EP1956109B1 - Two-phase stainless steel - Google Patents

Two-phase stainless steel Download PDF

Info

Publication number
EP1956109B1
EP1956109B1 EP08001223.0A EP08001223A EP1956109B1 EP 1956109 B1 EP1956109 B1 EP 1956109B1 EP 08001223 A EP08001223 A EP 08001223A EP 1956109 B1 EP1956109 B1 EP 1956109B1
Authority
EP
European Patent Office
Prior art keywords
phase
stainless steel
less
mass
cast article
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP08001223.0A
Other languages
German (de)
French (fr)
Other versions
EP1956109A1 (en
Inventor
Takanobu c/o Yamaha Marine Kabushiki Kaisha Suzuki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yamaha Motor Co Ltd
Original Assignee
Yamaha Motor Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yamaha Motor Co Ltd filed Critical Yamaha Motor Co Ltd
Publication of EP1956109A1 publication Critical patent/EP1956109A1/en
Application granted granted Critical
Publication of EP1956109B1 publication Critical patent/EP1956109B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/001Ferrous alloys, e.g. steel alloys containing N
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/02Ferrous alloys, e.g. steel alloys containing silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/04Ferrous alloys, e.g. steel alloys containing manganese

Definitions

  • the present invention relates to a method to manufacture a cast article of a two-phase stainless steel having a ferrite phase and an austenite phase and also relates to a cast article of the two-phase stainless steel produced by the method.
  • EP-A-0 261 346 discloses a highly pitting residual duplex stainless steel alloy, which comprises, In weight percentage, C: 0.10% and below; Si: 1.5% and below; Mn: 2.0% and below; Cr: 25.0% to 27.0%; Ni: 5.0% to 7.5%; Cu: 1.5% to 3.5%; N: 0.15% and below; Mo: 0.5% and below; and the remaining portion being substantially Fe.
  • a preferred composition of the highly pitting residual duplex stainless steel alloy comprises, In weight percentage, C: 0.02%; Si: 0.5%; Mn: 0.8%; Cr: 25.7%; Ni: 6.0%; Cu: 2.8%; N: 0.07%; Mo: 0.5% max; and the remaining portion being substantially Fe.
  • a two-phase stainless steel having a ferrite phase and an austenite phase is now used as a raw material of various members because of its excellent corrosion resistance.
  • Patent Document 1 proposes a two-phase stainless steel for a large-sized article.
  • the proposed stainless steel is composed of up to 0.02 mass % of C, up to 2.0 mass % of Si, up to 2.0 mass % of Mn, up to 0.04 mass % of P, up to 0.04 mass % of S, 3 to 7 mass % of Ni, 17 to 27 mass % of Cr, 0.5 to 6.0 mass % of Mo, 1 to 5 mass % of Cu, up to 3 mass % of W, 0.05 to 0.3 mass % of N, 0.0005 to 0.0015 mass % of B and the balance being Fe.
  • the contents of individual elements of the proposed stainless steel are optimized to prevent a ⁇ phase, carbides and nitrides from being formed during the fabrication of a thick cast product such as a propeller blade for a large marine vessel because of slow cooling rate, to adversely affect both corrosion resistance and toughness of the product.
  • Patent Document 2 proposes a two-phase stainless steel having high mechanical strength and corrosion resistance against seawater.
  • the disclosed stainless steel is composed of up to 0.06 mass % of C, 1.5 to 3.5 mass % of Si, 0.1 to 3.0 mass % of Mn, 2 to 8 mass % of Ni, 18 to 28 mass % of Cr, 0.1 to 0.9 mass % of Mo, 0.03 to 0.2 mass % of N, and the balance being Fe.
  • the austenite and ferrite phases are formed by using Cr and various other elements. Namely, the inclusion of various elements within respective ranges required is essential in order to form the austenite and ferrite phases within a desired ratio thereof.
  • Mo is also an essential element to improve corrosion resistance, especially corrosion against a reducing environment, of the two-phase stainless steel.
  • Mo is not only expensive but also tends to adversely affect the mechanical property such as toughness of the stainless steel as the content thereof increases.
  • a stainless steel has been hitherto used for a cast article having a thinner portion thereof, such as a propeller blade of a propulsion unit for small watercrafts.
  • a melt poured into a mold is liable to be cooled at the thinner potion forming section of the mold and its fluidity is therefore apt to be reduced there.
  • the melt cannot flow sufficiently into the thinner portion forming section. This is likely to cause defects, such as incomplete filling, in the cast product.
  • the pouring temperature is increased to ensure a sufficient difference from the melting point for prevention of occurrence of the incomplete filling, then the temperature of the melt introduced into the mold will be also increased correspondingly, resulting in application of a great thermal load to the mold and generation of a gas during casting operation.
  • the use of such a high temperature melt is therefore disadvantageous.
  • said object is solved by a cast article of a two-phase stainless steel having the features of independent claim 1. Moreover said object is also solved by a method to manufacture a cast article cast article according to claim 3.
  • a cast article in the form of a propeller blade for a propulsion unit of a small watercraft wherein the cast article comprises a two-phase stainless steel having a ferrite phase and an austenite phase containing specific contents of C, Si, Mn, Ni, Cr, Cu, N and Fe, and unavoidable impurities, and having an area ratio of the ferrite phase in a range between 20% and 60%.
  • a cast article of a two-phase stainless steel capable of providing a wide temperature range over which the melt thereof has a suitable fluidity without increasing the pouring temperature and, therefore, capable of easily affording a cast article having a thinner portion.
  • the specific contents in mass % are: up to 0.08 % of C, not less than 0.5 % but not more than 1.5 % of Si, up to 1.0 % of Mn, not less than 4.0 % but not more than 8.0 % of Ni, not less than 23 % but not more than 27 % of Cr, not less than 2.0 % but not more than 6.0 % of Cu, not less than 0.05 % but not more than 0.3 % of N, and the balance being Fe and unavoidable impurities.
  • the two-phase stainless steel has a melting point of not higher than 1,450°C, and being used as a casting material of a cast article comprising a portion having a thickness of 3mm or less.
  • a method to manufacture a cast article in the form of a propeller blade for a propulsion unit of a small watercraft wherein the cast article comprises a two-phase stainless steel having a ferrite phase and an austenite phase, by preparing a melt including specific contents of C, Si, Mn, Ni, Cr, Cu, N and Fe, and substantially free of Mo addition, and adjusting an area ratio of the ferrite phase in a range between 20% and 60%.
  • the melt is prepared with the specific contents in mass %: up to 0.08 % of C, not less than 0.5 % but not more than 1.5 % of Si, up to 1.0 % of Mn, not less than 4.0 % but not more than 8.0 % of Ni, not less than 23 % but not more than 27 % of Cr, not less than 2.0 % but not more than 6.0 % of Cu, not less than 0.05 % but not more than 0.3 % of N, and the balance being Fe and unavoidable impurities.
  • FIG. 1 shows a propeller, as a cast article of an embodiment, for a propulsion unit of a small watercraft.
  • Reference numeral 10 denotes a propeller formed of a certain two-phase stainless steel.
  • the propeller has a central base section 11 and a pair of blades 12 extending in radial, opposite directions from the base section 11, which are formed in one body.
  • Each blade 12 includes its wide surface portion preferably having a thickness of 3 mm or less, more preferably 2 mm or less.
  • the propeller 10 is formed using a casting mold including two hollow potions, one for forming the central base portion 11 and the others for forming casting blades 12. The two hollow portions are in communication with each other.
  • the melt to be poured into the casting mold includes constituent elements whose amounts are selected to obtain a specified two-phase stainless steel of the propeller formed.
  • the propeller 10 is formed by pouring the melt into the casting mold at a pouring temperature of for example 1,550 to 1,650°C and then leaving as it is for heat release.
  • the two-phase stainless steel as a material configuring such propeller 10 comprises C, Si, Mn, Ni, Cr, Cu, N and the balance.
  • the balance includes Fe and unavoidable impurities.
  • the stainless steel is substantially free of expensive Mo.
  • the two-phase stainless steel has a ferrite phase and an austenite phase and a reduced melting point.
  • the balance of the two-phase stainless steel is Fe and unavoidable impurities such as P and S.
  • impurities may possibly include Mo.
  • the amount of impurity Mo is not more than 0.3 mass %, it may be further removed, or may be used as it is without removal, because the Mo content, which is an unavoidable impurity, is very small.
  • the contents of the components described above are selected within the respective ranges thereof to adjust the area ratio of the ferrite phase and the austenite phase.
  • the area ratio of the ferrite phase should be not less than 20 % but not more than 60 % in order for the stainless steel to exhibit well balanced corrosion resistance, particularly pitting corrosion resistance and mechanical strength.
  • the area ratio of the ferrite phase varies depending on cooling rate and the like production conditions, but may be suitably controlled by adjustment of mixing proportions of the elements of the two-phase stainless steel in terms of the Cr equivalent (ferrite forming elements) and Ni equivalent (austenite forming elements) which may be expressed by the following formulas (1) and (2), for example:
  • FIG. 2 shows a schematic phase diagram which gives the area ratio of the ferrite phase as a function of the nickel equivalent vs. the chromium equivalent.
  • the proportion of constituent elements is adjusted so that the Cr equivalent and Ni equivalent fall within the region S where the area ratio of the ferrite phase is not less than 20 % but not more than 60 %. Because the strength is apt to be reduced due to excessive small area ratio of the ferrite phase, wile the corrosion resistance is apt to be deteriorated due to excessive large area ratio of the ferrite phase.
  • the area ratios of the ferrite phase and the austenite ratios are adjusted in such a manner described above and the contents of the component elements also described above are adjusted so that the melting point of the two-phase stainless steel of the embodiment is adjusted preferably to a 1,450°C or lower, more preferably 1,430°C or lower.
  • the melting point is preferable to be low as far as possible. Because, if it is determined to be excessively high then the temperature of the melt must be determined to be higher. The fluidity of the melt would be otherwise apt to be reduced, causing difficulty of forming the thin portion.
  • the two-phase stainless steel described above contains specific content of C, Si, Mn, Ni, Cr, Cu, N and Fe, and unavoidable impurities; has the ferrite phase and the austenite phase; and has an area ratio of the ferrite phase in a range between 20% and 60%. Therefore, the two-phase stainless steel of the present teaching can show well-balanced mechanical strength and corrosion resistance even though Mo is not added thereto.
  • a two-phase stainless steel can be provided which is inexpensive and durable in practical use with a less number of kinds of component elements.
  • this two-phase stainless steel has a melting point of 1450°C or less, a wider range of the temperature in which the melt can flow is easily secured without a higher pouring temperature being determined.
  • the thermal load applied to the casting mold is therefore not increased and the fluidity of the melt is improved.
  • molding defects hardly occur in the blades 12 even though the blades 12 have a thin portion of 3mm or less thick.
  • the propeller 10 of such two-phase stainless steel can be fabricated inexpensively because of less kinds of component elements and has a well fluidity of the melt thereof for avoiding casting defects of the blades 12, resulting in easy production thereof.
  • a mechanical strength and a corrosion resistance sufficient to resist against stresses generated and applied corresponding to a propulsive force in normal temperature water and seawater can be secured.
  • Stainless steels containing components shown in Table 1 and the balance containing Fe and unavoidable impurities were prepared and determined for their liquid phase line temperatures (as melting points) and area ratios of the ferrite phase ( ⁇ phase) and austenite phase ( ⁇ phase) by actual measurement and by simulation.
  • Example 6 and Comparative Example 1 were tested for tensile test and impact test for test pieces thereof as follows.
  • the substantially Mo-free two-phase stainless steel of Example 6 has equal or higher tensile strength and impact strength as compared with the Mo-containing stainless steel of Comparative Example 1.
  • propellers as shown in FIG. 1 were prepared by casting.
  • the minimum thickness of the blades 12 of the propeller 10 was 1.6 mm.
  • the propellers 10 made of the stainless steels of Example 6 and Comparative Example 1 were each subjected to a corrosion test.
  • aqueous brine solution spray test as the corrosion test was carried out under conditions in accordance with JIS Z 2371. Thus a 5 % by weight aqueous brine solution having its temperature of 35°C was sprayed over the test piece. The test piece was then allowed to stand for 4 days to check rust formation with naked eyes.
  • Example 6 No rust was observed on surfaces of the test pieces of Example 6 and Comparative Example 1. Thus, it was revealed that the stainless steel of Example 6 has corrosion resistance similar to the stainless steel Comparative Example 1.
  • a two-phase stainless steel comprising, in mass %: up to 0.08 % of C, not less than 0.5 % but not more than 1.5 % of Si, up to 1.0 % of Mn, not less than 4.0 % but not more than 8.0 % of Ni, not less than 23 % but not more than 27 % of Cr, not less than 2.0 % but not more than 6.0 % of Cu, not less than 0.05 % but not more than 0.3 % of N, and the balance being Fe and unavoidable impurities, and comprising a ferrite phase and an austenite phase with an area ratio of the ferrite phase being not less than 20 % but not more than 60 % (second aspect).
  • a two-phase stainless steel having a melting point of not higher than 1,450°C, and being used as a casting material of a cast article comprising a portion having a thickness of 3mm or less (third aspect).
  • a cast article of a two-phase stainless steel comprising the two-phase stainless steel according to any one of the first to third aspects (fourth aspect).
  • a cast article in the form of a propeller blade for a propulsion unit of a small watercraft comprising the two-phase stainless steel according to the third aspect (fifth aspect).
  • a two-phase stainless steel of the first aspect comprising Fe as a major component and further containing C, Si, Mn, Ni, Cr, Cu, N and unavoidable impurities, and comprising a ferrite phase and an austenite phase with an area ratio of the ferrite phase being not less than 20 % but not more than 60 %.
  • a two-phase stainless steel of the second aspect comprising, in mass %: up to 0.08 % of C, not less than 0.5 % but not more than 1.5 % of Si, up to 1.0 % of Mn, not less than 4.0 % but not more than 8.0 % of Ni, not less than 23 % but not more than 27 % of Cr, not less than 2.0 % but not more than 6.0 % of Cu, not less than 0.05 % but not more than 0.3 % of N, and the balance being Fe and unavoidable impurities, and comprising a ferrite phase and an austenite phase with an area ratio of the ferrite phase being not less than 20 % but not more than 60 %.
  • a two-phase stainless steel of the third aspect having a melting point of not higher than 1,450°C, and being used as a casting material of a cast article comprising a portion having a thickness of 3mm or less.
  • a cast article of a two-phase stainless steel of the fourth aspect comprising the two-phase stainless steel according to any one of the first to third aspects.
  • a cast article in the form of a propeller blade for a propulsion unit of a small watercraft of the fifth aspect comprising the two-phase stainless steel according to the third aspect.
  • the two-phase stainless steel according to the first or second aspect contains Fe as a major component, and C, Si, Mn, Ni, Cr, Cu, N and unavoidable impurities; has the ferrite phase and the austenite phase; and has an area ratio of the ferrite phase in a range between 20% and 60% that is obtained by adjustment of contents of the component elements. Therefore, the two-phase stainless steel of the present teaching can show well-balanced mechanical strength and corrosion resistance even though Mo is not added thereto.
  • a two-phase stainless steel can be provided which is inexpensive and durable in practical use with a less number of kinds of component elements.
  • the two-phase stainless steel according to the third aspect having a melting point of 1450°C or less is used as a material of cast article including a thin portion having a thickness of 3 mm or less, a wider range of the temperature in which the melt can flow is easily secured without a higher pouring temperature being determined.
  • the thermal load applied to the casting mold is therefore not increased and the fluidity of the melt is improved.
  • molding defects hardly occur in the blades 12 even though the blades 12 have a thin portion of 3mm or less thick.
  • the two-phase stainless cast article of the fourth aspect comprises the substantially Mo-free, 2-phase stainless steel according to claim 1 or 2, it is given corrosion resistance and mechanical strength enough to be used in contact with water and seawater.
  • the two-phase stainless steel cast article of the fifth aspect is directed to a propeller having blades and made of two-phase stainless steel according to the first or second aspect, for a propulsion unit of a small watercraft, the blades having widely extending thin portions.
  • the propeller 10 of such two-phase stainless steel can be fabricated with well fluidity of the melt thereof for avoiding casting defects of the blades 12, resulting in easy production.
  • a mechanical strength and a corrosion resistance enough to resist against stresses generated and applied corresponding to a propulsive force in water and seawater of normal temperature can be secured. Accordingly, a propeller can be provided, which is easily fabricated and given corrosion resistance and mechanical strength enough to be used in practical use.
  • the description in particular discloses, in order to provide an inexpensive, substantially Mo-free, ferrite-austenite two-phase stainless steel having satisfactory mechanical strength and corrosion resistance in practical use, an embodiment of the stainless steel which has a ferrite phase area ratio of 20 to 60 % and a composition containing, in mass %, not more than 0.08 % of C, 0. 5 to 1.5 % of Si, not more than 1.0 % of Mn, 4.0 to 8.0 % of Ni, 23 to 27 % of Cr, 2.0 to 6.0 % of Cu, 0.05 to 0.3 % of N, and the balance being Fe and unavoidable impurities.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Continuous Casting (AREA)

Description

  • The present invention relates to a method to manufacture a cast article of a two-phase stainless steel having a ferrite phase and an austenite phase and also relates to a cast article of the two-phase stainless steel produced by the method.
  • The document EP-A-0 261 346 discloses a highly pitting residual duplex stainless steel alloy, which comprises, In weight percentage, C: 0.10% and below; Si: 1.5% and below; Mn: 2.0% and below; Cr: 25.0% to 27.0%; Ni: 5.0% to 7.5%; Cu: 1.5% to 3.5%; N: 0.15% and below; Mo: 0.5% and below; and the remaining portion being substantially Fe. According to EP-A-0 261 345 a preferred composition of the highly pitting residual duplex stainless steel alloy comprises, In weight percentage, C: 0.02%; Si: 0.5%; Mn: 0.8%; Cr: 25.7%; Ni: 6.0%; Cu: 2.8%; N: 0.07%; Mo: 0.5% max; and the remaining portion being substantially Fe.
  • A two-phase stainless steel having a ferrite phase and an austenite phase is now used as a raw material of various members because of its excellent corrosion resistance.
  • Patent Document 1 as specified later proposes a two-phase stainless steel for a large-sized article. The proposed stainless steel is composed of up to 0.02 mass % of C, up to 2.0 mass % of Si, up to 2.0 mass % of Mn, up to 0.04 mass % of P, up to 0.04 mass % of S, 3 to 7 mass % of Ni, 17 to 27 mass % of Cr, 0.5 to 6.0 mass % of Mo, 1 to 5 mass % of Cu, up to 3 mass % of W, 0.05 to 0.3 mass % of N, 0.0005 to 0.0015 mass % of B and the balance being Fe.
  • The contents of individual elements of the proposed stainless steel are optimized to prevent a σ phase, carbides and nitrides from being formed during the fabrication of a thick cast product such as a propeller blade for a large marine vessel because of slow cooling rate, to adversely affect both corrosion resistance and toughness of the product.
  • Patent Document 2, as specified later, proposes a two-phase stainless steel having high mechanical strength and corrosion resistance against seawater. The disclosed stainless steel is composed of up to 0.06 mass % of C, 1.5 to 3.5 mass % of Si, 0.1 to 3.0 mass % of Mn, 2 to 8 mass % of Ni, 18 to 28 mass % of Cr, 0.1 to 0.9 mass % of Mo, 0.03 to 0.2 mass % of N, and the balance being Fe.
    • Patent Document 1: JP-B-3270498
    • Patent Document 2: JP-A-H09-302446
  • In the known two-phase stainless steel, the austenite and ferrite phases are formed by using Cr and various other elements. Namely, the inclusion of various elements within respective ranges required is essential in order to form the austenite and ferrite phases within a desired ratio thereof.
  • Of such elements, similar to Cr, Mo is also an essential element to improve corrosion resistance, especially corrosion against a reducing environment, of the two-phase stainless steel. However, Mo is not only expensive but also tends to adversely affect the mechanical property such as toughness of the stainless steel as the content thereof increases. Although an attempt has been made to reduce the Mo content in the aforementioned JP-A-H09-302446 , Mo must be inevitably used in order to obtain the desired corrosion resistance.
  • A stainless steel has been hitherto used for a cast article having a thinner portion thereof, such as a propeller blade of a propulsion unit for small watercrafts. In producing such a cast article having a thinner portion, a melt poured into a mold is liable to be cooled at the thinner potion forming section of the mold and its fluidity is therefore apt to be reduced there. When the difference between the pouring temperature and the melting point of the stainless steel is small, therefore, the melt cannot flow sufficiently into the thinner portion forming section. This is likely to cause defects, such as incomplete filling, in the cast product.
  • If the pouring temperature is increased to ensure a sufficient difference from the melting point for prevention of occurrence of the incomplete filling, then the temperature of the melt introduced into the mold will be also increased correspondingly, resulting in application of a great thermal load to the mold and generation of a gas during casting operation. The use of such a high temperature melt is therefore disadvantageous.
  • It is therefore an object of the present invention to provide a cast article comprising a two-phase stainless steel which is substantially free of Mo, which uses a reduced number of kinds of elements, and which shows satisfactory mechanical strength and corrosion resistance and a method for manufacturing such cast article of a two-phase stainless steel.
  • According to the present invention said object is solved by a cast article of a two-phase stainless steel having the features of independent claim 1. Moreover said object is also solved by a method to manufacture a cast article cast article according to claim 3.
  • Accordingly, it is provided a cast article in the form of a propeller blade for a propulsion unit of a small watercraft, wherein the cast article comprises a two-phase stainless steel having a ferrite phase and an austenite phase containing specific contents of C, Si, Mn, Ni, Cr, Cu, N and Fe, and unavoidable impurities, and having an area ratio of the ferrite phase in a range between 20% and 60%.
  • With the present teaching, there is provided a cast article of a two-phase stainless steel capable of providing a wide temperature range over which the melt thereof has a suitable fluidity without increasing the pouring temperature and, therefore, capable of easily affording a cast article having a thinner portion.
  • The specific contents in mass % are: up to 0.08 % of C, not less than 0.5 % but not more than 1.5 % of Si, up to 1.0 % of Mn, not less than 4.0 % but not more than 8.0 % of Ni, not less than 23 % but not more than 27 % of Cr, not less than 2.0 % but not more than 6.0 % of Cu, not less than 0.05 % but not more than 0.3 % of N, and the balance being Fe and unavoidable impurities.
  • Further, preferably the two-phase stainless steel has a melting point of not higher than 1,450°C, and being used as a casting material of a cast article comprising a portion having a thickness of 3mm or less.
  • Accordingly, it is also provided a method to manufacture a cast article in the form of a propeller blade for a propulsion unit of a small watercraft, wherein the cast article comprises a two-phase stainless steel having a ferrite phase and an austenite phase, by preparing a melt including specific contents of C, Si, Mn, Ni, Cr, Cu, N and Fe, and substantially free of Mo addition, and adjusting an area ratio of the ferrite phase in a range between 20% and 60%.
  • The melt is prepared with the specific contents in mass %: up to 0.08 % of C, not less than 0.5 % but not more than 1.5 % of Si, up to 1.0 % of Mn, not less than 4.0 % but not more than 8.0 % of Ni, not less than 23 % but not more than 27 % of Cr, not less than 2.0 % but not more than 6.0 % of Cu, not less than 0.05 % but not more than 0.3 % of N, and the balance being Fe and unavoidable impurities.
  • In the following, the present invention is explained in greater detail with respect to several embodiments thereof in conjunction with the accompanying drawings, wherein:
  • FIG. 1
    is a plan view, schematically illustrating a propeller of a small watercraft, and
    FIG. 2
    is a phase diagram, schematically showing phase constitution as a function of the Ni equivalent vs. Cr equivalent.
    Description of Reference Numerals:
  • 10
    propeller
    11
    central base section
    12
    blade (thin portion)
  • An embodiment of the present teaching will be hereinafter described.
  • FIG. 1 shows a propeller, as a cast article of an embodiment, for a propulsion unit of a small watercraft.
  • Reference numeral 10 denotes a propeller formed of a certain two-phase stainless steel. The propeller has a central base section 11 and a pair of blades 12 extending in radial, opposite directions from the base section 11, which are formed in one body. Each blade 12 includes its wide surface portion preferably having a thickness of 3 mm or less, more preferably 2 mm or less.
  • The propeller 10 is formed using a casting mold including two hollow potions, one for forming the central base portion 11 and the others for forming casting blades 12. The two hollow portions are in communication with each other. The melt to be poured into the casting mold includes constituent elements whose amounts are selected to obtain a specified two-phase stainless steel of the propeller formed. The propeller 10 is formed by pouring the melt into the casting mold at a pouring temperature of for example 1,550 to 1,650°C and then leaving as it is for heat release.
  • The two-phase stainless steel as a material configuring such propeller 10 comprises C, Si, Mn, Ni, Cr, Cu, N and the balance. The balance includes Fe and unavoidable impurities. Thus, the stainless steel is substantially free of expensive Mo. Yet, the two-phase stainless steel has a ferrite phase and an austenite phase and a reduced melting point.
  • The reason for selecting the contents of constitutional elements are as follows:
    • Carbon (C) is highly effective to form a stable austenite phase and to improve the strength of the two-phase stainless steel. If the C content is excessively high, however, chromium carbide is apt to be formed so that the corrosion resistance of the steel is deteriorated and, further, the steel becomes brittle. Additionally, as the C content increases, the melting point of the steel decreases but the strength of the steel is adversely affected. Accordingly, the C content is preferable to be low, i.e. up to 0.08 mass % in this case.
    • Silicon (Si) is a deoxidizer and is somewhat effective to stabilize the ferrite phase. Further, the melting point of the steel decreases as an increase of the Si content. Since Mo which is a ferrite-stabilizing element is not used in the present teaching, the use of Si in a relatively large amount is desired. Accordingly, the Si content is preferable to be high, i.e. not less than 0.5 mass % but not more than 1.5 mass %.
    • Manganese (Mn) is a deoxidizer and, as well as Ni, contributes to an increase of solid solution of N in the two-phase stainless steel. Mn is also less effective to stabilize the austenite phase. The melting point of the stainless steel decreases with an increase of the Mn content. The use of Mn in an excessive amount, however, adversely affects corrosion resistance such as pitching corrosion resistance. Accordingly, the Mn content is preferably up to 1.0 mass %.
    • Nickel (Ni) improves mechanical properties and moldability, contributes to maintain corrosion resistance and stabilize an austenite phase. Ni also has a small influence upon the melting point of the stainless steel although depending upon the amount thereof. Because Mo which is a ferrite-stabilizing element is not used in the present teaching, Ni which is an austenite stabilizing element and has small influence upon the melting point is not desired to be used in a large amount. Accordingly, the Ni content is preferable to be low, i.e. not less than 4.0 mass % but not more than 8.0 mass %.
    • Chromium (Cr) a main component which contributes to impart corrosion resistance to the two-phase stainless steel and stabilizes a ferrite phase. The higher the Cr content, the better is the corrosion resistance due to an improved stability of a passive film. Cr also has a small influence upon the melting point of the steel although depending upon the amount thereof. Because Mo which is a ferrite-stabilizing element and contributes to corrosion resistance is not used in the present teaching, Cr which is a ferrite stabilizing element and contributes to improve corrosion resistance is desired to be used in a large amount. However, too large an amount of Cr adversely affects the mechanical properties and moldability. Accordingly, the Cr content is preferably not less than 23 mass % but not more than 27 mass %.
    • Copper (Cu) imparts corrosion resistance to the two-phase stainless steel. The melting point of the steel can be reduced by increasing the Cu content. Since Mo which contributes to improve corrosion resistance is not used in the present teaching, the Cu content is desired to be high. However, too high a Cu content causes brittleness of the steel. Accordingly, the Cu content is preferably not less than 2.0 mass % but not more than 6.0 mass %.
    • Nitrogen (N) can increase the strength of the two-phase stainless steel even in a small amount and is highly effective to stabilize an austenite phase. The N content has little influence upon the melting point of the steel. Too large an amount of N is undesirable because of the precipitation of nitrides. Accordingly, the N content is preferably not less than 0.05 mass % but not more than 0.3 mass %.
  • The balance of the two-phase stainless steel is Fe and unavoidable impurities such as P and S. Such impurities may possibly include Mo. As long as the amount of impurity Mo is not more than 0.3 mass %, it may be further removed, or may be used as it is without removal, because the Mo content, which is an unavoidable impurity, is very small.
  • To obtain the two-phase stainless steel of the present teaching, the contents of the components described above are selected within the respective ranges thereof to adjust the area ratio of the ferrite phase and the austenite phase. The area ratio of the ferrite phase should be not less than 20 % but not more than 60 % in order for the stainless steel to exhibit well balanced corrosion resistance, particularly pitting corrosion resistance and mechanical strength.
  • The area ratio of the ferrite phase varies depending on cooling rate and the like production conditions, but may be suitably controlled by adjustment of mixing proportions of the elements of the two-phase stainless steel in terms of the Cr equivalent (ferrite forming elements) and Ni equivalent (austenite forming elements) which may be expressed by the following formulas (1) and (2), for example:
  • Formula 1


  •         Cr equivalent = %Cr + %Mo *+ 1.5×%Si + 0.5×%Nb     (1)

             Ni equivalent = %Ni + 30×%C + 0.5×%Mn + 30×%N     (2)

    wherein individual %elements show the contents of these elements in terms of mass %, and %Nb is taken into account only when it is present.
  • FIG. 2 shows a schematic phase diagram which gives the area ratio of the ferrite phase as a function of the nickel equivalent vs. the chromium equivalent. In the present teaching, the proportion of constituent elements is adjusted so that the Cr equivalent and Ni equivalent fall within the region S where the area ratio of the ferrite phase is not less than 20 % but not more than 60 %. Because the strength is apt to be reduced due to excessive small area ratio of the ferrite phase, wile the corrosion resistance is apt to be deteriorated due to excessive large area ratio of the ferrite phase.
  • Further, the area ratios of the ferrite phase and the austenite ratios are adjusted in such a manner described above and the contents of the component elements also described above are adjusted so that the melting point of the two-phase stainless steel of the embodiment is adjusted preferably to a 1,450°C or lower, more preferably 1,430°C or lower. The melting point is preferable to be low as far as possible. Because, if it is determined to be excessively high then the temperature of the melt must be determined to be higher. The fluidity of the melt would be otherwise apt to be reduced, causing difficulty of forming the thin portion.
  • As the two-phase stainless steel described above: contains specific content of C, Si, Mn, Ni, Cr, Cu, N and Fe, and unavoidable impurities; has the ferrite phase and the austenite phase; and has an area ratio of the ferrite phase in a range between 20% and 60%. Therefore, the two-phase stainless steel of the present teaching can show well-balanced mechanical strength and corrosion resistance even though Mo is not added thereto. For the propeller 10 brought in contact with water or seawater, a two-phase stainless steel can be provided which is inexpensive and durable in practical use with a less number of kinds of component elements.
  • Also, as this two-phase stainless steel has a melting point of 1450°C or less, a wider range of the temperature in which the melt can flow is easily secured without a higher pouring temperature being determined. The thermal load applied to the casting mold is therefore not increased and the fluidity of the melt is improved. As a result, molding defects hardly occur in the blades 12 even though the blades 12 have a thin portion of 3mm or less thick.
  • The propeller 10 of such two-phase stainless steel can be fabricated inexpensively because of less kinds of component elements and has a well fluidity of the melt thereof for avoiding casting defects of the blades 12, resulting in easy production thereof. A mechanical strength and a corrosion resistance sufficient to resist against stresses generated and applied corresponding to a propulsive force in normal temperature water and seawater can be secured.
  • Example
  • The following examples and comparative examples will be described and illustrated.
  • Stainless steels containing components shown in Table 1 and the balance containing Fe and unavoidable impurities were prepared and determined for their liquid phase line temperatures (as melting points) and area ratios of the ferrite phase (α phase) and austenite phase (γ phase) by actual measurement and by simulation.
  • The results are shown in Table 1. [Table 1]
    C Si Mn Ni Cr Cu Mo N Liquid phase line temperature (°C) α phase γ phase
    Comparative Example 1 0.054 0.7 0.58 8.87 22.98 0.15 3.31 0.13 1453 - -
    Comparative Example 2 0.05 0.8 0.8 7 25.00 2.5 3.00 0.15 1425 41.8 57
    Example 1 0.05 0.8 0.8 7 25.00 2.5 0 0.15 1425 24.4 74.6
    Example 2 0.05 0.8 0.8 7 25.00 4 0 0.15 1404 30.2 65.2
    Example 3 0.05 1.2 0.8 6 25.00 4 0 0.15 1409 40.4 54.7
    Example 4 0.05 1.2 0.8 6 25.00 4 0 0.2 1405 34.4 60.4
    Example 5 0.05 1.2 0.8 6 25.00 4 0 0.3 1399 28.8 65.8
    Example 6 0.050 1.17 0.82 5.59 25.10 4.00 0 0.15 - 50 50
    Note 1: %mass for element
    Note 2: measurement value as to Comparative Example 1 and Example 1
  • [Strength test]
  • Example 6 and Comparative Example 1 were tested for tensile test and impact test for test pieces thereof as follows.
  • Using the test pieces having the same shape, a tensile test was carried out by the metallic material tensile test in accordance with JIS Z2371.
  • Using the test pieces having the same shape, an impact test was carried out by metallic material impact test in accordance with JIS Z2371.
  • The test results are summarized in Table 2. [Table 2]
    Tensile strength (MPa) 0.2 % Proof strength (MPa) Elongation after fracture (%) Impact strength (J/cm2)
    Comparative Example 1 654 430 12.7 66.4
    Example 6 734 450 11.3 105
  • As is evident from the results shown in Table 2, the substantially Mo-free two-phase stainless steel of Example 6 has equal or higher tensile strength and impact strength as compared with the Mo-containing stainless steel of Comparative Example 1.
  • Casting test
  • Using the stainless steels of Example 6 and Comparative Example 1, propellers as shown in FIG. 1 were prepared by casting.
  • The minimum thickness of the blades 12 of the propeller 10 was 1.6 mm.
  • As a result, a good cast propeller could be obtained using the stainless steel of Example 6. On the other hand, due to a high melting point, the blades 12 made of the stainless steel of Comparative Example 1 had casting defects when the same pouring temperature was used to thereby reduce the temperature range. It was revealed that the stainless steel of Example 6 was able to give a thin cast article more easily than that of Comparative Example 1.
  • Corrosion resistance test
  • The propellers 10 made of the stainless steels of Example 6 and Comparative Example 1 were each subjected to a corrosion test.
  • An aqueous brine solution spray test as the corrosion test was carried out under conditions in accordance with JIS Z 2371. Thus a 5 % by weight aqueous brine solution having its temperature of 35°C was sprayed over the test piece. The test piece was then allowed to stand for 4 days to check rust formation with naked eyes.
  • No rust was observed on surfaces of the test pieces of Example 6 and Comparative Example 1. Thus, it was revealed that the stainless steel of Example 6 has corrosion resistance similar to the stainless steel Comparative Example 1.
  • The description above discloses, amongst others, an embodiment of a two-phase stainless steel comprising Fe as a major component and further containing C, Si, Mn, Ni, Cr, Cu, N and unavoidable impurities as indicated in claim 1, and comprising a ferrite phase and an austenite phase with an area ratio of the ferrite phase being not less than 20 % but not more than 60 % (first aspect).
  • There is disclosed an embodiment of a two-phase stainless steel comprising, in mass %: up to 0.08 % of C, not less than 0.5 % but not more than 1.5 % of Si, up to 1.0 % of Mn, not less than 4.0 % but not more than 8.0 % of Ni, not less than 23 % but not more than 27 % of Cr, not less than 2.0 % but not more than 6.0 % of Cu, not less than 0.05 % but not more than 0.3 % of N, and the balance being Fe and unavoidable impurities, and comprising a ferrite phase and an austenite phase with an area ratio of the ferrite phase being not less than 20 % but not more than 60 % (second aspect).
  • Further, preferably there is disclosed a two-phase stainless steel having a melting point of not higher than 1,450°C, and being used as a casting material of a cast article comprising a portion having a thickness of 3mm or less (third aspect).
  • Further, preferably there is disclosed a cast article of a two-phase stainless steel, comprising the two-phase stainless steel according to any one of the first to third aspects (fourth aspect).
  • Further, there is disclosed an embodiment of a cast article in the form of a propeller blade for a propulsion unit of a small watercraft, comprising the two-phase stainless steel according to the third aspect (fifth aspect).
  • To solve the problems mentioned above, the description above discloses a two-phase stainless steel of the first aspect comprising Fe as a major component and further containing C, Si, Mn, Ni, Cr, Cu, N and unavoidable impurities, and comprising a ferrite phase and an austenite phase with an area ratio of the ferrite phase being not less than 20 % but not more than 60 %.
  • Further, it discloses a two-phase stainless steel of the second aspect comprising, in mass %: up to 0.08 % of C, not less than 0.5 % but not more than 1.5 % of Si, up to 1.0 % of Mn, not less than 4.0 % but not more than 8.0 % of Ni, not less than 23 % but not more than 27 % of Cr, not less than 2.0 % but not more than 6.0 % of Cu, not less than 0.05 % but not more than 0.3 % of N, and the balance being Fe and unavoidable impurities, and comprising a ferrite phase and an austenite phase with an area ratio of the ferrite phase being not less than 20 % but not more than 60 %.
  • Further, it discloses a two-phase stainless steel of the third aspect having a melting point of not higher than 1,450°C, and being used as a casting material of a cast article comprising a portion having a thickness of 3mm or less.
  • Further, it discloses a cast article of a two-phase stainless steel of the fourth aspect comprising the two-phase stainless steel according to any one of the first to third aspects.
  • Further, it discloses a cast article in the form of a propeller blade for a propulsion unit of a small watercraft of the fifth aspect comprising the two-phase stainless steel according to the third aspect.
  • Effect
  • As the two-phase stainless steel according to the first or second aspect: contains Fe as a major component, and C, Si, Mn, Ni, Cr, Cu, N and unavoidable impurities; has the ferrite phase and the austenite phase; and has an area ratio of the ferrite phase in a range between 20% and 60% that is obtained by adjustment of contents of the component elements. Therefore, the two-phase stainless steel of the present teaching can show well-balanced mechanical strength and corrosion resistance even though Mo is not added thereto. For the propeller 10 brought in contact with water or seawater, a two-phase stainless steel can be provided which is inexpensive and durable in practical use with a less number of kinds of component elements.
  • Also, as the two-phase stainless steel according to the third aspect having a melting point of 1450°C or less is used as a material of cast article including a thin portion having a thickness of 3 mm or less, a wider range of the temperature in which the melt can flow is easily secured without a higher pouring temperature being determined. The thermal load applied to the casting mold is therefore not increased and the fluidity of the melt is improved. As a result, molding defects hardly occur in the blades 12 even though the blades 12 have a thin portion of 3mm or less thick.
  • As the two-phase stainless cast article of the fourth aspect comprises the substantially Mo-free, 2-phase stainless steel according to claim 1 or 2, it is given corrosion resistance and mechanical strength enough to be used in contact with water and seawater.
  • The two-phase stainless steel cast article of the fifth aspect is directed to a propeller having blades and made of two-phase stainless steel according to the first or second aspect, for a propulsion unit of a small watercraft, the blades having widely extending thin portions. The propeller 10 of such two-phase stainless steel can be fabricated with well fluidity of the melt thereof for avoiding casting defects of the blades 12, resulting in easy production. A mechanical strength and a corrosion resistance enough to resist against stresses generated and applied corresponding to a propulsive force in water and seawater of normal temperature can be secured. Accordingly, a propeller can be provided, which is easily fabricated and given corrosion resistance and mechanical strength enough to be used in practical use.
  • The description, in particular discloses, in order to provide an inexpensive, substantially Mo-free, ferrite-austenite two-phase stainless steel having satisfactory mechanical strength and corrosion resistance in practical use, an embodiment of the stainless steel which has a ferrite phase area ratio of 20 to 60 % and a composition containing, in mass %, not more than 0.08 % of C, 0. 5 to 1.5 % of Si, not more than 1.0 % of Mn, 4.0 to 8.0 % of Ni, 23 to 27 % of Cr, 2.0 to 6.0 % of Cu, 0.05 to 0.3 % of N, and the balance being Fe and unavoidable impurities.

Claims (3)

  1. Cast article in the form of a propeller blade for a propulsion unit of a small watercraft, wherein the cast article comprises a two-phase stainless steel having a ferrite phase and an austenite phase, containing specific contents of C, Si, Mn, Ni, Cr, Cu, N and Fe, and unavoidable impurities, and having an area ratio of the ferrite phase in a range between 20% and 60%, wherein the specific contents of the two-phase stainless steel in mass % are:
    up to 0.08 % of C,
    not less than 0.5 % but not more than 1.5 % of Si,
    up to 1.0 % of Mn,
    not less than 4.0 % but not more than 8.0 % of Ni,
    not less than 23 % but not more than 27 % of Cr,
    not less than 2.0 % but not more than 6.0 % of Cu,
    not less than 0.05 % but not more than 0.3 % of N, and
    the balance being Fe and unavoidable impurities.
  2. Cast article according to claim 1, characterized in that the two-phase stainless steel has a melting point of not higher than 1,450°C, and characterized by comprising a portion having a thickness of 3 mm or less.
  3. Method to manufacture a cast article in the form of a propeller blade for a propulsion unit of a small watercraft, wherein the cast article comprises a two-phase stainless steel having a ferrite phase and an austenite phase, by preparing a melt including specific contents of C, Si, Mn, Ni, Cr, Cu, N and Fe, and substantially free of Mo addition, and adjusting an area ratio of the ferrite phase in a range between 20% and 60%, wherein the melt is prepared with the specific contents in mass %:
    up to 0.08 % of C,
    not less than 0.5 % but not more than 1.5 % of Si,
    up to 1.0%ofMn,
    not less than 4.0 % but not more than 8.0 % of Ni,
    not less than 23 % but not more than 27 % of Cr,
    not less than 2.0 % but not more than 6.0 % of Cu,
    not less than 0.05 % but not more than 0.3 % of N, and
    the balance being Fe and unavoidable impurities.
EP08001223.0A 2007-01-23 2008-01-23 Two-phase stainless steel Active EP1956109B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2007012845A JP2008179844A (en) 2007-01-23 2007-01-23 Two-phase stainless steel and casting of two-phase stainless steel

Publications (2)

Publication Number Publication Date
EP1956109A1 EP1956109A1 (en) 2008-08-13
EP1956109B1 true EP1956109B1 (en) 2014-05-07

Family

ID=39167477

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08001223.0A Active EP1956109B1 (en) 2007-01-23 2008-01-23 Two-phase stainless steel

Country Status (5)

Country Link
US (1) US20080175742A1 (en)
EP (1) EP1956109B1 (en)
JP (1) JP2008179844A (en)
CN (1) CN101230435B (en)
CA (1) CA2592890A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020158111A1 (en) 2019-01-30 2020-08-06 Jfeスチール株式会社 Duplex stainless steel, seamless steel pipe, and production method for duplex stainless steel

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE451465B (en) * 1984-03-30 1987-10-12 Sandvik Steel Ab FERRIT-AUSTENITIC STAINLESS STEEL MICROLEGATED WITH MOLYBID AND COPPER AND APPLICATION OF THE STEEL
US4740254A (en) * 1984-08-06 1988-04-26 Sandusky Foundry & Machine Co. Pitting resistant duplex stainless steel alloy
US4612069A (en) * 1984-08-06 1986-09-16 Sandusky Foundry & Machine Company Pitting resistant duplex stainless steel alloy
JP3270498B2 (en) 1991-11-06 2002-04-02 株式会社クボタ Duplex stainless steel with excellent crack and corrosion resistance
EP0750053B1 (en) * 1994-12-16 2001-10-10 Sumitomo Metal Industries, Ltd. Duplex stainless steel excellent in corrosion resistance
WO1996039543A2 (en) * 1995-06-05 1996-12-12 Pohang Iron & Steel Co., Ltd. Duplex stainless steel, and its manufacturing method
JPH09302446A (en) 1996-05-10 1997-11-25 Daido Steel Co Ltd Duplex stainless steel
US6033497A (en) * 1997-09-05 2000-03-07 Sandusky International, Inc. Pitting resistant duplex stainless steel alloy with improved machinability and method of making thereof
SE513247C2 (en) * 1999-06-29 2000-08-07 Sandvik Ab Ferrite austenitic steel alloy
SE524951C2 (en) * 2001-09-02 2004-10-26 Sandvik Ab Use of a duplex stainless steel alloy
SE527175C2 (en) * 2003-03-02 2006-01-17 Sandvik Intellectual Property Duplex stainless steel alloy and its use
SE527178C2 (en) * 2003-03-02 2006-01-17 Sandvik Intellectual Property Use of a duplex stainless steel alloy

Also Published As

Publication number Publication date
CA2592890A1 (en) 2008-07-23
US20080175742A1 (en) 2008-07-24
CN101230435A (en) 2008-07-30
JP2008179844A (en) 2008-08-07
EP1956109A1 (en) 2008-08-13
CN101230435B (en) 2010-09-08

Similar Documents

Publication Publication Date Title
KR101888300B1 (en) High Entropy Alloy Based Chromium, Iron, Manganese, Nickel and Vanadium
KR100596660B1 (en) Austenitic stainless steel
EP2229463B1 (en) Corrosion resistant lean austenitic stainless steel
EP2279276B1 (en) Stainless steel product, use of the product and method of its manufacture
JP5335502B2 (en) Martensitic stainless steel with excellent corrosion resistance
EP2885440B1 (en) High-chromium heat-resistant steel
US11505853B2 (en) High manganese steel having superior low-temperature toughness and yield strength and manufacturing method thereof
KR20170110018A (en) Cryogenic High Entropy Alloy
US20170088910A1 (en) Corrosion and cracking resistant high manganese austenitic steels containing passivating elements
CA2210797A1 (en) Improvements in and relating to carbide-free bainitic steels and methods of producing such steels
KR20120074638A (en) Ultra thick steel sheet for pressure vessel having excellent central properties and hydrogen induced cracking resistance, and method for manufacturing the same
KR101211032B1 (en) High-nitrogen austenitic stainless steels with good Eco-index and excellent pitting corrosion resistance, and fabrication methods thereof
KR101465088B1 (en) Low carbon high strength steel plates with good low temperature toughness and manufacturing method for the same
KR101301994B1 (en) Method of manufacturing clad steel of ship
JP2001107195A (en) Low carbon high hardness and high corrosion resistance martensitic stainless steel and its producing method
EP1956109B1 (en) Two-phase stainless steel
KR20150074691A (en) Duplex stainless steel with supper corrosion resistance and manufacturing method thereof
EP3395988B1 (en) High-strength structural steel sheet excellent in hot resistance and manufacturing method thereof
EP1705260B1 (en) Steel
CN102703835A (en) Hot-work die steel for aluminum die-casting mould
EP3730655B1 (en) High strength steel plate and manufacturing method therefor
US20030091458A1 (en) Maraging type spring steel
KR101203539B1 (en) High nitrogen austenitic stainless steels with high mechanical properties and excellent resistance to pitting corrosion and fabrication methods thereof
EP4144880A1 (en) Low-thermal-expansion casting and production method for same
KR101726091B1 (en) High manganese steel for thick plate having low temperature toughness and yield strength and method for manufacturing the same

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA MK RS

17P Request for examination filed

Effective date: 20090129

17Q First examination report despatched

Effective date: 20090309

AKX Designation fees paid

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: YAMAHA HATSUDOKI KABUSHIKI KAISHA

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602008031968

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: C22C0038420000

Ipc: C22C0038000000

RIC1 Information provided on ipc code assigned before grant

Ipc: C22C 38/00 20060101AFI20131015BHEP

Ipc: C22C 38/02 20060101ALI20131015BHEP

Ipc: C22C 38/42 20060101ALI20131015BHEP

Ipc: C22C 38/04 20060101ALI20131015BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20131211

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 666775

Country of ref document: AT

Kind code of ref document: T

Effective date: 20140515

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602008031968

Country of ref document: DE

Effective date: 20140618

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 666775

Country of ref document: AT

Kind code of ref document: T

Effective date: 20140507

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20140507

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140807

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140808

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140907

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140908

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602008031968

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20150210

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602008031968

Country of ref document: DE

Effective date: 20150210

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150123

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20150123

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150131

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150131

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150123

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150123

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20080123

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230526

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20240119

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20240129

Year of fee payment: 17

Ref country code: FR

Payment date: 20240124

Year of fee payment: 17