably 0.020% or more, is preferable in view of obtaining this effect. Whereas, any excessive addition may allow large amounts of oxide and nitride to remain in the steel, similarly to Ti, to thereby degrade the toughness. It is therefore preferable to limit the amount of addition to 0.20% or less, and more preferably 0.15% or less.
  • the martensitic stainless steel of this invention further contains any one or more of steel components which consist of B: 0.001-0.01%, Mg: 0.001-0.01%, Ca: 0.001-0.01%, and Zr: 0.020-0.20%.
  • B 0.001-0.01%
  • Mg 0.001-0.01%
  • Ca 0.001-0.01%
  • Zr 0.020-0.20%.
  • B contributes to improvement in the toughness, and is also effective for improving the hot workability. Addition in an amount of 0.001% or more is preferable in view of obtaining this effect. Whereas, any excessive addition may adversely affect the hot workability. It is therefore preferable to limit the amount of addition to 0.01% or less, and more preferably 0.008% or less.
  • Mg is effective for improving the hot workability. Addition in an amount of 0.001 % or more is preferable in view of obtaining this effect. Whereas, any excessive addition may adversely affect the hot workability.
  • the amount of addition is preferably limited to 0.01% or less, and more preferably 0.008% or less.
  • Ca is effective for improving the hot workability, and also for improving the machinability. Addition in an amount of 0.001% or more is preferable in view of obtaining these effects. Whereas, any excessive addition may adversely affect the hot workability. It is therefore preferable to limit the amount of addition to 0.01% or less, and more preferably 0.008% or less.
  • Zr contributes to improvement in the toughness. Addition in an amount of 0.020% or more, and more preferably 0.030% or more, is preferable in view of obtaining the effect. Whereas, any excessive addition may adversely affect the toughness and ductility. It is therefore preferable to limit the amount of addition to 0.20% or less, and more preferably 0.15% or less.
  • the martensitic stainless steel of this invention can further contain either of, or both of steel components which consist of Te: 0.005-0.10% and Se: 0.02-0.40%.
  • Te 0.005-0.10%
  • Se 0.02-0.40%.
  • Te contributes to improvement in the machinability. Addition in an amount of 0.005% or more, and more preferably 0.01% or more, is preferable in view of obtaining the effect. Whereas, any excessive addition may adversely affect the toughness and hot workability. It is therefore preferable to limit the amount of addition to 0.10% or less, and more preferably 0.05% or less.
  • Se contributes to improvement in the machinability.
  • Addition in an amount of 0.02% or more, and more preferably 0.05% or more, is preferable in view of obtaining the effect. Whereas, any excessive addition may adversely affect the toughness. It is therefore preferable to limit the amount of addition to 0.40% or less, and more preferably 0.20% or less.
  • the martensitic stainless steel of this invention preferably has a mean grain size of the prior austenitic grain in the tempered martensitic structure of 50 ⁇ m or less, and more preferably 40 ⁇ m or less.
  • the size of the prior austenitic grain affects the toughness. A mean grain size exceeding 50 ⁇ m may result in a degraded toughness.
  • Alloys having chemical compositions listed in Table 1 were melted in a pressurizable high-frequency induction furnace, homogenized under heating, and hot-forged to thereby produce 24-mm diameter round rods.
  • the rods were annealed by heating at a temperature of Ac3+50°C for 4 hours, cooled at a cooling rate of 15°C/h down to 650°C, and then allowed to cool in the air.
  • Test samples were collected after these processes, and subjected to measurements of anneal hardness, and limit compressibility for crack generation by compression test.
  • Hardness of the samples after annealing was measured as Rockwell B-scale hardness using a Rockwell hardness test specified by JIS-Z2245.
  • Limit compressibility for crack generation was measured by a compression test. Compression test pieces were columns of 15 mm in diameter and 22.5 mm in height, and were compressed using a 600-t hydraulic press machine. Ten each test pieces were measured under the individual reduction ratios, and a reduction ratio allowing the number of test pieces causing crack generation to decrease to as small as 5 or less (50% or less) was defined as limit compressibility for crack generation.
  • test pieces were hardened by oil quenching after being kept at 1000 to 1100°C for one hour, subjected to sub-zero treatment in liquid nitrogen, and tempered by being kept at 450°C for one hour and then allowed to cool in the air.
  • Test samples were collected after these processes, and subjected to measurement of hardening-and-temper hardness, salt spray test, measurement of pitting corrosion potential, and Charpy impact test. Mean grain size of the prior austenitic grain was also measured.
  • Hardness of the samples after hardening and tempering was measured as Rockwell C-scale hardness using a Rockwell hardness test specified by JIS-Z2245.
  • test was conducted conforming to a method specified by JIS-Z2371. After the test, the test pieces were evaluated by a four-level rating based on ratios of corroded area, where A: not corroded, B: corroded only in 5% area or less, C: 5-20%, both ends inclusive, and D: over 20%.
  • Ten fields of view of 0.1 mm 2 were randomly observed under an optical microscope (ca. 400x magnification), so as to measure grain sizes of the prior austenitic grain in the tempered martensite structure, and thereby a mean value was determined.
  • Comparative Example 1 Similar test was conducted as Comparative Example 1, using SUS440C, a representative of currently-available material.
  • the SUS440C (Comparative Example 1) was melted in a high-frequency induction furnace, homogenized under heating, and hot-forged to thereby produce a 24-mm diameter round rod.
  • the rods were annealed by being heated at 850°C for 4 hours, cooled at a cooling rate of 15°C/h down to 650°C, and then allowed to cool in the air.
  • the rods were then hardened by oil quenching after being kept at 1050°C for one hour, subjected to sub-zero treatment in liquid nitrogen, and tempered by being kept at 200°C for one hour and then allowed to cool in the air.
  • Comparative Example 13 Similar test was also conducted as Comparative Example 13, using SUS316.
  • the SUS316 (Comparative Example 13) was melted in a high-frequency induction furnace, homogenized under heating, and hot-forged to thereby produce a 24-mm diameter round rod.
  • the rod was then solution-treated by keeping it at 1050°C for one hour and by water quenching. Test samples were collected after these processes, and subjected to the above-described salt spray test and measurement of pitting potential.
  • Variants A to F concern alloys, which have compositions close to the invention. Results of the measurements are shown in Table 2.
  • Inventive Example 4 89 >80 59 A 0.43 18 25 Inventive Example 5 92 >80 58 A 0.49 15 25 Inventive Example 6 91 >80 62 A 0.43 15
  • the martensitic stainless steel of this invention is suitable for use as components in need of certain levels of hardness, wear resistance, corrosion resistance, cold workability and toughness, including cylinder liner, shaft, bearing, gear, pin, bolt, screw, roll, turbine blade, mold, die, valve, valve seat, cutting tool and nozzle.

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Claims (3)

  1. Martensitischer rostfreier Stahl, in Masseprozent bestehend aus:
    0,20 bis 0,50 % C; 0,05 % oder mehr und weniger als 0,20 % Si; 0,05 bis 2,0 % Mn; 0,03 % oder weniger P; 0,03% oder weniger S; 0,05 bis 3,0 % Cu; 0,05 bis 3,0 % Ni; 13,0 bis 20,0 % Cr; 0,2 bis 4,0 % Mo; 0,01 bis 1,0 % V; 0,030 % oder weniger Al; weniger als 0,020 % Ti; 0,020 % oder weniger O; 0,30 bis 0,80 % N; einer oder mehrerer Stahlkomponenten, bestehend aus 0,001 bis 0,01 % B, 0,001 bis 0,01 % Mg, 0,001 bis 0,01 % Ca und 0,020 bis 0,20 % Zr; und weiters einer oder mehrere Stahlkomponenten, bestehend aus 0,05 bis 4,0 % Co, 0,020 bis 0,20 % W, 0,020 bis 0,20 % Ta und 0,010 bis 0,20 % Nb; und der Rest aus Fe und unvermeidbaren Verunreinigungen.
  2. Martensitischer rostfreier Stahl nach Anspruch 1, weiters enthaltend einen oder beide Stahlkomponenten, die aus 0,005 bis 0,10 % Te und 0,02 bis 0,40 % Se bestehen.
  3. Martensitischer rostfreier Stahl nach Anspruch 1 oder 2, der eine durchschnittliche Korngröße des zuvor austenitischen Korns in der getemperten martensitischen Struktur von 50 µm oder weniger aufweist.
EP05104370A 2004-06-04 2005-05-24 Martensitischer rostfreier Stahl Expired - Fee Related EP1602740B1 (de)

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JP4427790B2 (ja) 2010-03-10
US20050271541A1 (en) 2005-12-08

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