EP2455508A1 - High strength / corrosion-resistant,.austenitic stainless steel with carbon - nitrogen complex additive, and method for manufacturing same - Google Patents

High strength / corrosion-resistant,.austenitic stainless steel with carbon - nitrogen complex additive, and method for manufacturing same Download PDF

Info

Publication number
EP2455508A1
EP2455508A1 EP09847378A EP09847378A EP2455508A1 EP 2455508 A1 EP2455508 A1 EP 2455508A1 EP 09847378 A EP09847378 A EP 09847378A EP 09847378 A EP09847378 A EP 09847378A EP 2455508 A1 EP2455508 A1 EP 2455508A1
Authority
EP
European Patent Office
Prior art keywords
stainless steel
austenitic stainless
content
nitrogen
less
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.)
Granted
Application number
EP09847378A
Other languages
German (de)
French (fr)
Other versions
EP2455508B1 (en
EP2455508A4 (en
Inventor
Sung-Joon Kim
Tae-Ho Lee
Chang-Seok Oh
Heon-Young Ha
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.)
Korea Institute of Machinery and Materials KIMM
Original Assignee
Korea Institute of Machinery and Materials KIMM
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
Priority claimed from KR1020090063487A external-priority patent/KR101089714B1/en
Priority claimed from KR1020090063486A external-priority patent/KR101089718B1/en
Application filed by Korea Institute of Machinery and Materials KIMM filed Critical Korea Institute of Machinery and Materials KIMM
Publication of EP2455508A1 publication Critical patent/EP2455508A1/en
Publication of EP2455508A4 publication Critical patent/EP2455508A4/en
Application granted granted Critical
Publication of EP2455508B1 publication Critical patent/EP2455508B1/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
    • C22C38/001Ferrous alloys, e.g. steel alloys containing N
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18Hardening; Quenching with or without subsequent tempering
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D6/00Heat treatment of ferrous alloys
    • C21D6/002Heat treatment of ferrous alloys containing Cr
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D6/00Heat treatment of ferrous alloys
    • C21D6/005Heat treatment of ferrous alloys containing Mn
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/021Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular fabrication or treatment of ingot or slab
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226Hot rolling
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/04Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
    • C21D8/0405Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing of ferrous alloys
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/04Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
    • C21D8/041Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing involving a particular fabrication or treatment of ingot or slab
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/04Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
    • C21D8/0421Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing characterised by the working steps
    • C21D8/0426Hot rolling
    • 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
    • C22C38/22Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • 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
    • C22C38/38Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
    • 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
    • C22C38/44Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • 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
    • C22C38/58Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D2211/00Microstructure comprising significant phases
    • C21D2211/001Austenite

Definitions

  • the present invention relates to a C + N austenitic stainless steel having high mechanical strength and excellent corrosion resistance, and a fabrication method thereof.
  • the austenitic stainless steels mainly depend on the addition of alloying elements for the improvement of most properties.
  • the most important technical subject in the development of new alloy is to ensure optimum properties including strength, ductility or corrosion resistance, with low fabrication costs by minimizing a content of a high priced alloying element or by replacing it with economical alloying elements.
  • nickel (Ni) is an effective austenite stabilizing element which contributes to the improvement of formability. More than 65 % of the total supply amount of nickel (Ni) is consumed for the production of austenitic stainless steels.
  • nickel (Ni) had kept increasing since 2001 by more than 700 % for the following six years, and particularly, it was doubled in 2007, therefore, the price of nickel (Ni) has become a major index in determining cost of stainless steels.
  • nickel (Ni) also gives adverse effects to human health and environment since nickel (Ni) can cause allergic reaction to human skin and give off toxic gas during recycling.
  • Nitrogen (N) is a highly effective austenite-stabilizing element, and provides various advantages, including solid solution hardening, less reduction in ductility accompanied by the increase in mechanical strength, and enhanced corrosion resistance. So far, the high-nitrogen stainless steel has not been commercialized due to the difficulty in the fabrication process to ensure high nitrogen (N) content in the steel. Recently, various studies have been conducted to develop effective fabrication processing methods, as a result, pressurized induction melting, pressurized electroslag remelting (PESR), powder metallurgy, and solution nitriding under nitrogen gas atmosphere have been suggested.
  • PESR pressurized electroslag remelting
  • the pressurizing processing is particularly required for the fabrication of a large-sized ingot of the high-nitrogen stainless steel, since the pressurizing processing ensures high nitrogen (N) content in the liquid metal and minimizes the delta ferrite gap, which significantly reduces the nitrogen (N) solubility during the solidification.
  • N nitrogen
  • a modification of conventional melting equipment or an incorporation of new equipments for the pressurizing process are inevitable to fabricate the high-nitrogen stainless steels employing the pressurized melting facility, therefore, the high-nitrogen stainless steel has not been commercialized yet.
  • H. Berns et al. disclosed austenitic steels in the International Patent Application No. PCT/EP2005/008960 , which contain minimum contents of nickel (Ni), 16 ⁇ 21 wt.% chromium (Cr), 16 ⁇ 21 wt.% manganese (Mn), 0.5-2 wt.% molybdenum (Mo), and 0.8 wt.% or more of carbon (C) and nitrogen (N) content ([C+N]), as a suggestion to solve the problems in the fabrication process mentioned above.
  • the invention disclosed by H. Berns et al. contains a relatively high manganese (Mn) content, which subsequently degrades corrosion resistance.
  • the present inventors have developed and completed a C+N austenitic stainless steel with an increased economic efficiency, high strength and excellent corrosion resistance, in which carbon (C) and nitrogen (N) as interstitial elements are added simultaneously instead of nickel (Ni). Therefore, the content of high priced nickel (Ni) can be minimized, and the strength and corrosion resistance can be improved through controlling the contents of the two interstitial elements of carbon (C) and nitrogen (N) (C+N, C/N) and those of the substitutional elements of manganese (Mn), chromium (Cr), molybdenum (Mo) and tungsten (W) (Mn+Cr, Mn/Cr, or 0.5W+Mo).
  • this alloy is further economically competitive than the conventional high-nitrogen stainless steels because it can be produced by the conventional melting furnace excluding pressurized process.
  • An aspect of the present invention is to resolve the problems mentioned above, and accordingly, it is an object of the present invention to provide a C+N austenitic stainless steel which has increased strength and excellent corrosion resistance through controlling the contents of the interstitial elements (C+N, C/N) and those of the substitutional elements (Mn+Cr, Mn/Cr, or 0.5W+Mo).
  • a C+N austenitic stainless steel is provided, to which carbon (C) and nitrogen (N) as interstitial elements are added simultaneously, so that the content of nickel (Ni) is minimized, which is high-priced alloying element, and harmful to an environment and a human health.
  • C carbon
  • N nitrogen
  • the developed austenitic stainless steel provides improved economic efficiency.
  • the austenitic stainless steel provides favorable mechanical properties of a tensile strength higher than 850 MPa and an uniform elongation more than 45 %, which are obtained through controlling the contents of the interstitial elements (C+N, C/N) and those of the substitutional elements (Mn+Cr, Mn/Cr, or 0.5W+Mo).
  • the invented alloy also provides an excellent corrosion resistance and a biocompatibility due to the highly alloyed nitrogen (N) and minimized content of nickel (Ni) which causes allergic reaction to the human body.
  • the austenitic stainless steel according to the present invention is efficiently applicable in the fabrication of a variety of functional components including medical biosubstances, watches and accessories, as well as the fields of the conventional structural austenitic stainless steel and offshore structures, desalination plants, materials for oil and gas installing/mining, and materials for transportation facilities, which require high level of strength and corrosion resistance.
  • FIG. 1 is a graphical representation of a variation of the nitrogen (N) solubility as a function of temperature of Fe-Cr-Mn based alloys and Fe-Cr-Mn-0.4C based alloys according to an embodiment of the present invention
  • FIG. 2 is a flowchart of a fabricating method for the C+N austenitic stainless steel with high mechanical strength and excellent corrosion resistance according to an embodiment of the present invention
  • FIG. 3 is a flowchart illustrating in detail the 4th step of adjusting of nitrogen (N) contents in the fabricating steps of the C+N austenitic stainless steel with high strength and excellent corrosion resistance according to an embodiment of the present invention.
  • FIG. 4 is a graphical representation for the comparison of pitting corrosion resistance among the examples of the present invention and comparative examples.
  • a C+N austenitic stainless steel with high strength and excellent corrosion resistance consists of: 8 to 12 wt.% manganese (Mn); 15 to 20 wt.% chromium (Cr); 2 wt.% or less nickel (Ni); 4 wt.% or less tungsten (W); 2 wt.% or less molybdenum (Mo); 0.6 to 1.0 wt.% of C+N content; a balance of iron (Fe); and unavoidable impurities.
  • the ratio of manganese (Mn) to chromium (Cr) ranges from 0.5 to 1.0.
  • the manganese (Mn) content in this invention is lower than that of the stainless steel disclosed by H. Berns et al. (i.e., 16 to 21 wt.% manganese (Mn)) in the International Patent Application No. PCT/EP2005/008960 , improved pitting resistance is obtained.
  • the total manganese (Mn) and chromium (Cr) content ([Mn+Cr]) is 30 wt.% or less.
  • the nitrogen (N) content is 0.3 wt.% or more.
  • the total tungsten (W) and molybdenum (Mo) content (0.5W+Mo) is 3 wt.% or less. If 0.5W+Mo content exceeds 3 wt.%, the manufacturing cost increases, the amount of remaining delta ferrite increases, and the harmful second phase is formed.
  • nickel (Ni) effectively stabilizes the austenitic phase, considering the high price and the adverse effect to environment and human health, the nickel (Ni) content is limited as low as possible. However, considering that the addition of a minute amount of nickel (Ni) to the austenitic stainless steel can improve hot and/or cold formability and suppress the formation of delta ferrite during solidification from the liquid phase, the nickel (Ni) is added within a limit of 2 wt.%.
  • Chromium (Cr) is an essential alloying element required to ensure the corrosion resistance for the stainless steel, and most austenitic stainless steels contain 15 wt.% or more chromium (Cr).
  • Cr chromium
  • excessively-added chromium (Cr) causes a formation of surplus delta ferrite remaining after solidification, and promotes a precipitation of various second phases during heat treatment, which degrade the corrosion resistance and formability of the stainless steel.
  • the chromium (Cr) content is limited within a range of 15 ⁇ 20 wt.% in the stainless steel.
  • Manganese (Mn) is an austenite-stabilizing element that can substitute for high-priced nickel (Ni).
  • manganese (Mn) works to increase nitrogen (N) solubility and, consequently, mechanical strength of the material is enhanced.
  • excessively-added manganese (Mn) usually combines with sulfur (S) or oxygen (O) in the stainless steel matrix, forming nonmetallic inclusions such as manganese sulfide (MnS) or manganese oxide (MnO).
  • the nonmetallic inclusions act as initiation sites for the pitting corrosion, thus they degrade the resistance to pitting corrosion of the austenitic stainless steel. Therefore, the manganese (Mn) content is limited within a range of 8 ⁇ 12 wt.%
  • Molybdenum (Mo) also improves corrosion resistance of an austenitic stainless steel, similar to chromium (Cr).
  • excessively-added molybdenum (Mo) can cause to increase the amount of delta ferrites remaining after solidification, and like chromium (Cr), induce a formation of harmful second phases.
  • alloying a large amount of Mo can increase the fabrication cost. Therefore, the molybdenum (Mo) content is limited to 2 wt.% or less.
  • Tungsten (W) can efficiently substitute for molybdenum (Mo), because tungsten (W) has an ability to stabilize the ferrite phase and to improve pitting corrosion resistance, corresponding to 1/2 equivalent of molybdenum (Mo) content.
  • tungsten (W) increases high-temperature strength and creep resistance of the stainless steel.
  • Tungsten (W) improves general corrosion resistance in a non-oxidizing atmosphere, promotes passivation of metals, and improves resistance to pitting corrosion of alloys.
  • tungsten (W) content is limited to 4 wt.% or less.
  • 0.5W+Mo content is limited to 3 wt.% or less.
  • carbon (C) is added to stabilize the austenite phase, and acts to improve the mechanical strength of the stainless steel through solid solution hardening.
  • C carbon
  • the excessive C can degrade the toughness, and form carbides such as M 23 C 6 or M 6 C at a grain boundary, which sensitize the grain boundary resulting in a decrease in the corrosion resistance.
  • the total content of carbon (C) and nitrogen (N) ([C+N]) in the stainless steel according to an embodiment of the present invention is limited within a range of 0.6 ⁇ 1.0 wt.%
  • FIG. 1 illustrates the result of the calculated nitrogen (N) solubility at 1 atm of partial pressure of nitrogen gas in Fe-Cr-Mn based ternary alloys (i.e., Fe-18Cr-10Mn, Fe-15Cr15Mn, and Fe-13Cr-20Mn alloys) in absence of carbon (C), and that in Fe-Cr-Mn-0.4C based ternary alloys containing 0.4 wt.% carbon (C).
  • the nitrogen (N) solubility in liquid phase metal decreases from 0.38 wt.% to 0.3 wt.% by the addition of carbon (C).
  • the loss of alloyed nitrogen (N) can be lowered. This phenomenon occurs due to the increased stability of the austenitic phase at high temperature and the decreased stability of the ferritic phase by the addition of carbon (C).
  • the targeted nitrogen (N) solubility can be achieved at atmospheric pressure (i.e., 1 atm of partial pressure of nitrogen gas).
  • the addition of carbon (C) does not show a noticeable influence on the free electron density of the steel, unlike nitrogen (N) in a predetermined content range.
  • the stainless steel exhibits a remarkably increased free electron density compared to those of the alloys where the only nitrogen (N) is added due to the synergistic effect between the two elements,.
  • the free electron density gradually increases with carbon (C) and nitrogen (N) content ([C+N]), and reaches the maximum value at 0.85 wt.% of [C+N] before it starts to decrease.
  • the total C+N content is limited within a range of 0.6 ⁇ 1.0 wt.% according to one embodiment of the present invention.
  • the fabrication method of a C+N austenitic stainless steel with high strength and excellent corrosion resistance includes the steps of: S100; charging of master alloy, in which a master alloy is charged into a vacuum melting furnace, and the chemical composition of the master alloy is (all in weight percent) pure iron, Fe-50%Mn, Fe-60%Cr, Fe-58.8%Cr-6.6%N, 75.1%Mn-17.4%Fe-6.8%C, tungsten (W) and/or molybdenum (Mo); S200; maintaining of vacuum, in which the vacuum melting furnace with the master alloy charged is maintained under vacuum; S300; melting of master alloy, in which the vacuum melting furnace is heated and the master alloy is melted; S400; adjusting of nitrogen (N) content, in which nitrogen gas is injected into the vacuum melting furnace; S500; agitating of melted alloy, in which the melted master alloy is agitated; S600; forming of ingot, in which an ingot is formed by pouring the melted alloy from the vacuum melting furnace
  • the maintaining of vacuum step (S200) is the step of maintaining the vacuum level inside the vacuum melting furnace at 10 -3 torr or lower.
  • the step of adjusting of N content includes two steps of; injecting nitrogen gas (S420), in which the nitrogen gas is injected to the vacuum melting furnace, and adjusting pressure (S440), in which the partial pressure of nitrogen gas in the vacuum melting furnace is adjusted to 1 atm.
  • the embodiments of the present invention are applicable to the fabrication of the austenitic stainless steel with high strength and excellent corrosion resistance in various forms of stainless steels including cast, forged and rolled stainless steels with economic manufacturing cost and raw material costs.
  • the austenitic stainless steel according to one embodiment of the present invention exhibits 850 MPa or higher of tensile strength and 45 % or higher of uniform elongation (see Table 2). Furthermore, the excellent corrosion resistance of the austenitic stainless steel according to one embodiment of the present invention was confirmed by measuring anodic polarization behavior in a 1 M NaCl solution at a potential scan rate (dV/dt) of 2 mV/s.
  • the austenitic stainless steel with carbon (C) and nitrogen (N) can be fabricated by the atmospheric induction melting process excluding the pressurizing process which was essential in the conventional fabrication of high-nitrogen steel. Since it is possible to fabricate the alloy with economic manufacturing cost, the price competitiveness of the developing alloy increases. Moreover, by controlling the contents of the interstitial elements (C+N, C/N), and those of the substitutional elements contents (Mn+Cr, Mn/Cr, or 0.5W+Mo), the high tensile strength (850 MPa or higher) and favorable uniform elongation (45 % or higher) assuring formability are successfully attained, and the corrosion resistance is improved.
  • the austenitic stainless steel according to the present invention is effectively applicable to not only the fields of the conventional structural austenitic stainless steels and offshore structures, desalination plants, materials for oil and gas installing/mining, and materials for transportation facilities, which require high level of mechanical strength and corrosion resistance, but also the fabrication of a variety of functional components including medical biosubstances, watches and accessories.
  • a ferrochromium master alloy e.g., Fe-60%Cr master alloy
  • Cr chromium
  • a ferromanganese master alloy e.g., Fe-50%Mn master alloy
  • Mn manganese
  • a master alloy consisting of Fe-50%Mn, Fe-60%Cr, pure iron, Fe-58.8%Cr-6.6%N for controlling the nitrogen (N) content, 75.1%Mn-17.4%Fe-6.8%C for controlling the carbon (C) content, tungsten (W) and/or molybdenum (Mo), was charged into a vacuum melting furnace.
  • the vacuum melting furnace was degassed until the vacuum level became 10 -3 torr or below, and the vacuum level was maintained.
  • the vacuum melting furnace was heated so that the master alloy and the pure iron were sufficiently melted.
  • nitrogen (N) content was adjusted by introducing nitrogen gas into the vacuum melting furnace when the master alloy and the pure iron were melted (at the step of S420), and by adjusting the internal partial pressure of nitrogen gas to 1 atm during melting (at the step of S440).
  • the melted alloy was agitated by electromagnetic induction agitation so that the segregation of the alloying element was avoided.
  • an ingot was formed by pouring the melted alloy from the vacuum melting furnace.
  • the ingot was fabricated in forms of a plate, tube, rod, wire or the like, through hot rolling, and at the step of S800, water quenching treatment was done to prevent the precipitation of carbides which generally degrade the mechanical properties and corrosion resistance.
  • the commercially-available austenitic stainless steels i.e., AISI 304, AISI 316, AISI 316L were used.
  • the austenitic stainless steels were fabricated according to a composition disclosed by H. Berns et al. in the Patent Application No. PCT/EP2005/008960 .
  • the examples fabricated according to the present invention exhibited superior mechanical properties, which were 476 ⁇ 559 MPa of yield strength, 868-980 MPa of tensile strength, and 46.3 ⁇ 62.1% of uniform elongation.
  • the examples fabricated according to the present invention exhibited comparable mechanical properties to those of the C+N austenitic stainless steels (comp. 4 and comp. 5) disclosed by H. Berns et al., which showed the yield strength of 500-533 MPa, the tensile strength of 940-1019 MPa, and the uniform elongation of 59.0 ⁇ 62.8%.
  • the austenitic stainless steel according to an embodiment of the present invention minimizes nickel (Ni) content and exhibits superior mechanical properties in comparison with the commercial austenitic stainless steels. Therefore, the austenitic stainless steel according to the present invention can replace the conventional austenitic stainless steels.
  • examples 1 to 8 according to the present invention did not exhibit an occurrence of the pitting corrosion. Contrarily, the pitting corrosion occurred at 0.311 ⁇ 0.496 V SCE on the commercial stainless steels of comparative examples 1 to 3, and also occurred at 0.557 ⁇ 0.692 V SCE on the conventional C+N stainless steel of comparative examples 4 and 5, respectively. Accordingly, it is clear that the austenitic stainless steels fabricated according to the embodiments of the present invention have superior resistance to pitting corrosion than those of the comparative examples.
  • the austenitic stainless steel according to the embodiments of the present invention has minimized nickel (Ni) content and exhibits superior mechanical properties with increased corrosion resistance. Therefore, the austenitic stainless steel according to the present invention can replace the conventional austenitic stainless steels.

Abstract

A C+N austenitic stainless steel with high mechanical strength and excellent corrosion resistance and a fabrication method thereof are provided. The C+N austenitic stainless steel consists of: 8 to 12 wt.% manganese (Mn); 15 to 20 wt.% chromium (Cr); 2 wt.% or less nickel (Ni); 4 wt.% or less tungsten (W); 2 wt.% or less molybdenum (Mo); 0.6 to 1.0 wt.% of total C+N content; a balance of iron (Fe); and unavoidable impurities. The austenitic stainless steel fabricated provides favorable mechanical properties of a tensile strength of 850 MPa or higher and an uniform elongation of 45 % or higher, which are obtained through controlling the contents of the interstitial elements (C+N, C/N) and those of the substitutional elements (Mn+Cr, Mn/Cr, or 0.5W+Mo). In addition, the alloy also provides an excellent corrosion resistance and a biocompatibility due to the minimized content of nickel (Ni) which causes allergic reaction to the human body. Therefore, the C+N austenitic stainless steel is efficiently applicable in the fabrication of a variety of functional components including medical biosubstances, watches and accessories, as well as the fields of the conventional structural austenitic stainless steel and offshore structures, desalination plants, materials for oil and gas installing/mining and materials for transportation facilities, which require high level of mechanical strength and corrosion resistance.

Description

    BACKGROUND OF THE INVENTION 1. Field of the Invention
  • The present invention relates to a C + N austenitic stainless steel having high mechanical strength and excellent corrosion resistance, and a fabrication method thereof.
  • 2. Description of the Related Art
  • Generally, unlike carbon steels whose mechanical properties such as strength and ductility can be improved through thermo-mechanical treatments or phase transformation by various heat treatments, it is difficult to improve the mechanical properties of austenitic stainless steels using the heat treatment methods. Thus, the austenitic stainless steels mainly depend on the addition of alloying elements for the improvement of most properties.
  • Therefore, the most important technical subject in the development of new alloy is to ensure optimum properties including strength, ductility or corrosion resistance, with low fabrication costs by minimizing a content of a high priced alloying element or by replacing it with economical alloying elements.
  • Most austenitic stainless steels reported in the previous studies or inventions contain 16∼20 wt.% chromium (Cr), 6∼12 wt.% nickel (Ni), 0∼2 wt.% molybdenum (Mo), and 0.03∼ 0.15 wt.% carbon (C), and exhibit 500∼600 MPa of tensile strength, and 40% of elongation.
  • Among the above-mentioned alloying elements, nickel (Ni) is an effective austenite stabilizing element which contributes to the improvement of formability. More than 65 % of the total supply amount of nickel (Ni) is consumed for the production of austenitic stainless steels.
  • Nevertheless, the price of nickel (Ni) had kept increasing since 2001 by more than 700 % for the following six years, and particularly, it was doubled in 2007, therefore, the price of nickel (Ni) has become a major index in determining cost of stainless steels. In addition to the economical point of view, nickel (Ni) also gives adverse effects to human health and environment since nickel (Ni) can cause allergic reaction to human skin and give off toxic gas during recycling.
  • Accordingly, in order to resolve the problems associated with the conventional stainless steels having a high content of nickel (Ni), Fe-Cr-Mn alloys (or STS 200 alloy), and high-nitrogen austenitic stainless steels with desirable physicochemical properties owing to the addition of nitrogen (N) have been developed.
  • Nitrogen (N) is a highly effective austenite-stabilizing element, and provides various advantages, including solid solution hardening, less reduction in ductility accompanied by the increase in mechanical strength, and enhanced corrosion resistance. So far, the high-nitrogen stainless steel has not been commercialized due to the difficulty in the fabrication process to ensure high nitrogen (N) content in the steel. Recently, various studies have been conducted to develop effective fabrication processing methods, as a result, pressurized induction melting, pressurized electroslag remelting (PESR), powder metallurgy, and solution nitriding under nitrogen gas atmosphere have been suggested.
  • However, the major obstacle to the commercialization of the high-nitrogen stainless steel is the requirement for a special fabrication processing facilities such as pressurized induction melting furnace or PESR, which requires expensive equipments and complicated processing steps.
  • The pressurizing processing is particularly required for the fabrication of a large-sized ingot of the high-nitrogen stainless steel, since the pressurizing processing ensures high nitrogen (N) content in the liquid metal and minimizes the delta ferrite gap, which significantly reduces the nitrogen (N) solubility during the solidification. Thus, a modification of conventional melting equipment or an incorporation of new equipments for the pressurizing process are inevitable to fabricate the high-nitrogen stainless steels employing the pressurized melting facility, therefore, the high-nitrogen stainless steel has not been commercialized yet.
  • Recently, H. Berns et al. disclosed austenitic steels in the International Patent Application No. PCT/EP2005/008960 , which contain minimum contents of nickel (Ni), 16∼21 wt.% chromium (Cr), 16∼21 wt.% manganese (Mn), 0.5-2 wt.% molybdenum (Mo), and 0.8 wt.% or more of carbon (C) and nitrogen (N) content ([C+N]), as a suggestion to solve the problems in the fabrication process mentioned above. However, the invention disclosed by H. Berns et al. contains a relatively high manganese (Mn) content, which subsequently degrades corrosion resistance.
  • The present inventors have developed and completed a C+N austenitic stainless steel with an increased economic efficiency, high strength and excellent corrosion resistance, in which carbon (C) and nitrogen (N) as interstitial elements are added simultaneously instead of nickel (Ni). Therefore, the content of high priced nickel (Ni) can be minimized, and the strength and corrosion resistance can be improved through controlling the contents of the two interstitial elements of carbon (C) and nitrogen (N) (C+N, C/N) and those of the substitutional elements of manganese (Mn), chromium (Cr), molybdenum (Mo) and tungsten (W) (Mn+Cr, Mn/Cr, or 0.5W+Mo). In addition, this alloy is further economically competitive than the conventional high-nitrogen stainless steels because it can be produced by the conventional melting furnace excluding pressurized process.
  • SUMMARY OF THE INVENTION
  • An aspect of the present invention is to resolve the problems mentioned above, and accordingly, it is an object of the present invention to provide a C+N austenitic stainless steel which has increased strength and excellent corrosion resistance through controlling the contents of the interstitial elements (C+N, C/N) and those of the substitutional elements (Mn+Cr, Mn/Cr, or 0.5W+Mo).
  • It is another object of the present invention to provide a fabrication method of the austenitic stainless steel described above.
  • In one embodiment, a C+N austenitic stainless steel is provided, to which carbon (C) and nitrogen (N) as interstitial elements are added simultaneously, so that the content of nickel (Ni) is minimized, which is high-priced alloying element, and harmful to an environment and a human health. As a result, the developed austenitic stainless steel provides improved economic efficiency.
  • With the fabrication method according to one embodiment of the present invention, it is possible to fabricate an alloy with economic manufacturing cost, and hence the price competitiveness of the alloy can be increased. Furthermore, the austenitic stainless steel according to one embodiment provides favorable mechanical properties of a tensile strength higher than 850 MPa and an uniform elongation more than 45 %, which are obtained through controlling the contents of the interstitial elements (C+N, C/N) and those of the substitutional elements (Mn+Cr, Mn/Cr, or 0.5W+Mo). In addition, the invented alloy also provides an excellent corrosion resistance and a biocompatibility due to the highly alloyed nitrogen (N) and minimized content of nickel (Ni) which causes allergic reaction to the human body. Therefore, the austenitic stainless steel according to the present invention is efficiently applicable in the fabrication of a variety of functional components including medical biosubstances, watches and accessories, as well as the fields of the conventional structural austenitic stainless steel and offshore structures, desalination plants, materials for oil and gas installing/mining, and materials for transportation facilities, which require high level of strength and corrosion resistance.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • The above and/or other aspects of what is described herein will be more apparent by describing certain exemplary embodiments with reference to the accompanying drawings, in which:
  • FIG. 1 is a graphical representation of a variation of the nitrogen (N) solubility as a function of temperature of Fe-Cr-Mn based alloys and Fe-Cr-Mn-0.4C based alloys according to an embodiment of the present invention;
  • FIG. 2 is a flowchart of a fabricating method for the C+N austenitic stainless steel with high mechanical strength and excellent corrosion resistance according to an embodiment of the present invention;
  • FIG. 3 is a flowchart illustrating in detail the 4th step of adjusting of nitrogen (N) contents in the fabricating steps of the C+N austenitic stainless steel with high strength and excellent corrosion resistance according to an embodiment of the present invention; and
  • FIG. 4 is a graphical representation for the comparison of pitting corrosion resistance among the examples of the present invention and comparative examples.
  • * Description of the main reference numerals of FIGs. 2 and 3 *
  • S100: charging of master alloy S200: maintaining of vacuum
    S300: melting of master alloy S400: adjusting of nitrogen content
    S420: injecting of nitrogen gas S440: adjusting of pressure
    S500: agitating of melted alloy S600: forming of ingot
    S700: hot rolling S800: water quenching
  • DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
  • Certain exemplary embodiments will now be described in greater detail with reference to the accompanying drawings.
  • According to one embodiment, a C+N austenitic stainless steel with high strength and excellent corrosion resistance, consists of: 8 to 12 wt.% manganese (Mn); 15 to 20 wt.% chromium (Cr); 2 wt.% or less nickel (Ni); 4 wt.% or less tungsten (W); 2 wt.% or less molybdenum (Mo); 0.6 to 1.0 wt.% of C+N content; a balance of iron (Fe); and unavoidable impurities.
  • The ratio of manganese (Mn) to chromium (Cr) (Mn/Cr) ranges from 0.5 to 1.0.
  • According to one embodiment, since the manganese (Mn) content in this invention is lower than that of the stainless steel disclosed by H. Berns et al. (i.e., 16 to 21 wt.% manganese (Mn)) in the International Patent Application No. PCT/EP2005/008960 , improved pitting resistance is obtained.
  • The total manganese (Mn) and chromium (Cr) content ([Mn+Cr]) is 30 wt.% or less.
  • The nitrogen (N) content is 0.3 wt.% or more.
  • The total tungsten (W) and molybdenum (Mo) content (0.5W+Mo) is 3 wt.% or less. If 0.5W+Mo content exceeds 3 wt.%, the manufacturing cost increases, the amount of remaining delta ferrite increases, and the harmful second phase is formed.
  • The alloying elements of the austenitic stainless steel according to an embodiment of the present invention will be explained in greater detail below.
  • Although nickel (Ni) effectively stabilizes the austenitic phase, considering the high price and the adverse effect to environment and human health, the nickel (Ni) content is limited as low as possible. However, considering that the addition of a minute amount of nickel (Ni) to the austenitic stainless steel can improve hot and/or cold formability and suppress the formation of delta ferrite during solidification from the liquid phase, the nickel (Ni) is added within a limit of 2 wt.%.
  • Chromium (Cr) is an essential alloying element required to ensure the corrosion resistance for the stainless steel, and most austenitic stainless steels contain 15 wt.% or more chromium (Cr). However, excessively-added chromium (Cr) causes a formation of surplus delta ferrite remaining after solidification, and promotes a precipitation of various second phases during heat treatment, which degrade the corrosion resistance and formability of the stainless steel. Hence, the chromium (Cr) content is limited within a range of 15∼20 wt.% in the stainless steel.
  • Manganese (Mn) is an austenite-stabilizing element that can substitute for high-priced nickel (Ni). In addition, when added to the stainless steel, manganese (Mn) works to increase nitrogen (N) solubility and, consequently, mechanical strength of the material is enhanced. However, excessively-added manganese (Mn) usually combines with sulfur (S) or oxygen (O) in the stainless steel matrix, forming nonmetallic inclusions such as manganese sulfide (MnS) or manganese oxide (MnO). The nonmetallic inclusions act as initiation sites for the pitting corrosion, thus they degrade the resistance to pitting corrosion of the austenitic stainless steel. Therefore, the manganese (Mn) content is limited within a range of 8∼12 wt.%
  • Molybdenum (Mo) also improves corrosion resistance of an austenitic stainless steel, similar to chromium (Cr). However, excessively-added molybdenum (Mo) can cause to increase the amount of delta ferrites remaining after solidification, and like chromium (Cr), induce a formation of harmful second phases. In addition, alloying a large amount of Mo can increase the fabrication cost. Therefore, the molybdenum (Mo) content is limited to 2 wt.% or less.
  • Tungsten (W) can efficiently substitute for molybdenum (Mo), because tungsten (W) has an ability to stabilize the ferrite phase and to improve pitting corrosion resistance, corresponding to 1/2 equivalent of molybdenum (Mo) content. In addition, tungsten (W) increases high-temperature strength and creep resistance of the stainless steel. And also, Tungsten (W) improves general corrosion resistance in a non-oxidizing atmosphere, promotes passivation of metals, and improves resistance to pitting corrosion of alloys. However, being a ferrite-stabilizing element, an excessive presence of tungsten (W) in stainless steels can increase the amount of delta ferrite, and also raise the fabrication cost similar to the molybdenum (Mo). Therefore, tungsten (W) content is limited to 4 wt.% or less. Furthermore, in order to attain high corrosion resistance with economic fabrication cost, 0.5W+Mo content is limited to 3 wt.% or less.
  • Nitrogen (N), along with carbon (C) and manganese (Mn), is added as the austenite-stabilizing element to substitute for nickel (Ni) with the above-mentioned problems, and to increase strength without causing considerable degradation of ductility, and to promote corrosion resistance including pitting corrosion resistance. Accordingly, 0.3 wt.% or more of nitrogen (N) content has to be used for such effects. However, excessive nitrogen (N) can cause degradation in ductility and ductile-to-brittle transition.
  • Like nitrogen (N), carbon (C) is added to stabilize the austenite phase, and acts to improve the mechanical strength of the stainless steel through solid solution hardening. However, the excessive C can degrade the toughness, and form carbides such as M23C6 or M6C at a grain boundary, which sensitize the grain boundary resulting in a decrease in the corrosion resistance.
  • For these reasons, the total content of carbon (C) and nitrogen (N) ([C+N]) in the stainless steel according to an embodiment of the present invention is limited within a range of 0.6∼1.0 wt.%
  • Meanwhile, FIG. 1 illustrates the result of the calculated nitrogen (N) solubility at 1 atm of partial pressure of nitrogen gas in Fe-Cr-Mn based ternary alloys (i.e., Fe-18Cr-10Mn, Fe-15Cr15Mn, and Fe-13Cr-20Mn alloys) in absence of carbon (C), and that in Fe-Cr-Mn-0.4C based ternary alloys containing 0.4 wt.% carbon (C). Referring to FIG. 1, the nitrogen (N) solubility in liquid phase metal decreases from 0.38 wt.% to 0.3 wt.% by the addition of carbon (C). However, since the decrease in the nitrogen (N) solubility is significantly restrained due to the reduction in the delta ferrite formation during the solidification by the addition of carbon (C), the loss of alloyed nitrogen (N) can be lowered. This phenomenon occurs due to the increased stability of the austenitic phase at high temperature and the decreased stability of the ferritic phase by the addition of carbon (C). On this concept, when the carbon (C) and nitrogen (N) are added simultaneously to the stainless steel matrix, the targeted nitrogen (N) solubility can be achieved at atmospheric pressure (i.e., 1 atm of partial pressure of nitrogen gas).
  • Furthermore, the reason for the limitation of the carbon (C) and nitrogen (N) content (C+N) within a range of 0.6∼1.0 wt.% will be explained below. Added nitrogen (N) increases a free electron density of the austenitic matrix, which in turn promotes metallic bonding character and strengthens the short-range ordering in the austenitic matrix. Due to such characteristic atomic bonding induced by the addition of nitrogen (N), it is possible to restrict the generation of harmful second phases by the segregation of an alloying element, and hence improve the ductility and the corrosion resistance. In other words, the physical basis of the improvement of general properties of the steel by the addition of nitrogen (N) can be found from the increase of free electron density. On the other hand, the addition of carbon (C) does not show a noticeable influence on the free electron density of the steel, unlike nitrogen (N) in a predetermined content range. However, in case of the combined addition of carbon (C) and nitrogen (N) to the stainless steel matrix, the stainless steel exhibits a remarkably increased free electron density compared to those of the alloys where the only nitrogen (N) is added due to the synergistic effect between the two elements,. The free electron density gradually increases with carbon (C) and nitrogen (N) content ([C+N]), and reaches the maximum value at 0.85 wt.% of [C+N] before it starts to decrease. Therefore, based on the above-mentioned physical basis, and also to prevent a generation of undesirable secondary precipitate phases caused by an excessive addition of carbon (C) and nitrogen (N), the total C+N content is limited within a range of 0.6∼1.0 wt.% according to one embodiment of the present invention.
  • Furthermore, the fabrication method of a C+N austenitic stainless steel with high strength and excellent corrosion resistance according to the present invention includes the steps of: S100; charging of master alloy, in which a master alloy is charged into a vacuum melting furnace, and the chemical composition of the master alloy is (all in weight percent) pure iron, Fe-50%Mn, Fe-60%Cr, Fe-58.8%Cr-6.6%N, 75.1%Mn-17.4%Fe-6.8%C, tungsten (W) and/or molybdenum (Mo); S200; maintaining of vacuum, in which the vacuum melting furnace with the master alloy charged is maintained under vacuum; S300; melting of master alloy, in which the vacuum melting furnace is heated and the master alloy is melted; S400; adjusting of nitrogen (N) content, in which nitrogen gas is injected into the vacuum melting furnace; S500; agitating of melted alloy, in which the melted master alloy is agitated; S600; forming of ingot, in which an ingot is formed by pouring the melted alloy from the vacuum melting furnace; S700; hot-rolling the formed ingot; and S800; water quenching for the hot-rolled stainless steel to prevent precipitation of carbide which affects detrimentally the mechanical property and the corrosion resistance.
  • The maintaining of vacuum step (S200) is the step of maintaining the vacuum level inside the vacuum melting furnace at 10-3 torr or lower.
  • The step of adjusting of N content (S400) includes two steps of; injecting nitrogen gas (S420), in which the nitrogen gas is injected to the vacuum melting furnace, and adjusting pressure (S440), in which the partial pressure of nitrogen gas in the vacuum melting furnace is adjusted to 1 atm.
  • The embodiments of the present invention are applicable to the fabrication of the austenitic stainless steel with high strength and excellent corrosion resistance in various forms of stainless steels including cast, forged and rolled stainless steels with economic manufacturing cost and raw material costs.
  • The austenitic stainless steel according to one embodiment of the present invention exhibits 850 MPa or higher of tensile strength and 45 % or higher of uniform elongation (see Table 2). Furthermore, the excellent corrosion resistance of the austenitic stainless steel according to one embodiment of the present invention was confirmed by measuring anodic polarization behavior in a 1 M NaCl solution at a potential scan rate (dV/dt) of 2 mV/s.
  • Consequently, the austenitic stainless steel with carbon (C) and nitrogen (N) according to an embodiment of the present invention can be fabricated by the atmospheric induction melting process excluding the pressurizing process which was essential in the conventional fabrication of high-nitrogen steel. Since it is possible to fabricate the alloy with economic manufacturing cost, the price competitiveness of the developing alloy increases. Moreover, by controlling the contents of the interstitial elements (C+N, C/N), and those of the substitutional elements contents (Mn+Cr, Mn/Cr, or 0.5W+Mo), the high tensile strength (850 MPa or higher) and favorable uniform elongation (45 % or higher) assuring formability are successfully attained, and the corrosion resistance is improved. Additionally, since the harmful nickel (Ni) content is minimized, the austenitic stainless steel according to the present invention is effectively applicable to not only the fields of the conventional structural austenitic stainless steels and offshore structures, desalination plants, materials for oil and gas installing/mining, and materials for transportation facilities, which require high level of mechanical strength and corrosion resistance, but also the fabrication of a variety of functional components including medical biosubstances, watches and accessories.
  • Exemplary embodiments and examples of the present invention will be explained in greater detail below. However, it should be understood that the embodiments and examples are explained only for the illustrative purpose, and therefore, the concept of the present invention is not limited by the exemplary embodiments.
  • Examples 1 to 8. Fabrication of austenitic stainless steel according to the present invention
  • In the fabrication of an austenitic stainless steel according to an embodiment of the present invention, a ferrochromium master alloy (e.g., Fe-60%Cr master alloy) was used as a chromium (Cr) source which hardly melts due to the high melting point, and a ferromanganese master alloy (e.g., Fe-50%Mn master alloy) was used as a manganese (Mn) source to prevent a generation of manganese (Mn) fume and a segregation in molten metal due to the low vapor pressure.
  • Referring to FIGs. 2 and 3, at the step of S100, a master alloy consisting of Fe-50%Mn, Fe-60%Cr, pure iron, Fe-58.8%Cr-6.6%N for controlling the nitrogen (N) content, 75.1%Mn-17.4%Fe-6.8%C for controlling the carbon (C) content, tungsten (W) and/or molybdenum (Mo), was charged into a vacuum melting furnace. At the step of S200, the vacuum melting furnace was degassed until the vacuum level became 10-3 torr or below, and the vacuum level was maintained. At the step of S300, the vacuum melting furnace was heated so that the master alloy and the pure iron were sufficiently melted. At the step of S400, nitrogen (N) content was adjusted by introducing nitrogen gas into the vacuum melting furnace when the master alloy and the pure iron were melted (at the step of S420), and by adjusting the internal partial pressure of nitrogen gas to 1 atm during melting (at the step of S440). At the step of S500, the melted alloy was agitated by electromagnetic induction agitation so that the segregation of the alloying element was avoided. At the step of S600, when the temperature of the melted metal of the master alloy and pure iron reached 1450 °C during the agitating step of S500, an ingot was formed by pouring the melted alloy from the vacuum melting furnace. At the step of S700, the ingot was fabricated in forms of a plate, tube, rod, wire or the like, through hot rolling, and at the step of S800, water quenching treatment was done to prevent the precipitation of carbides which generally degrade the mechanical properties and corrosion resistance.
  • Comparative examples 1 to 3. Commercial austenitic stainless steels
  • The commercially-available austenitic stainless steels (i.e., AISI 304, AISI 316, AISI 316L) were used.
  • Comparative examples 4 and 5
  • The austenitic stainless steels were fabricated according to a composition disclosed by H. Berns et al. in the Patent Application No. PCT/EP2005/008960 .
  • The compositions of the austenitic stainless steels of the examples and the comparative examples are listed in table 1. [Table 1] (wt.%)
    Alloy Cr Mn Ni Mo W N C C+N
    Ex.1 18.10 9.47 - 2.17 - 0.38 0.48 0.86
    Ex.2 17.85 9.72 1.25 2.05 - 0.42 0.49 0.91
    Ex.3 17.98 9.79 - - 2.01 0.39 0.48 0.87
    Ex.4 17.71 9.85 1.21 - 2.00 0.36 0.55 0.91
    Ex.5 18.12 9.63 0.10 1.16 2.00 0.38 0.53 0.91
    Ex.6 17.73 9.97 1.23 1.15 1.99 0.39 0.52 0.91
    Ex.7 17.68 9.84 - - 3.80 0.41 0.56 0.97
    Ex.8 17.65 9.73 1.17 - 3.77 0.43 0.54 0.97
    Comp.1 18.00 2.00 8.00 - - - 0.08 0.08
    Comp.2 17.00 2.00 12.00 2.50 - - 0.08 0.08
    Comp.3 17.00 2.00 12.00 2.50 - - 0.03 0.03
    Comp.4 18.54 17.86 0.45 0.52 - 0.54 0.66 1.20
    Comp.5 17.97 17.8 0.36 0.51 - 0.58 0.48 1.06
  • Experiment 1. Measurement of tensile properties
  • The tensile properties of the examples and the comparative examples fabricated according to the embodiments of the present invention are listed in table 2. [Table 2]
    Alloy Yield strength (MPa) Tensile strength (Mpa) Uniform elongation (%)
    Ex.1 529 980 62.1
    Ex.2 559 973 46.3
    Ex.3 537 960 52.3
    Ex.4 493 903 59.3
    Ex.5 523 899 51.1
    Ex.6 528 927 49.4
    Ex.7 476 868 55.7
    Ex.8 532 930 50.8
    Comp.1 205 515 40.0 (total elongation)
    Comp.2 205 515 40.0 (total elongation)
    Comp.3 170 480 40.4 (total elongation)
    Comp.4 533 1019 62.8
    Comp.5 500 940 59.0
  • As table 2 illustrates, compared to the commercial austenitic stainless steels of comparative examples 1 to 3 which exhibited the yield strength of 170∼205 MPa, the tensile strength of 480∼515 MPa, and the elongation of 40 %, the examples fabricated according to the present invention exhibited superior mechanical properties, which were 476∼559 MPa of yield strength, 868-980 MPa of tensile strength, and 46.3∼62.1% of uniform elongation.
  • Furthermore, the examples fabricated according to the present invention exhibited comparable mechanical properties to those of the C+N austenitic stainless steels (comp. 4 and comp. 5) disclosed by H. Berns et al., which showed the yield strength of 500-533 MPa, the tensile strength of 940-1019 MPa, and the uniform elongation of 59.0∼62.8%.
  • Accordingly, the austenitic stainless steel according to an embodiment of the present invention minimizes nickel (Ni) content and exhibits superior mechanical properties in comparison with the commercial austenitic stainless steels. Therefore, the austenitic stainless steel according to the present invention can replace the conventional austenitic stainless steels.
  • Experiment 2. Measurement of corrosion resistance
  • In order to measure the corrosion resistance of the austenitic stainless steels according to the present invention, anodic polarization behavior of the sample was observed, as a result, the pitting potential was measured. Samples of austenitic stainless steels according to the examples of the present invention and comparative examples were immersed in a 1 M NaCl solution at a room temperature, and the potential was increased at a potential scan rate (dV/dt) of 2 mV/s. The polarization responses are represented in FIG. 4 and the measured pitting potentials are listed in table 3. [Table 3]
    Alloy Pitting potentials (Epit), VSCE
    Ex 1 No pitting (1.0 or above)
    Ex.2 No pitting (1.0 or above)
    Ex.3 No pitting (1.0 or above)
    Ex.4 No pitting (1.0 or above)
    Ex.5 No pitting (1.0 or above)
    Ex.6 No pitting (1.0 or above)
    Ex.7 No pitting (1.0 or above)
    Ex.8 No pitting (1.0 or above)
    Comp.1 0.311
    Comp.2 0.417
    Comp.3 0.496
    Comp.4 0.557
    Comp.5 0.692
  • As illustrated in FIG. 4 and table 3, examples 1 to 8 according to the present invention did not exhibit an occurrence of the pitting corrosion. Contrarily, the pitting corrosion occurred at 0.311∼0.496 VSCE on the commercial stainless steels of comparative examples 1 to 3, and also occurred at 0.557∼0.692 VSCE on the conventional C+N stainless steel of comparative examples 4 and 5, respectively. Accordingly, it is clear that the austenitic stainless steels fabricated according to the embodiments of the present invention have superior resistance to pitting corrosion than those of the comparative examples.
  • Consequently, compared to the commercial austenitic stainless steels or conventional C+N austenitic stainless steels, the austenitic stainless steel according to the embodiments of the present invention has minimized nickel (Ni) content and exhibits superior mechanical properties with increased corrosion resistance. Therefore, the austenitic stainless steel according to the present invention can replace the conventional austenitic stainless steels.
  • The foregoing exemplary embodiments and advantages are merely exemplary and are not to be construed as limiting the present inventive concept. The present teaching can be readily applied to other types of apparatuses. Also, the description of the exemplary embodiments of the present invention is intended to be illustrative, and not to limit the scope of the claims, and many alternatives, modifications, and variations will be apparent to those skilled in the art.

Claims (12)

  1. The C+N austenitic stainless steel with high mechanical strength and excellent corrosion resistance consisting of: 8 to 12 wt.% manganese (Mn); 15 to 20 wt.% chromium (Cr); 2 wt.% or less nickel (Ni); 0.6 to 1.0 wt.% of total C+N content; 4 wt.% or less tungsten (W); 2 wt.% or less molybdenum (Mo); a balance of iron (Fe); and unavoidable impurities.
  2. The C+N austenitic stainless steel of claim 1, consisting of 8 to 12 wt.% manganese (Mn); 15 to 20 wt.% chromium (Cr); 2 wt.% or less nickel (Ni); 1 to 4 wt.% tungsten (W); 0.6 to 1.0 wt.% of total C+N content; a balance of iron (Fe); and unavoidable impurities.
  3. The C+N austenitic stainless steel of claim 1, consisting of 8 to 12 wt.% manganese (Mn); 15 to 20 wt.% chromium (Cr); 2 wt.% or less nickel (Ni); 2 wt.% or less molybdenum (Mo); 0.6 to 1.0 wt.% of total C+N content; a balance of iron (Fe); and unavoidable impurities.
  4. The C+N austenitic stainless steel of claim 1, consisting of 8 to 12 wt.% manganese (Mn); 15 to 20 wt.% chromium (Cr); 2 wt.% or less nickel (Ni); 1 to 4 wt.% tungsten (W); 2 wt.% or less molybdenum (Mo); 0.6 to 1.0 wt.% of total C+N content; a balance of iron (Fe); and unavoidable impurities.
  5. The C+N austenitic stainless steel of claim 1, wherein the ratio of manganese (Mn) to chromium (Cr) (Mn/Cr) ranges from 0.5 to 1.0.
  6. The C+N austenitic stainless steel of claim 1, wherein the total content of manganese (Mn) and chromium (Cr) ([Mn+Cr]) is 30 wt.% or less.
  7. The C+N austenitic stainless steel of claim 1, wherein the nitrogen (N) content is 0.3 wt.% or more.
  8. The C+N austenitic stainless steel of claim 1, wherein the total content of tungsten (W) and molybdenum (Mo) (0.5W+Mo) is 3 wt.% or less.
  9. The C+N austenitic stainless steel of claim 1, having mechanical properties including a tensile strength of 850 MPa or higher, and an uniform elongation of 45% or more.
  10. A fabrication method of the C+N austenitic stainless steel with high mechanical strength and excellent corrosion resistance of claim 1, the fabrication method comprising:
    master alloy charging in which a master alloy is charged into a vacuum melting furnace;
    vacuum maintaining in which the vacuum melting furnace with the master alloy charged therein is maintained under vacuum;
    master alloy melting in which the vacuum melting furnace is heated and the master alloy is melted;
    nitrogen (N) content adjusting in which nitrogen gas is injected into the vacuum melting furnace;
    melted alloy agitating in which the melted master alloy is agitated;
    ingot forming in which an ingot is formed by pouring the agitated melted alloy from the vacuum melting furnace;
    hot-rolling the formed ingot; and
    performing water quenching of the hot-rolled stainless steel to prevent precipitation of carbide which degrades the mechanical property and corrosion resistance.
  11. The fabrication method of claim 10, in the vacuum maintaining step, the vacuum level inside the vacuum melting furnace is kept at 10-3 torr or lower.
  12. The fabrication method of claim 10, wherein the nitrogen (N) content adjusting comprises:
    nitrogen gas injecting in which nitrogen gas is injected to the interior of the vacuum melting furnace; and
    pressure adjusting in which the partial pressure of nitrogen gas of the interior of the vacuum melting furnace is adjusted to 1 atm.
EP09847378.8A 2009-07-13 2009-08-20 High strength / corrosion-resistant,.austenitic stainless steel with carbon - nitrogen complex additive, and method for manufacturing same Active EP2455508B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
KR1020090063487A KR101089714B1 (en) 2009-07-13 2009-07-13 C+N austenitic stainless steel with high strength and corrosion resistance having tungsten and fabrication method thereof
KR1020090063486A KR101089718B1 (en) 2009-07-13 2009-07-13 C+N austenitic stainless steel with high strength and corrosion resistance having tungsten and molybdenum, and fabrication method thereof
PCT/KR2009/004642 WO2011007921A1 (en) 2009-07-13 2009-08-20 High strength / corrosion-resistant,.austenitic stainless steel with carbon - nitrogen complex additive, and method for manufacturing same

Publications (3)

Publication Number Publication Date
EP2455508A1 true EP2455508A1 (en) 2012-05-23
EP2455508A4 EP2455508A4 (en) 2014-03-05
EP2455508B1 EP2455508B1 (en) 2016-11-23

Family

ID=43449524

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09847378.8A Active EP2455508B1 (en) 2009-07-13 2009-08-20 High strength / corrosion-resistant,.austenitic stainless steel with carbon - nitrogen complex additive, and method for manufacturing same

Country Status (5)

Country Link
US (1) US20110226391A1 (en)
EP (1) EP2455508B1 (en)
JP (1) JP5272078B2 (en)
CN (1) CN102428200B (en)
WO (1) WO2011007921A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014206582A3 (en) * 2013-06-27 2015-12-23 Nivarox-Far S.A. Timepiece spring made of austenitic stainless steel
EP3147380A1 (en) 2015-09-25 2017-03-29 The Swatch Group Research and Development Ltd. Nickel-free austenitic stainless steel
WO2018083311A1 (en) * 2016-11-04 2018-05-11 Richemont International Sa Timepiece resonator

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013114825A (en) * 2011-11-25 2013-06-10 Nisshin Steel Co Ltd Electrode laminate and lithium ion secondary battery using the same
KR101377251B1 (en) * 2011-12-13 2014-03-26 한국기계연구원 C+N austenitic stainless steel having good low-temperature toughness and a fabrication method or the same
EP2617839A1 (en) * 2012-01-18 2013-07-24 MeKo Laserstrahl-Materialbearbeitungen e.K. Nickel-free iron alloy for stents
CN103266283A (en) * 2013-05-17 2013-08-28 江苏星火特钢有限公司 Non-magnetic stainless steel for ore selection equipment
EP2813906A1 (en) * 2013-06-12 2014-12-17 Nivarox-FAR S.A. Part for clockwork
EP2924514B1 (en) * 2014-03-24 2017-09-13 Nivarox-FAR S.A. Clockwork spring made of austenitic stainless steel
CN104367362A (en) * 2014-11-04 2015-02-25 无锡贺邦金属制品有限公司 Alloy microscopy vascular clamp with antiallergic function
CN106148852A (en) * 2015-04-02 2016-11-23 上海微创医疗器械(集团)有限公司 A kind of alloy material and implantable medical devices
EP3249059A1 (en) * 2016-05-27 2017-11-29 The Swatch Group Research and Development Ltd. Method for thermal treatment of austenitic steels and austenitic steels thus obtained
US10639719B2 (en) 2016-09-28 2020-05-05 General Electric Company Grain boundary engineering for additive manufacturing
CN113737091A (en) * 2021-07-22 2021-12-03 洛阳双瑞特种装备有限公司 Steel for low-magnetism high-strength corrosion-resistant fastener and fastener
CN114606430B (en) * 2022-03-01 2023-05-12 兴机电器有限公司 Low-carbon Fe-Mn-Al-Si TWIP steel and preparation method thereof
CN115652210B (en) * 2022-11-07 2023-05-12 鞍钢股份有限公司 Austenitic stainless steel billet with ultralow carbide content and manufacturing method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2118072A1 (en) * 1971-04-14 1972-10-26 Prvni brnenska strojirna, oborovy podmk, Brunn (Tschechoslowakei) Austenitic steel with high cavitation and erosion resistanc
EP1229142A1 (en) * 2001-02-05 2002-08-07 Daido Tokushuko Kabushiki Kaisha High strength, high corrosion-resistant and non-magnetic stainless steel

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB744599A (en) * 1952-05-30 1956-02-08 Armco Int Corp Stainless steel articles for use at high temperatures
US2698785A (en) * 1952-12-31 1955-01-04 Armco Steel Corp Age-hardening austenitic stainless steel
GB778597A (en) * 1955-02-15 1957-07-10 Ford Motor Co Improvements in or relating to the manufacture of nitrogen-rich wrought austenitic alloys
BE758798A (en) * 1969-11-12 1971-05-12 Crucible Inc AUSTENITIC STAINLESS STEEL
JPH09249940A (en) * 1996-03-13 1997-09-22 Sumitomo Metal Ind Ltd High strength steel excellent insulfide stress cracking resistance and its production
JP4116134B2 (en) * 1998-02-27 2008-07-09 日本冶金工業株式会社 Austenitic stainless steel excellent in high temperature sag resistance and method for producing the same
JP2000192194A (en) * 1998-12-24 2000-07-11 Hitachi Metals Ltd Metal plate of high hardness and high expansion alloy excellent in thermal setting resistance, and its manufacture
EP1194605A1 (en) * 1999-06-24 2002-04-10 Basf Aktiengesellschaft Nickel-poor austenitic steel
JP4178670B2 (en) * 1999-06-28 2008-11-12 セイコーエプソン株式会社 Manganese alloy steel and shaft, screw member
KR100538692B1 (en) * 2003-12-09 2005-12-23 한국기계연구원 High nitrogen stainless steel and method for manufacturing the hige nttrogen stainless steel utllizing low pressure induction melitng
KR100641577B1 (en) * 2005-04-19 2006-10-31 주식회사 포스코 Austenitic Stainless steel with High Mn and N
DE102006033973A1 (en) * 2006-07-20 2008-01-24 Technische Universität Bergakademie Freiberg Stainless austenitic cast steel and its use
KR100926965B1 (en) * 2007-10-02 2009-11-17 한국기계연구원 High strength, high ductility stainless steel rolled sheet using transformation organic plasticity
CN101372721A (en) * 2008-09-19 2009-02-25 山西太钢不锈钢股份有限公司 High vacuum induction furnace nitrogen-containing steel smelting nitrogen pickup method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2118072A1 (en) * 1971-04-14 1972-10-26 Prvni brnenska strojirna, oborovy podmk, Brunn (Tschechoslowakei) Austenitic steel with high cavitation and erosion resistanc
EP1229142A1 (en) * 2001-02-05 2002-08-07 Daido Tokushuko Kabushiki Kaisha High strength, high corrosion-resistant and non-magnetic stainless steel

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
J SIMMONS: "Strain hardening and plastic flow properties of nitrogen-alloyed Fe-17Cr-(8-10)Mn-5Ni austenitic stainless steels", ACTA MATERIALIA, vol. 45, no. 6, 1 June 1997 (1997-06-01), pages 2467-2475, XP055097199, ISSN: 1359-6454, DOI: 10.1016/S1359-6454(96)00343-6 *
See also references of WO2011007921A1 *
WHITE W ET AL: "Metallographic observations on the formation and occurrence of ferrite, sigma phase, and carbides in austenitic stainless steels", METALLOGRAPHY, AMERICAN ELSEVIER, NEW YORK, NY, US, vol. 3, no. 1, 1 March 1970 (1970-03-01), pages 35-50, XP023901147, ISSN: 0026-0800, DOI: 10.1016/0026-0800(70)90003-0 [retrieved on 1970-03-01] *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014206582A3 (en) * 2013-06-27 2015-12-23 Nivarox-Far S.A. Timepiece spring made of austenitic stainless steel
US10048649B2 (en) 2013-06-27 2018-08-14 Nivarox-Far S.A. Timepiece spring made of austenitic stainless steel
EP3147380A1 (en) 2015-09-25 2017-03-29 The Swatch Group Research and Development Ltd. Nickel-free austenitic stainless steel
EP3147378A1 (en) 2015-09-25 2017-03-29 The Swatch Group Research and Development Ltd. Nickel-free austenitic stainless steel
WO2018083311A1 (en) * 2016-11-04 2018-05-11 Richemont International Sa Timepiece resonator
EP3327151A1 (en) * 2016-11-04 2018-05-30 Richemont International S.A. Resonator for a clock piece

Also Published As

Publication number Publication date
US20110226391A1 (en) 2011-09-22
CN102428200A (en) 2012-04-25
CN102428200B (en) 2014-04-02
EP2455508B1 (en) 2016-11-23
EP2455508A4 (en) 2014-03-05
JP2011526969A (en) 2011-10-20
WO2011007921A1 (en) 2011-01-20
JP5272078B2 (en) 2013-08-28

Similar Documents

Publication Publication Date Title
EP2455508B1 (en) High strength / corrosion-resistant,.austenitic stainless steel with carbon - nitrogen complex additive, and method for manufacturing same
JP6214692B2 (en) Austenitic thin stainless steel
KR101535695B1 (en) Austenitic stainless steel low in nickel containing stabilizing elements
JP5335502B2 (en) Martensitic stainless steel with excellent corrosion resistance
RU2394114C2 (en) Austenite steel not containing or with low contents of nickel and item for overhead or underground construction made out of this steel
CN110499455A (en) A kind of age-hardening austenitic stainless steel and preparation method thereof
EP2857126A2 (en) Corrosion and wear resistant cold work tool steel
KR20110136840A (en) Corrosion-resistant austenitic steel
US20130149188A1 (en) C+n austenitic stainless steel having good low-temperature toughness and a fabrication method thereof
KR101089718B1 (en) C+N austenitic stainless steel with high strength and corrosion resistance having tungsten and molybdenum, and fabrication method thereof
CN104726789B (en) Low nickel stainless steel
KR100956283B1 (en) An austenitic stainless steel with high strength and corrosion resistance having carbon and nitrogen
KR101211032B1 (en) High-nitrogen austenitic stainless steels with good Eco-index and excellent pitting corrosion resistance, and fabrication methods thereof
EP3126537B1 (en) Dual-phase stainless steel
EP0446188A1 (en) Stainless steel
JP6388967B2 (en) Duplex stainless steel
KR101089714B1 (en) C+N austenitic stainless steel with high strength and corrosion resistance having tungsten and fabrication method thereof
KR101203539B1 (en) High nitrogen austenitic stainless steels with high mechanical properties and excellent resistance to pitting corrosion and fabrication methods thereof
EP0445094A1 (en) High strength stainless steel
US5242655A (en) Stainless steel
KR101746404B1 (en) Lean duplex stainless steel with improved corrosion resistance and formability and method of manufacturing the same
KR101450177B1 (en) A fabrication method of high nitrogen-low nickel duplex stainless steels
US20180363112A1 (en) Lean duplex stainless steel and method of manufacturing the same
KR101306263B1 (en) High-nitrogen low-nickel duplex stainless steels with an excellent pitting corrosion resistance
JP2019127613A (en) High hardness precipitation hardening stainless steel having excellent hot workability and requiring no sub-zero treatment

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

17P Request for examination filed

Effective date: 20111124

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 MK MT NL NO PL PT RO SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20140204

RIC1 Information provided on ipc code assigned before grant

Ipc: C22C 38/38 20060101AFI20140129BHEP

Ipc: C22C 38/44 20060101ALI20140129BHEP

17Q First examination report despatched

Effective date: 20150407

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20160715

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 MK MT NL NO PL PT RO SE SI SK SM 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: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 848002

Country of ref document: AT

Kind code of ref document: T

Effective date: 20161215

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602009042700

Country of ref document: DE

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

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: 20161123

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20161123

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 848002

Country of ref document: AT

Kind code of ref document: T

Effective date: 20161123

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

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: 20170224

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: 20161123

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: 20161123

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: 20161123

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: 20170223

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

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: 20161123

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: 20161123

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: 20161123

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: 20161123

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: 20170323

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: 20161123

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: 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: 20161123

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: 20161123

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: 20161123

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: 20161123

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: 20161123

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602009042700

Country of ref document: DE

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

Ref country code: SM

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: 20161123

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: 20161123

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: 20170223

Ref country code: IT

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: 20161123

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: 20170824

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: 20161123

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: 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: 20161123

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

Ref country code: LI

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

Effective date: 20170831

Ref country code: CH

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

Effective date: 20170831

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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 NON-PAYMENT OF DUE FEES

Effective date: 20170820

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: IE

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

Effective date: 20170820

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 NON-PAYMENT OF DUE FEES

Effective date: 20170820

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: 20090820

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

Ref country code: CY

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

Effective date: 20161123

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

Ref country code: MK

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: 20161123

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: 20161123

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

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: 20170323

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 602009042700

Country of ref document: DE

Representative=s name: DEHNS GERMANY PATENT AND TRADEMARK ATTORNEYS, DE

Ref country code: DE

Ref legal event code: R081

Ref document number: 602009042700

Country of ref document: DE

Owner name: KOREA INSTITUTE OF MATERIALS SCIENCE, CHANGWON, KR

Free format text: FORMER OWNER: KOREA INSTITUTE OF MACHINERY & MATERIALS, DAJEON, KR

Ref country code: DE

Ref legal event code: R082

Ref document number: 602009042700

Country of ref document: DE

Representative=s name: DEHNS GERMANY, DE

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20210325 AND 20210331

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

Ref country code: GB

Payment date: 20230629

Year of fee payment: 15

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

Ref country code: FR

Payment date: 20230703

Year of fee payment: 15

Ref country code: DE

Payment date: 20230627

Year of fee payment: 15