EP3395989A1 - Austenitic steel material having excellent hydrogen-embrittlement resistance - Google Patents

Austenitic steel material having excellent hydrogen-embrittlement resistance Download PDF

Info

Publication number
EP3395989A1
EP3395989A1 EP16879356.0A EP16879356A EP3395989A1 EP 3395989 A1 EP3395989 A1 EP 3395989A1 EP 16879356 A EP16879356 A EP 16879356A EP 3395989 A1 EP3395989 A1 EP 3395989A1
Authority
EP
European Patent Office
Prior art keywords
steel material
less
austenitic steel
hydrogen
austenite
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
EP16879356.0A
Other languages
German (de)
French (fr)
Other versions
EP3395989A4 (en
EP3395989B1 (en
Inventor
Soon-Gi Lee
Sung-Kyu Kim
Sang-Deok Kang
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.)
Posco Holdings Inc
Original Assignee
Posco 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 Posco Co Ltd filed Critical Posco Co Ltd
Publication of EP3395989A1 publication Critical patent/EP3395989A1/en
Publication of EP3395989A4 publication Critical patent/EP3395989A4/en
Application granted granted Critical
Publication of EP3395989B1 publication Critical patent/EP3395989B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C21D6/004Heat treatment of ferrous alloys containing Cr and Ni
    • 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 of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • 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
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/06Ferrous alloys, e.g. steel alloys containing aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/08Ferrous alloys, e.g. steel alloys containing nickel
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/12Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/16Ferrous alloys, e.g. steel alloys containing copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous 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
    • 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
    • C21D2211/008Martensite

Definitions

  • the present disclosure relates to an austenitic steel material having high hydrogen-embrittlement resistance, and more particularly, to an austenitic steel material having high hydrogen-embrittlement resistance and suitable for applications such as high-pressure hydrogen gas tanks, pipes, and transfer facilities.
  • Hydrogen vehicles including high-pressure gas containers for storing hydrogen compressed to high pressure, are the most common type of hydrogen vehicles, and such containers are required to have high strength for durability against high pressure, low hydrogen permeability for minimizing the loss of hydrogen caused by the penetration of hydrogen, and high hydrogen-embrittlement resistance for preventing embrittlement caused by hydrogen permeation.
  • FCC-structure materials having high hydrogen permeability may be suitable therefor.
  • a representative FCC-structure material used for these applications is Cr-Ni-based austenitic stainless steel.
  • Such austenitic stainless steels are used as materials for high-pressure gas containers or liners and pipes of high-pressure gas containers owing to their high hydrogen-embrittlement resistance under high-pressure hydrogen gas environments.
  • Japanese Patent Application Laid-open Publication No. H5-98391 and International Patent Publication No. 2014-111285 disclose a technique of increasing the strength of austenitic stainless steel by cold working.
  • ductility and toughness decrease, and the stability of austenite decreases, thereby causing the formation of strain-induced martensite.
  • this technique is not suitable for hydrogen containers.
  • Korean Patent Application Laid-Open Publication No. 10-2006-0018250 discloses a technique of securing the stability of austenite by performing a cold working process twice in different directions. According to the technique, however, chromium (Cr) and nickel (Ni), expensive alloying elements, are added in large amounts to increase the stability of austenite, thereby incurring high costs.
  • Korean Patent Application Laid-Open Publication No. 10-2011-0004491 and Korean Patent Application Laid-Open Publication No. 10-2013-0045931 disclose a technique of guaranteeing the formation of stable austenite and thus improving the hydrogen-embrittlement resistance of austenitic stainless steel by replacing nickel (Ni), an expensive alloying element, with manganese (Mn), an inexpensive alloying element.
  • Ni nickel
  • Mn manganese
  • this technique still uses a large amount of an expensive alloying element, commercialization of the technique is limited in terms of economical aspects.
  • An aspect of the present disclosure may provide an austenitic steel material having high hydrogen-embrittlement resistance without expensive alloying elements.
  • an austenitic steel material having high hydrogen-embrittlement resistance may include, by wt%, carbon (C): 0.1% to 0.5%, copper (Cu): 5% or less (excluding 0%), nitrogen (N) : 1% or less (excluding 0%), manganese (Mn) : [Mn] ⁇ 10.7[C]+24.5, chromium (Cr): 10% or less, nickel (Ni): 5% or less, molybdenum (Mo): 5% or less, silicon (Si): 4% or less, aluminum (Al): 5% or less, and a balance of iron (Fe) and inevitable impurities, wherein the austenitic steel material has a T-El 2 /T-El 1 ratio of 0.5 or greater, where T-El 2 is an elongation at break in a tensile test performed under high-pressure hydrogen conditions of 25°C and 70 MPa, and T-El 1 is an elongation at break in
  • the austenitic steel material of the present disclosure has high hydrogen-embrittlement resistance without expensive alloying elements.
  • Containers for storing and transferring hydrogen are basically required to have low hydrogen permeability, and thus it is needed to guarantee the formation of an FCC structure having low hydrogen permeability in the case of steel materials for hydrogen containers. In particular, it is necessary to stably maintain the FCC structure in spite of externally-caused deformation such as deformation caused by plastic working or plastic deformation caused by an external load applied during use.
  • the inventors have tried to improve the hydrogen-embrittlement resistance of steel materials by properly adjusting a relationship between carbon and manganese while relatively decreasing the content of carbon, and as a result, the inventors have invented the present invention.
  • alloying elements of the austenitic steel material and the content ranges of the alloying elements will be described in detail.
  • the content of each element is given in wt% unless otherwise mentioned.
  • Carbon (C) is an element stabilizing austenite and increasing the strength of the steel material. Particularly, carbon (C) decreases transformation points Ms and Md at which austenite transforms into ⁇ -martensite or ⁇ -martensite during a cooling or processing process. If the content of carbon (C) is insufficient, the stability of austenite is insufficient, and austenite easily undergoes strain-induced transformation into ⁇ -martensite or ⁇ -martensite by external stress. Therefore, an FCC structure may not be maintained, and thus hydrogen-embrittlement resistance may markedly decrease.
  • the content of carbon (C) be within the range of 0.1% or greater, more preferably within the range of 0.15% or greater, and even more preferably within the range of 0.2% or greater.
  • the content of carbon (C) may be adjusted to be within the range of 0.5% or less, and more preferably within the range of 0.45% or less.
  • the content of manganese (Mn) may be determined by considering a relationship with carbon (C) and other alloying elements.
  • FIG. 1 illustrates a manganese content range for improving hydrogen-embrittlement resistance by stably guaranteeing austenite or ⁇ -martensite having low hydrogen permeability after a room-temperature tensile test.
  • the graph of FIG. 1 shows results that the inventors have obtained through various experiments.
  • the content of manganese (Mn) may preferably be adjusted to be within the range of -10.7[C]+24.5(%) or greater on the condition that the contents of the other elements are within ranges proposed in the present disclosure. If the content of manganese (Mn) is less than - 10.7[C]+24.5(%), the stability of austenite may decrease, and thus a BCC-based microstructure may be formed by deformation, thereby decreasing hydrogen-embrittlement resistance.
  • Copper (Cu) stabilizes austenite guaranteeing hydrogen-embrittlement resistance and facilitates slipping by increasing stacking fault energy. If the content of carbon (C) is high, since copper (Cu) has very low solid solubility in carbides and diffuses slowly in austenite, copper (Cu) concentrates along boundaries of carbide nuclei formed in austenite, thereby suppressing the diffusion of carbon (C) and effectively retarding the growth of carbides. As a result, copper (Cu) suppresses the formation of carbides. Owing to this suppression of carbide formation, sites to which carbon (C) diffuses are decreased, thereby improving the hydrogen-embrittlement resistance of the steel material and the ductility and toughness of the steel material as well.
  • the content of copper (Cu) is 0.5% or greater, this effect of suppressing the formation of carbides may be sufficiently obtained.
  • the content of copper (Cu) is excessively high, the hot workability of the steel material may deteriorate. Therefore, according to the present disclosure, it may be preferable that the content of copper (Cu) be adjusted to be within the range of 5% or less, and more preferably within the range of 3.5% or less.
  • nitrogen (N) is an element stabilizing austenite and thus improving the toughness of the steel material. Particularly, like carbon (C), nitrogen (N) is very effective in improving the strength of the steel material by the effect of solid solution strengthening. Moreover, as illustrated in Formula 1, nitrogen (N) is known as an element effectively increasing stacking fault energy and thus promoting slipping. In the present disclosure, however, intended properties may be obtained without great difficulties even when nitrogen (N) is not added. Conversely, if the content of nitrogen (N) is excessively high, coarse nitrides may be formed, and thus the surface quality and properties of the steel material may deteriorate. Thus, it may be preferable that the content of nitrogen (N) be adjusted to be within the range of 1% or less, and more preferably within the range of 0.5% or less.
  • the austenitic steel material of the present disclosure may further include chromium (Cr), nickel (Ni), molybdenum (Mo), silicon (Si), and aluminum (Al).
  • chromium (Cr) When the content of chromium (Cr) is within a proper range, chromium (Cr) increases hydrogen-embrittlement resistance by stabilizing austenite, and increases the strength of the steel material dissolved in austenite. Furthermore, chromium (Cr) is an element improving the corrosion resistance of the steel material. In the present disclosure, however, intended properties may be obtained without great difficulties even when chromium (Cr) is not added. In addition, since chromium (Cr) is a carbide forming element, if the content of chromium (Cr) is excessively high, carbides may be formed along austenite grain boundaries. Therefore, sites facilitating hydrogen diffusion may be provided, and the toughness of the steel material may decrease. Therefore, according to the present disclosure, it may be preferable that the content of chromium (Cr) be adjusted to be within the range of 10% or less, and more preferably within the range of 8% or less.
  • Nickel (Ni) is an element very effective in stabilizing austenite. Particularly, nickel (Ni) decreases transformation points Ms and Md at which austenite transforms into ⁇ -martensite or ⁇ -martensite during a cooling or processing process. Moreover, as illustrated in Formula 1, nickel (Ni) is known as an element effectively increasing stacking fault energy and thus promoting slipping. In the present disclosure, however, intended properties may be obtained without great difficulties even when nickel (Ni) is not added. Since nickel (Ni) is an expensive element, if the content of nickel (Ni) is excessively high, the economical feasibility of the steel material decreases. Therefore, according to the present disclosure, it may be preferable that the content of nickel (Ni) be within the range of 5% or less.
  • molybdenum (Mo) stabilizes austenite and improves the hydrogen-embrittlement resistance of the steel material by decreasing transformation points Ms and Md at which austenite transforms into ⁇ -martensite or ⁇ -martensite during a cooling or processing process.
  • molybdenum (Mo) dissolves in the steel material and improves the strength of the steel material.
  • molybdenum (Mo) segregates along grain boundaries of austenite, thereby improving the stability of grain boundaries and decreasing the energy of grain boundaries. As a result, molybdenum (Mo) suppresses the precipitation of carbides along grain boundaries.
  • molybdenum (Mo) is known as an element effectively increasing stacking fault energy and thus promoting slipping. In the present disclosure, however, intended properties may be obtained without great difficulties even when molybdenum (Mo) is not added. Since molybdenum (Mo) is an expensive element, if the content of molybdenum (Mo) is excessively high, the economical feasibility of the steel material decreases. Therefore, according to the present disclosure, it may be preferable that the content of molybdenum (Mo) be adjusted to be within the range of 5% or less, and more preferably, within the range of 4% or less.
  • Silicon (Si) improves the castability of molten steel.
  • silicon (Si) added to the austenitic steel material, dissolves in the austenitic steel material and effectively increases the strength of the austenitic steel material.
  • intended properties may be obtained without great difficulties even when silicon (Si) is not added. If the content of silicon (Si) is excessively high, stacking fault energy decreases, thereby causing partial dislocations and concentration of stress and thus decreasing the hydrogen-embrittlement resistance of the steel material. Therefore, according to the present disclosure, it may be preferable that the content of silicon (Si) be within the range of 4% or less.
  • aluminum (Al) stabilizes austenite and improves the hydrogen-embrittlement resistance of the steel material by decreasing transformation points Ms and Md at which austenite transforms into ⁇ -martensite or ⁇ -martensite during a cooling or processing process.
  • aluminum (Al) dissolves in the steel material and increases the strength of the steel material.
  • aluminum (Al) affects the mobility of carbon (C) in the steel material and effectively suppresses the formation of carbides, thereby increasing the toughness of the steel material.
  • aluminum (Al) induces cross slips by markedly increasing stacking fault energy, and suppresses partial dislocations and thus decreases concentration of stress, thereby increasing hydrogen-embrittlement resistance.
  • intended properties may be obtained without great difficulties even when aluminum (Al) is not added.
  • aluminum (Al) may be added in an amount of 0.2% or greater so as to further improve hydrogen-embrittlement resistance.
  • the content of aluminum (Al) is excessively high, the castability and surface quality of steel may deteriorate because of the formation of oxides and nitrides.
  • the other element of the austenitic steel material is iron (Fe).
  • Fe iron
  • impurities of raw materials or manufacturing environments may be inevitably included in the austenitic steel material, and such impurities may not be removed from the austenitic steel material.
  • Such impurities are well-known to those of ordinary skill in the art, and thus descriptions thereof will not be given in the present disclosure.
  • addition of effective elements other than the above-described elements is not excluded.
  • the austenitic steel material of the present disclosure may have stacking fault energy (SEF) expressed by Formula 1 below within the range of 30 mJ/m 2 or greater.
  • SFE mJ / m 2 1.6 Ni ⁇ 1.3 Mn + 0.06 Mn 2 ⁇ 1.7 Cr + 0.01 Cr 2 + 15 Mo ⁇ 5.6 Si + 1.6 Cu + 5.5 Al ⁇ 60 ( C + 1.2 N ) 1 / 2 + 26.3 C + 1.2 N Cr + Mn + Mo 1 / 2 + 0.6 Ni Cr + Mn ⁇ 1 / 2 (where each of [Ni], [Mn], [Cr], [Mo], [Si], [Cu], [Al], [C], and [N] refers to the content (wt%) of a corresponding element).
  • high-manganese steels having a high manganese content like the austenitic steel material of the present disclosure have relatively low stacking fault energy compared to general carbon steels and thus easily have partial dislocations, and since slipping of such partial dislocations is limited to particular slip planes, dislocation accumulation and stress concentration are easily caused.
  • concentration of stress facilitates diffusion of hydrogen, and thus a phenomenon in which the fracture strength of a material decreases because of diffusion of hydrogen, that is, embrittlement caused by hydrogen, is likely to occur in high-manganese steels like the austenitic steel material of the present disclosure. Therefore, according to the present disclosure, the deformation behavior of the austenitic steel material is particularly controlled by adjusting stacking fault energy through control of alloying elements and contents thereof. Based on results of research conducted by the inventors, the inventors have found that if stacking fault energy defined by Formula 1 above is adjusted to be 30 mJ/m 2 or greater, the possibility of hydrogen embrittlement is markedly reduced.
  • the degree of work hardening of a steel material caused by concentration of stress may be measured by measuring a strain hardening rate in a tensile test.
  • the austenitic steel material of the present disclosure may have a strain hardening rate of 14000 N/mm 2 or less in a tensile test performed under atmospheric conditions of 25°C and 1 atm.
  • the strain hardening rate may be calculated from true strain and true stress. If the strain hardening rate in a tensile test is greater than 14000 N/mm 2 , concentration of stress caused by dislocations is excessively high, and thus hydrogen easily diffuses and accumulates. Thus, hydrogen embrittlement may occur.
  • the austenitic steel material of the present disclosure may have a tensile strength of 800 MPa or less in a tensile test performed under atmospheric conditions of 25°C and 1 atm. If the tensile strength of the austenitic steel material is greater than 800 MPa, hydrogen-embrittlement resistance may deteriorate because of high work hardening caused by concentration of stress.
  • the austenitic steel material of the present disclosure may have a microstructure including austenite in an area fraction of 95% or greater. If the area fraction of austenite is less than 95%, intended hydrogen-embrittlement resistance may not be obtained.
  • the microstructure of the austenitic steel material of the present disclosure may be austenite, or ⁇ -martensite and austenite after a tensile test performed under atmospheric conditions of 25°C and 1 atm. If the microstructure of the austenitic steel material has ferrite, intended hydrogen-embrittlement resistance may not be obtained.
  • the austenitic steel material of the present disclosure may be manufactured by a general steel material manufacturing method using a steel slab having the above-described composition.
  • the austenitic steel material of the present disclosure may be manufactured by reheating, rough rolling, finish rolling, and cooling a steel slab having the above-described composition.
  • the temperature of the finish rolling process may be adjusted to be greater than a non-crystallization temperature. If the finish rolling process is performed at a temperature equal to or lower than the non-crystallization temperature, the strength of the steel material may be excessively high due to excessive formation and accumulation of dislocations, thereby promoting concentration of stress and fracture caused by hydrogen. In addition, ferrite inducing hydrogen embrittlement during tensile deformation may be early formed, and thus it may be difficult to obtain intended hydrogen-embrittlement resistance.
  • the steel material may be cooled through an accelerated cooling process after a rolling process, so as to suppress the formation of carbides.
  • the reason for this is that if carbides are formed, the elongation of the steel material decreases, and in particular, hydrogen accumulates along boundaries between carbides and austenite, thereby decreasing hydrogen-embrittlement resistance.
  • elements such as carbon (C), chromium (Cr), and molybdenum (Mo) are main carbide forming elements, whether or not to perform accelerated cooling and the rate of accelerated cooling are determined according to the contents of such elements as expressed by the following formula. Cooling rate ° C / s ⁇ 15 C + Cr + Mo (where each of [C], [Cr], and [Mo] refers to the content (wt%) of a corresponding element).
  • each of Inventive Examples 1 to 5 satisfying the composition ranges proposed in the present disclosure had stable austenite without ferrite, a low strain hardening rate, and low tensile strength.
  • Inventive Examples 1 to 5 were rolled at a finish rolling temperature higher than a non-crystallization temperature, the formation and accumulation of dislocations were suppressed, and since Inventive Examples 1 to 5 were cooled at a cooling rate satisfying the range proposed in the present disclosure, the formation of carbides was effectively suppressed.
  • austenitic steel materials having high hydrogen-embrittlement resistance that is, having a high elongation at break ratio, could be obtained.
  • Comparative Example 1 had carbon and manganese contents outside the ranges proposed in the present disclosure and particularly, a high strain hardening rate because of an excessively high carbon content, and thus, the elongation at break ratio of Comparative Example 1 was low. That is, Comparative Example 1 had poor hydrogen-embrittlement resistance.
  • Comparative Example 2 having a manganese content outside of the range proposed in the present disclosure, austenite was unstable, and thus ferrite susceptible to hydrogen embrittlement was formed after tensile deformation. That is, Comparative Example 2 had poor hydrogen-embrittlement resistance.
  • Comparative Example 3 having carbon and manganese contents and stacking fault energy within the ranges proposed in the present disclosure but a copper content greater than the range proposed in the present disclosure, cracks were formed in the rolled material, and thus a normal specimen could not obtained.
  • Comparative Example 4 had a carbon content greater than the range proposed in the present disclosure, Comparative Example 4 had a high strain hardening rate and carbides excessively precipitated along austenite grain boundaries, and thus the hydrogen-embrittlement resistance of Comparative Example 4 was poor.
  • Comparative Example 5 had a manganese content outside the range proposed in the present disclosure, an intended microstructure could not be obtained, and thus the hydrogen-embrittlement resistance of Comparative Example 5 was poor.
  • FIG. 2 is an image of a fracture surface of a specimen of Inventive Example 1 after the room-temperature tensile test. Referring to FIG. 2 , fracture occurred in a dimple type which is typical of ductile fracture.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)

Abstract

Disclosed is an austenitic material having excellent hydrogen-embrittlement resistance, comprising, by weight, 0.1-0.5% of C, 5% or less (0% exclusive) of Cu, 1% or less (0% exclusive) of N, a content of Mn satisfying Mn ‰¥-10.7C+24.5, 10% or less of Cr, 5% or less of Ni, 5% or less of Mo, 4% or less of Si, 5% or less of Al, and a balance amount of Fe and inevitable impurities, with a T-El 2 /T-El 1 ratio of 0.5 or higher, wherein T-El 1 is an elongation at break according to a tensile test at 25°C under an atmospheric condition of 1 atm and T-El 2 is an elongation at break according to a tensile test at 25°C under a hydrogen condition of 70 MPa.

Description

    [Technical Field]
  • The present disclosure relates to an austenitic steel material having high hydrogen-embrittlement resistance, and more particularly, to an austenitic steel material having high hydrogen-embrittlement resistance and suitable for applications such as high-pressure hydrogen gas tanks, pipes, and transfer facilities.
  • [Background Art]
  • Many efforts have been made to reduce environmental pollutants and greenhouse gas emissions for the prevention of global warming and environmental pollution. Thereamong, a technology using hydrogen as an energy source has made a great deal of progress in recent years. Unlike fossil fuels such as coal and petroleum, hydrogen, the most environmentally friendly energy source, is attracting attention as a novel energy source for the future with little emission of pollutants. In particular, there is great interest in hydrogen as a fuel for hydrogen vehicles using fuel cells.
  • Hydrogen vehicles, including high-pressure gas containers for storing hydrogen compressed to high pressure, are the most common type of hydrogen vehicles, and such containers are required to have high strength for durability against high pressure, low hydrogen permeability for minimizing the loss of hydrogen caused by the penetration of hydrogen, and high hydrogen-embrittlement resistance for preventing embrittlement caused by hydrogen permeation.
  • Basically, hydrogen storage containers and facilities are aimed at reducing storage loss caused by penetration of hydrogen, and thus face centered cubic (FCC)-structure materials having high hydrogen permeability may be suitable therefor. A representative FCC-structure material used for these applications is Cr-Ni-based austenitic stainless steel. Such austenitic stainless steels are used as materials for high-pressure gas containers or liners and pipes of high-pressure gas containers owing to their high hydrogen-embrittlement resistance under high-pressure hydrogen gas environments.
  • In recent years, however, hydrogen gas is used at high pressures on the level of tens or hundreds of megapascals (MPa) for enabling long-distance driving and the storage of a large amount of hydrogen through a single operation of charging hydrogen. Therefore, in the case of using austenitic stainless steels having ordinary strength, a large thickness is required to withstand loads under high-pressure conditions, and thus, it may be difficult to avoid an increase in the weight and size of containers or facilities, thereby limiting commercialization thereof.
  • As a technique for solving these problems, Japanese Patent Application Laid-open Publication No. H5-98391 and International Patent Publication No. 2014-111285 disclose a technique of increasing the strength of austenitic stainless steel by cold working. However, when strength is increased by cold working, ductility and toughness decrease, and the stability of austenite decreases, thereby causing the formation of strain-induced martensite. Thus, this technique is not suitable for hydrogen containers. In addition, Korean Patent Application Laid-Open Publication No. 10-2006-0018250 discloses a technique of securing the stability of austenite by performing a cold working process twice in different directions. According to the technique, however, chromium (Cr) and nickel (Ni), expensive alloying elements, are added in large amounts to increase the stability of austenite, thereby incurring high costs.
  • In addition, Korean Patent Application Laid-Open Publication No. 10-2011-0004491 and Korean Patent Application Laid-Open Publication No. 10-2013-0045931 disclose a technique of guaranteeing the formation of stable austenite and thus improving the hydrogen-embrittlement resistance of austenitic stainless steel by replacing nickel (Ni), an expensive alloying element, with manganese (Mn), an inexpensive alloying element. However, since this technique still uses a large amount of an expensive alloying element, commercialization of the technique is limited in terms of economical aspects.
  • [Disclosure] [Technical Problem]
  • An aspect of the present disclosure may provide an austenitic steel material having high hydrogen-embrittlement resistance without expensive alloying elements.
  • [Technical Solution]
  • According to an aspect of the present disclosure, an austenitic steel material having high hydrogen-embrittlement resistance may include, by wt%, carbon (C): 0.1% to 0.5%, copper (Cu): 5% or less (excluding 0%), nitrogen (N) : 1% or less (excluding 0%), manganese (Mn) : [Mn]≥10.7[C]+24.5, chromium (Cr): 10% or less, nickel (Ni): 5% or less, molybdenum (Mo): 5% or less, silicon (Si): 4% or less, aluminum (Al): 5% or less, and a balance of iron (Fe) and inevitable impurities, wherein the austenitic steel material has a T-El2/T-El1 ratio of 0.5 or greater, where T-El2 is an elongation at break in a tensile test performed under high-pressure hydrogen conditions of 25°C and 70 MPa, and T-El1 is an elongation at break in a tensile test performed under atmospheric conditions of 25°C and 1 atm.
  • [Advantageous Effects]
  • One of various effects of the present disclosure is that the austenitic steel material of the present disclosure has high hydrogen-embrittlement resistance without expensive alloying elements.
  • [Description of Drawings]
    • FIG. 1 is a graph illustrating carbon and manganese content ranges according to the present disclosure.
    • FIG. 2 is an image of a fracture surface of a specimen of Inventive Example 1 after a room-temperature tensile test.
    [Best Mode]
  • Containers for storing and transferring hydrogen are basically required to have low hydrogen permeability, and thus it is needed to guarantee the formation of an FCC structure having low hydrogen permeability in the case of steel materials for hydrogen containers. In particular, it is necessary to stably maintain the FCC structure in spite of externally-caused deformation such as deformation caused by plastic working or plastic deformation caused by an external load applied during use.
  • Furthermore, in recent years, attempts have been constantly made to address the above-described economical demerits of austenitic stainless steels, existing steel materials having high hydrogen-embrittlement resistance, by replacing expensive nickel with inexpensive manganese and adding carbon to stabilize austenite at room temperature. However, in such high-carbon, high-manganese austenitic steel materials, planar slips easily occur because partial dislocations easily develop owing to low stacking fault energy, and thus dislocations easily accumulate on slip planes to result in high work hardening. In addition, the addition of carbon for stabilizing austenite induces dynamic strain aging and thus markedly improves work hardening of the steel materials. Therefore, such high-carbon, high-manganese austenitic steel materials are not suitable for applications requiring hydrogen-embrittlement resistance.
  • Thus, the inventors have tried to improve the hydrogen-embrittlement resistance of steel materials by properly adjusting a relationship between carbon and manganese while relatively decreasing the content of carbon, and as a result, the inventors have invented the present invention.
  • Hereinafter, an austenitic steel material having high hydrogen-embrittlement resistance will be described in detail, according to an aspect of the present disclosure.
  • First, alloying elements of the austenitic steel material and the content ranges of the alloying elements will be described in detail. In the following description, the content of each element is given in wt% unless otherwise mentioned.
  • Carbon (C): 0.1% to 0.5%
  • Carbon (C) is an element stabilizing austenite and increasing the strength of the steel material. Particularly, carbon (C) decreases transformation points Ms and Md at which austenite transforms into ε-martensite or α-martensite during a cooling or processing process. If the content of carbon (C) is insufficient, the stability of austenite is insufficient, and austenite easily undergoes strain-induced transformation into ε-martensite or α-martensite by external stress. Therefore, an FCC structure may not be maintained, and thus hydrogen-embrittlement resistance may markedly decrease. Therefore, according to the present disclosure, it may be preferable that the content of carbon (C) be within the range of 0.1% or greater, more preferably within the range of 0.15% or greater, and even more preferably within the range of 0.2% or greater. However, if the content of carbon (C) is excessively high, dislocations and dynamic strain aging may occur to result in an increase in the work hardening of the steel material and a decrease in the hydrogen-embrittlement resistance of the steel material, and carbides may easily precipitate to result in a decrease in the ductility or toughness of the steel material. Therefore, according to the present disclosure, it may be preferable that the content of carbon (C) be adjusted to be within the range of 0.5% or less, and more preferably within the range of 0.45% or less.
  • Manganese (Mn): [Mn]≥10.7[C]+24.5 (where each of [Mn] and [C] refers to the weight percent (wt%) of a corresponding element)
  • In the present disclosure, the content of manganese (Mn) may be determined by considering a relationship with carbon (C) and other alloying elements. FIG. 1 illustrates a manganese content range for improving hydrogen-embrittlement resistance by stably guaranteeing austenite or ε-martensite having low hydrogen permeability after a room-temperature tensile test. The graph of FIG. 1 shows results that the inventors have obtained through various experiments.
  • That is, to obtain a microstructure having high hydrogen-embrittlement resistance before and after a tensile test, the content of manganese (Mn) may preferably be adjusted to be within the range of -10.7[C]+24.5(%) or greater on the condition that the contents of the other elements are within ranges proposed in the present disclosure. If the content of manganese (Mn) is less than - 10.7[C]+24.5(%), the stability of austenite may decrease, and thus a BCC-based microstructure may be formed by deformation, thereby decreasing hydrogen-embrittlement resistance.
  • Copper (Cu): 5% or less (excluding 0%)
  • Copper (Cu) stabilizes austenite guaranteeing hydrogen-embrittlement resistance and facilitates slipping by increasing stacking fault energy. If the content of carbon (C) is high, since copper (Cu) has very low solid solubility in carbides and diffuses slowly in austenite, copper (Cu) concentrates along boundaries of carbide nuclei formed in austenite, thereby suppressing the diffusion of carbon (C) and effectively retarding the growth of carbides. As a result, copper (Cu) suppresses the formation of carbides. Owing to this suppression of carbide formation, sites to which carbon (C) diffuses are decreased, thereby improving the hydrogen-embrittlement resistance of the steel material and the ductility and toughness of the steel material as well. In the present disclosure, if the content of copper (Cu) is 0.5% or greater, this effect of suppressing the formation of carbides may be sufficiently obtained. However, if the content of copper (Cu) is excessively high, the hot workability of the steel material may deteriorate. Therefore, according to the present disclosure, it may be preferable that the content of copper (Cu) be adjusted to be within the range of 5% or less, and more preferably within the range of 3.5% or less.
  • Nitrogen (N): 1% or less (excluding 0%)
  • Like carbon (C), nitrogen (N) is an element stabilizing austenite and thus improving the toughness of the steel material. Particularly, like carbon (C), nitrogen (N) is very effective in improving the strength of the steel material by the effect of solid solution strengthening. Moreover, as illustrated in Formula 1, nitrogen (N) is known as an element effectively increasing stacking fault energy and thus promoting slipping. In the present disclosure, however, intended properties may be obtained without great difficulties even when nitrogen (N) is not added. Conversely, if the content of nitrogen (N) is excessively high, coarse nitrides may be formed, and thus the surface quality and properties of the steel material may deteriorate. Thus, it may be preferable that the content of nitrogen (N) be adjusted to be within the range of 1% or less, and more preferably within the range of 0.5% or less.
  • In addition to the above-described elements, the austenitic steel material of the present disclosure may further include chromium (Cr), nickel (Ni), molybdenum (Mo), silicon (Si), and aluminum (Al).
  • Chromium (Cr): 10% or less
  • When the content of chromium (Cr) is within a proper range, chromium (Cr) increases hydrogen-embrittlement resistance by stabilizing austenite, and increases the strength of the steel material dissolved in austenite. Furthermore, chromium (Cr) is an element improving the corrosion resistance of the steel material. In the present disclosure, however, intended properties may be obtained without great difficulties even when chromium (Cr) is not added. In addition, since chromium (Cr) is a carbide forming element, if the content of chromium (Cr) is excessively high, carbides may be formed along austenite grain boundaries. Therefore, sites facilitating hydrogen diffusion may be provided, and the toughness of the steel material may decrease. Therefore, according to the present disclosure, it may be preferable that the content of chromium (Cr) be adjusted to be within the range of 10% or less, and more preferably within the range of 8% or less.
  • Nickel (Ni): 5% or less
  • Nickel (Ni) is an element very effective in stabilizing austenite. Particularly, nickel (Ni) decreases transformation points Ms and Md at which austenite transforms into ε-martensite or α-martensite during a cooling or processing process. Moreover, as illustrated in Formula 1, nickel (Ni) is known as an element effectively increasing stacking fault energy and thus promoting slipping. In the present disclosure, however, intended properties may be obtained without great difficulties even when nickel (Ni) is not added. Since nickel (Ni) is an expensive element, if the content of nickel (Ni) is excessively high, the economical feasibility of the steel material decreases. Therefore, according to the present disclosure, it may be preferable that the content of nickel (Ni) be within the range of 5% or less.
  • Molybdenum (Mo): 5% or less
  • If molybdenum (Mo) is added to the steel material in an appropriate amount, molybdenum (Mo) stabilizes austenite and improves the hydrogen-embrittlement resistance of the steel material by decreasing transformation points Ms and Md at which austenite transforms into ε-martensite or α-martensite during a cooling or processing process. In addition, molybdenum (Mo) dissolves in the steel material and improves the strength of the steel material. In addition, molybdenum (Mo) segregates along grain boundaries of austenite, thereby improving the stability of grain boundaries and decreasing the energy of grain boundaries. As a result, molybdenum (Mo) suppresses the precipitation of carbides along grain boundaries. Moreover, as illustrated in Formula 1, molybdenum (Mo) is known as an element effectively increasing stacking fault energy and thus promoting slipping. In the present disclosure, however, intended properties may be obtained without great difficulties even when molybdenum (Mo) is not added. Since molybdenum (Mo) is an expensive element, if the content of molybdenum (Mo) is excessively high, the economical feasibility of the steel material decreases. Therefore, according to the present disclosure, it may be preferable that the content of molybdenum (Mo) be adjusted to be within the range of 5% or less, and more preferably, within the range of 4% or less.
  • Silicon (Si): 4% or less
  • Silicon (Si) improves the castability of molten steel. In particular, silicon (Si), added to the austenitic steel material, dissolves in the austenitic steel material and effectively increases the strength of the austenitic steel material. In the present disclosure, however, intended properties may be obtained without great difficulties even when silicon (Si) is not added. If the content of silicon (Si) is excessively high, stacking fault energy decreases, thereby causing partial dislocations and concentration of stress and thus decreasing the hydrogen-embrittlement resistance of the steel material. Therefore, according to the present disclosure, it may be preferable that the content of silicon (Si) be within the range of 4% or less.
  • Aluminum (Al): 5% or less
  • If aluminum (Al) is added to the steel material in an appropriate amount, aluminum (Al) stabilizes austenite and improves the hydrogen-embrittlement resistance of the steel material by decreasing transformation points Ms and Md at which austenite transforms into ε-martensite or α-martensite during a cooling or processing process. In addition, aluminum (Al) dissolves in the steel material and increases the strength of the steel material. In addition, aluminum (Al) affects the mobility of carbon (C) in the steel material and effectively suppresses the formation of carbides, thereby increasing the toughness of the steel material. In addition, aluminum (Al) induces cross slips by markedly increasing stacking fault energy, and suppresses partial dislocations and thus decreases concentration of stress, thereby increasing hydrogen-embrittlement resistance. In the present disclosure, however, intended properties may be obtained without great difficulties even when aluminum (Al) is not added. Preferably, aluminum (Al) may be added in an amount of 0.2% or greater so as to further improve hydrogen-embrittlement resistance. Conversely, if the content of aluminum (Al) is excessively high, the castability and surface quality of steel may deteriorate because of the formation of oxides and nitrides. Thus, it may be preferable that the content of aluminum (Al) be adjusted to be within the range of 5% or less.
  • The other element of the austenitic steel material is iron (Fe). However, impurities of raw materials or manufacturing environments may be inevitably included in the austenitic steel material, and such impurities may not be removed from the austenitic steel material. Such impurities are well-known to those of ordinary skill in the art, and thus descriptions thereof will not be given in the present disclosure. In addition, addition of effective elements other than the above-described elements is not excluded.
  • For example, the austenitic steel material of the present disclosure may have stacking fault energy (SEF) expressed by Formula 1 below within the range of 30 mJ/m2 or greater. SFE mJ / m 2 = 1.6 Ni 1.3 Mn + 0.06 Mn 2 1.7 Cr + 0.01 Cr 2 + 15 Mo 5.6 Si + 1.6 Cu + 5.5 Al 60 ( C + 1.2 N ) 1 / 2 + 26.3 C + 1.2 N Cr + Mn + Mo 1 / 2 + 0.6 Ni Cr + Mn } 1 / 2
    Figure imgb0001
    (where each of [Ni], [Mn], [Cr], [Mo], [Si], [Cu], [Al], [C], and [N] refers to the content (wt%) of a corresponding element).
  • In general, high-manganese steels having a high manganese content like the austenitic steel material of the present disclosure have relatively low stacking fault energy compared to general carbon steels and thus easily have partial dislocations, and since slipping of such partial dislocations is limited to particular slip planes, dislocation accumulation and stress concentration are easily caused. Such concentration of stress facilitates diffusion of hydrogen, and thus a phenomenon in which the fracture strength of a material decreases because of diffusion of hydrogen, that is, embrittlement caused by hydrogen, is likely to occur in high-manganese steels like the austenitic steel material of the present disclosure. Therefore, according to the present disclosure, the deformation behavior of the austenitic steel material is particularly controlled by adjusting stacking fault energy through control of alloying elements and contents thereof. Based on results of research conducted by the inventors, the inventors have found that if stacking fault energy defined by Formula 1 above is adjusted to be 30 mJ/m2 or greater, the possibility of hydrogen embrittlement is markedly reduced.
  • The degree of work hardening of a steel material caused by concentration of stress may be measured by measuring a strain hardening rate in a tensile test. For example, the austenitic steel material of the present disclosure may have a strain hardening rate of 14000 N/mm2 or less in a tensile test performed under atmospheric conditions of 25°C and 1 atm. The strain hardening rate may be calculated from true strain and true stress. If the strain hardening rate in a tensile test is greater than 14000 N/mm2, concentration of stress caused by dislocations is excessively high, and thus hydrogen easily diffuses and accumulates. Thus, hydrogen embrittlement may occur.
  • For example, the austenitic steel material of the present disclosure may have a tensile strength of 800 MPa or less in a tensile test performed under atmospheric conditions of 25°C and 1 atm. If the tensile strength of the austenitic steel material is greater than 800 MPa, hydrogen-embrittlement resistance may deteriorate because of high work hardening caused by concentration of stress.
  • For example, the austenitic steel material of the present disclosure may have a microstructure including austenite in an area fraction of 95% or greater. If the area fraction of austenite is less than 95%, intended hydrogen-embrittlement resistance may not be obtained.
  • For example, the microstructure of the austenitic steel material of the present disclosure may be austenite, or ε-martensite and austenite after a tensile test performed under atmospheric conditions of 25°C and 1 atm. If the microstructure of the austenitic steel material has ferrite, intended hydrogen-embrittlement resistance may not be obtained.
  • The austenitic steel material of the present disclosure may be manufactured by a general steel material manufacturing method using a steel slab having the above-described composition. For example, the austenitic steel material of the present disclosure may be manufactured by reheating, rough rolling, finish rolling, and cooling a steel slab having the above-described composition.
  • In this case, the temperature of the finish rolling process may be adjusted to be greater than a non-crystallization temperature. If the finish rolling process is performed at a temperature equal to or lower than the non-crystallization temperature, the strength of the steel material may be excessively high due to excessive formation and accumulation of dislocations, thereby promoting concentration of stress and fracture caused by hydrogen. In addition, ferrite inducing hydrogen embrittlement during tensile deformation may be early formed, and thus it may be difficult to obtain intended hydrogen-embrittlement resistance.
  • In addition, the steel material may be cooled through an accelerated cooling process after a rolling process, so as to suppress the formation of carbides. The reason for this is that if carbides are formed, the elongation of the steel material decreases, and in particular, hydrogen accumulates along boundaries between carbides and austenite, thereby decreasing hydrogen-embrittlement resistance. Since elements such as carbon (C), chromium (Cr), and molybdenum (Mo) are main carbide forming elements, whether or not to perform accelerated cooling and the rate of accelerated cooling are determined according to the contents of such elements as expressed by the following formula. Cooling rate ° C / s 15 C + Cr + Mo
    Figure imgb0002
    (where each of [C], [Cr], and [Mo] refers to the content (wt%) of a corresponding element).
  • [Mode for Invention]
  • Hereinafter, the present disclosure will be described more specifically through examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The scope of the present invention is defined by the appended claims, and modifications and variations reasonably made therefrom.
  • Slabs having compositions shown in Table 1 below were prepared, and then rolled materials were manufactured by hot rolling and cooling the slabs. At that time, the same process conditions were applied to all the examples except finish rolling temperatures and cooling rates as shown in Table 2 below. Referring to Table 2, a cooling rate in Comparative Example 5 is not stated, and this means that simple air cooling was performed.
  • Thereafter, microstructures of the rolled materials were observed, and the fraction of austenite in each of the rolled materials was measured. Then, a tensile test was performed on the rolled materials under atmospheric conditions of 25°C and 1 atm, and then the tensile strength, strain hardening rate, elongation at break T-El1, and ferrite fraction of each of the rolled materials were measured. Independently of this, a tensile test was performed on the rolled materials under high-pressure hydrogen conditions of 25°C and 70 MPa, and elongation at break T-El2 was measured. Results thereof are shown in Table 3 below. [Table 1]
    No. Alloying composition (wt%) □① (wt%)
    C Mn Cu N Cr Ni Mo Si Al
    *CE1 0.62 18.2 0.06 0.012 0.13 17.866
    CE2 0.46 16 0.13 0.021 0.2 19.578
    CE3 0.42 23.2 5.32 0.016 1.52 20.006
    CE4 0.83 15.2 0.32 0.017 5.3 0.32 15.619
    CE5 0.13 19.5 0.021 0.2 23.109
    **IE1 0.41 31.8 0.015 1.72 20.113
    IE2 0.29 29.8 0.35 0.022 0.86 21.397
    IE3 0.42 27.3 0.51 0.022 2.08 1.51 20.006
    IE4 0.28 31.2 0.022 1.08 1.75 0.35 21.504
    IE5 0.38 28.5 1.1 0.018 0.16 0.31 1.74 20.434
    where □① refers to -10.7C (wt%) + 24.5
    *CE: Comparative Example, **IE: Inventive Example
    [Table 2]
    No. Finish rolling temperature (°C) Cooling rate (°C/sec)
    Comparative Example 1 910 11.5
    Comparative Example 2 870 5.6
    Comparative Example 3 865 7.2
    Comparative Example 4 892 15.2
    Comparative Example 5 856 -
    Inventive Example 1 912 15.4
    Inventive Example 2 905 12.7
    Inventive Example 3 922 13.6
    Inventive Example 4 915 20.4
    Inventive Example 5 932 15.6
    [Table 3]
    No. Stacking fault energy (mJ/m2) Before tensile test After tensile test elongation at break ratio
    Austenite fraction (area%) Ferrite fraction (area%) Tensile strength (MPa) Strain hardening rate (N/mm2)
    *CE1 19.7 100 0 1015 18653 0.1
    CE2 5.5 96 12 948 19320 0.13
    CE3 34.9 100 Not measured (cracks)
    CE4 30.0 92.5 0 1135 21396 0.07
    CE5 -5.1 62 28 832 17504 0.08
    **IE1 53.0 100 0 760 9854 0.75
    IE2 31.5 100 0 658 4850 0.97
    IE3 42.9 100 0 715 6512 0.91
    IE4 33.3 100 0 672 4385 0.96
    IE5 42.2 100 0 675 5214 0.92
    *CE: Comparative Example, **IE: Inventive Example
  • Referring to Table 3, after tensile deformation at room temperature, each of Inventive Examples 1 to 5 satisfying the composition ranges proposed in the present disclosure had stable austenite without ferrite, a low strain hardening rate, and low tensile strength. In particular, since Inventive Examples 1 to 5 were rolled at a finish rolling temperature higher than a non-crystallization temperature, the formation and accumulation of dislocations were suppressed, and since Inventive Examples 1 to 5 were cooled at a cooling rate satisfying the range proposed in the present disclosure, the formation of carbides was effectively suppressed. As a result, austenitic steel materials having high hydrogen-embrittlement resistance, that is, having a high elongation at break ratio, could be obtained.
  • However, Comparative Example 1 had carbon and manganese contents outside the ranges proposed in the present disclosure and particularly, a high strain hardening rate because of an excessively high carbon content, and thus, the elongation at break ratio of Comparative Example 1 was low. That is, Comparative Example 1 had poor hydrogen-embrittlement resistance.
  • Particularly, in Comparative Example 2 having a manganese content outside of the range proposed in the present disclosure, austenite was unstable, and thus ferrite susceptible to hydrogen embrittlement was formed after tensile deformation. That is, Comparative Example 2 had poor hydrogen-embrittlement resistance.
  • In Comparative Example 3 having carbon and manganese contents and stacking fault energy within the ranges proposed in the present disclosure but a copper content greater than the range proposed in the present disclosure, cracks were formed in the rolled material, and thus a normal specimen could not obtained.
  • Since Comparative Example 4 had a carbon content greater than the range proposed in the present disclosure, Comparative Example 4 had a high strain hardening rate and carbides excessively precipitated along austenite grain boundaries, and thus the hydrogen-embrittlement resistance of Comparative Example 4 was poor.
  • In addition, since Comparative Example 5 had a manganese content outside the range proposed in the present disclosure, an intended microstructure could not be obtained, and thus the hydrogen-embrittlement resistance of Comparative Example 5 was poor.
  • FIG. 2 is an image of a fracture surface of a specimen of Inventive Example 1 after the room-temperature tensile test. Referring to FIG. 2, fracture occurred in a dimple type which is typical of ductile fracture.
  • While exemplary embodiments have been shown and described above, it will be apparent to those skilled in the art that modifications and other embodiments could be made therefrom. That is, such modifications and other embodiments could be made without departing from the scope of the present invention as defined by the appended claims.

Claims (6)

  1. An austenitic steel material having high hydrogen-embrittlement resistance, the austenitic steel material comprising, by wt%, carbon (C): 0.1% to 0.5%, copper (Cu): 5% or less (excluding 0%), nitrogen (N): 1% or less (excluding 0%), manganese (Mn): [Mn]≥10.7[C]+24.5 where each of [Mn] and [C] refers to a weight percent (wt%) of a corresponding element, chromium (Cr): 10% or less, nickel (Ni): 5% or less, molybdenum (Mo): 5% or less, silicon (Si): 4% or less, aluminum (Al): 5% or less, and a balance of iron (Fe) and inevitable impurities,
    wherein the austenitic steel material has a T-El2/T-El1 ratio of 0.5 or greater, where T-El2 is an elongation at break in a tensile test performed under hydrogen conditions of 25°C and 70 MPa, and T-El1 is an elongation at break in a tensile test performed under atmospheric conditions of 25°C and 1 atm.
  2. The austenitic steel material of claim 1, wherein the austenitic steel material has stacking fault energy (SFE) defined by Formula 1 below within a range of 30 mJ/m2 or greater, SFE mJ / m 2 = 1.6 Ni 1.3 Mn + 0.06 Mn 2 1.7 Cr + 0.01 Cr 2 + 15 Mo 5.6 Si + 1.6 Cu + 5.5 Al 60 ( C + 1.2 N ) 1 / 2 + 26.3 C + 1.2 N Cr + Mn + Mo 1 / 2 + 0.6 Ni Cr + Mn } 1 / 2
    Figure imgb0003
    where each of [Ni], [Mn], [Cr], [Mo], [Si], [Cu], [Al], [C], and [N] refers to a content (wt%) of a corresponding element.
  3. The austenitic steel material of claim 1, wherein the austenitic steel material has a strain hardening rate of 14000 N/mm2 or less in the tensile test performed under the atmospheric conditions of 25°C and 1 atm.
  4. The austenitic steel material of claim 1, wherein the austenitic steel material has a tensile strength of 800 MPa or less in the tensile test performed under the atmospheric conditions of 25°C and 1 atm.
  5. The austenitic steel material of claim 1, wherein the austenitic steel material has a microstructure comprising austenite in an area fraction of 95% or greater (including 100%) .
  6. The austenitic steel material of claim 1, wherein after the tensile test performed under the atmospheric conditions of 25°C and 1 atm, the austenitic steel material has a microstructure formed of austenite, or formed of ε-martensite and austenite.
EP16879356.0A 2015-12-22 2016-12-22 Austenitic steel material having excellent hydrogen-embrittlement resistance Active EP3395989B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR20150184291 2015-12-22
PCT/KR2016/015085 WO2017111489A1 (en) 2015-12-22 2016-12-22 Austenitic steel material having excellent hydrogen-embrittlement resistance

Publications (3)

Publication Number Publication Date
EP3395989A1 true EP3395989A1 (en) 2018-10-31
EP3395989A4 EP3395989A4 (en) 2018-11-14
EP3395989B1 EP3395989B1 (en) 2020-07-15

Family

ID=59089865

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16879356.0A Active EP3395989B1 (en) 2015-12-22 2016-12-22 Austenitic steel material having excellent hydrogen-embrittlement resistance

Country Status (7)

Country Link
US (1) US20190010590A1 (en)
EP (1) EP3395989B1 (en)
JP (1) JP6703608B2 (en)
KR (1) KR20180085797A (en)
CN (1) CN108431275A (en)
CA (1) CA3009463C (en)
WO (1) WO2017111489A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021152222A1 (en) 2020-01-30 2021-08-05 Psa Automobiles Sa Method for analysing hydrogen embrittlement of bare or coated steel parts used in motor vehicles

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111684107B (en) * 2018-03-02 2021-03-19 株式会社德山 Stainless steel parts and methods of making the same
KR102255827B1 (en) * 2018-10-25 2021-05-26 주식회사 포스코 Low-temperature austenitic high manganese steel having excellent surface quality and manufacturing method for the same
EP4515012A1 (en) * 2022-04-29 2025-03-05 United States Steel Corporation Low ni-containing steel alloys with hydrogen degradation resistance
JP7424550B1 (en) 2022-07-14 2024-01-30 Jfeスチール株式会社 High-strength steel plate for hydrogen transport steel pipes, manufacturing method thereof, and steel pipes for hydrogen transport
WO2024071358A1 (en) 2022-09-29 2024-04-04 Jfeスチール株式会社 High-strength line pipe steel material having excellent fracture toughness in hydrogen, method for manufacturing same, steel tube for high-strength line pipes, and method for manufacturing same
KR102803122B1 (en) 2022-12-01 2025-05-07 리녹스 주식회사 Manufacturing method of stainless steel with improved resistance to hydrogen brittleness
EP4628604A4 (en) 2023-02-14 2026-03-18 Jfe Steel Corp HIGH-STRENGTH STEEL SHEET FOR HYDROGEN TRANSPORTING STEEL PIPES, METHOD FOR MANUFACTURING THEM AND HYDROGEN TRANSPORTING STEEL PIPES

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5681656A (en) * 1979-12-10 1981-07-03 Japan Steel Works Ltd:The Nonmagnetic steel for cryogenic temperature high magnetic field apparatus
JPS5928561A (en) * 1982-08-11 1984-02-15 Sumitomo Metal Ind Ltd Non-magnetic steel high in volume electric resistivity
JPH0215148A (en) * 1988-07-02 1990-01-18 Sumitomo Metal Ind Ltd High mn nonmagnetic steel having excellent corrosion resistance
JPH04259325A (en) * 1991-02-13 1992-09-14 Sumitomo Metal Ind Ltd Production of hot rolled high strength steel sheet excellent in workability
DE69226946T2 (en) * 1991-12-30 1999-05-12 Pohang Iron & Steel Co. Ltd., Pohang City, Kyung Sang Book AUSTENITIC MANGANIC STEEL SHEET WITH HIGH DEFORMABILITY, STRENGTH AND WELDABILITY AND METHOD
FR2796083B1 (en) * 1999-07-07 2001-08-31 Usinor PROCESS FOR MANUFACTURING IRON-CARBON-MANGANESE ALLOY STRIPS, AND STRIPS THUS PRODUCED
FR2829775B1 (en) * 2001-09-20 2003-12-26 Usinor PROCESS FOR THE MANUFACTURE OF ROLLED AND WELDED TUBES COMPRISING A FINAL STRETCHING OR HYDROFORMING STAGE AND WELDED TUBE THUS OBTAINED
JP4529872B2 (en) * 2005-11-04 2010-08-25 住友金属工業株式会社 High Mn steel material and manufacturing method thereof
KR100742833B1 (en) * 2005-12-24 2007-07-25 주식회사 포스코 High manganese hot-dip galvanized steel sheet with excellent corrosion resistance and manufacturing method
DE102008056844A1 (en) * 2008-11-12 2010-06-02 Voestalpine Stahl Gmbh Manganese steel strip and method of making the same
KR20110072791A (en) * 2009-12-23 2011-06-29 주식회사 포스코 Austenitic high strength steel sheet with excellent ductility and delayed fracture resistance and its manufacturing method
JP5003785B2 (en) * 2010-03-30 2012-08-15 Jfeスチール株式会社 High tensile steel plate with excellent ductility and method for producing the same
KR101543916B1 (en) * 2013-12-25 2015-08-11 주식회사 포스코 Steels for low temperature services having superior deformed surface quality and method for production thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021152222A1 (en) 2020-01-30 2021-08-05 Psa Automobiles Sa Method for analysing hydrogen embrittlement of bare or coated steel parts used in motor vehicles
FR3106898A1 (en) 2020-01-30 2021-08-06 Psa Automobiles Sa PROCESS FOR ANALYSIS OF HYDROGEN FRAGILIZATION OF BARE OR COATED STEEL PARTS USED IN MOTOR VEHICLES

Also Published As

Publication number Publication date
CA3009463A1 (en) 2017-06-29
KR20180085797A (en) 2018-07-27
JP2019505675A (en) 2019-02-28
CN108431275A (en) 2018-08-21
JP6703608B2 (en) 2020-06-03
WO2017111489A1 (en) 2017-06-29
US20190010590A1 (en) 2019-01-10
EP3395989A4 (en) 2018-11-14
CA3009463C (en) 2020-09-22
EP3395989B1 (en) 2020-07-15

Similar Documents

Publication Publication Date Title
EP3395989B1 (en) Austenitic steel material having excellent hydrogen-embrittlement resistance
EP4414473A1 (en) High-strength steel with good weather resistance and manufacturing method therefor
CN102449180B (en) High strength steel sheet having excellent hydrogen embrittlement resistance
CN103060715B (en) A kind of ultra-high strength and toughness steel plate and manufacture method thereof with low yielding ratio
JP4390081B2 (en) Seamless steel pipe for oil well with excellent resistance to sulfide stress cracking and method for producing the same
EP2617853B1 (en) High-strength hot-rolled steel sheet having superior fatigue resistance properties and method for producing same
JP6451545B2 (en) High Mn steel for high-pressure hydrogen gas, method for producing the same, and piping, container, valve and joint made of the steel
EP2520684B9 (en) Austenite steel material having superior ductility
US11634785B2 (en) Steel material showing excellent hydrogen-induced cracking resistance and method for preparing same
EP3392362B1 (en) Wear resistant steel material excellent in toughness and internal quality, and method for manufacturing same
EP2889390A1 (en) Highly strong, highly tough and highly corrosion-resistant martensitic stainless steel
EP3480332A1 (en) High strength steel plate having excellent low yield ratio characteristics and low temperature toughness and method for manufacturing same
US20180216207A1 (en) Formable lightweight steel having improved mechanical properties and method for producing semi-finished products from said steel
EP3730654A1 (en) Wear-resistant steel having excellent hardness and impact toughness, and method for producing same
US11634800B2 (en) High-strength austenite-based high-manganese steel material and manufacturing method for same
JP2025541555A (en) Low thermal expansion steel with improved low temperature impact toughness and manufacturing method thereof
KR102403849B1 (en) High strength austenitic stainless steel with excellent productivity and cost saving effect, and method for manufacturing the same
JP2019143227A (en) High Mn austenitic stainless steel
EP4438761A1 (en) Hot-rolled steel sheet and method for manufacturing same
CN117684100A (en) Heat-free martensitic corrosion-resistant steel and its manufacturing method
KR101736590B1 (en) Non heat treated wire rod having excellent high strength and method for manafacturing thereof
EP3674426B1 (en) Method for production of ni-containing steel plate
KR101758514B1 (en) Hot rolled steel sheet having excellent weldabity and expandability for pipe and method for manufacturing the same
EP4397781A1 (en) Hot-rolled ferritic stainless steel sheet having excellent formability and method for manufacturing same
JP2020100866A (en) Cr-BASED STAINLESS STEEL HAVING EXCELLENT HYDROGEN EMBRITTLEMENT RESISTANCE AND LOW-TEMPERATURE EMBRITTLEMENT RESISTANCE

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

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

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20180720

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL 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 RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

A4 Supplementary search report drawn up and despatched

Effective date: 20181011

RIC1 Information provided on ipc code assigned before grant

Ipc: C22C 38/02 20060101ALI20181005BHEP

Ipc: C22C 38/00 20060101ALI20181005BHEP

Ipc: C22C 38/04 20060101ALI20181005BHEP

Ipc: C22C 38/08 20060101ALI20181005BHEP

Ipc: C22C 38/38 20060101ALI20181005BHEP

Ipc: C22C 38/12 20060101ALI20181005BHEP

Ipc: C22C 38/16 20060101AFI20181005BHEP

Ipc: C22C 38/06 20060101ALI20181005BHEP

Ipc: C22C 38/44 20060101ALI20181005BHEP

Ipc: C22C 38/58 20060101ALI20181005BHEP

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
RIC1 Information provided on ipc code assigned before grant

Ipc: C22C 38/12 20060101ALI20190801BHEP

Ipc: C21D 8/00 20060101ALI20190801BHEP

Ipc: C22C 38/08 20060101ALI20190801BHEP

Ipc: C22C 38/00 20060101ALI20190801BHEP

Ipc: C22C 38/02 20060101ALI20190801BHEP

Ipc: C22C 38/16 20060101AFI20190801BHEP

Ipc: C21D 6/00 20060101ALI20190801BHEP

Ipc: C22C 38/06 20060101ALI20190801BHEP

Ipc: C22C 38/44 20060101ALI20190801BHEP

Ipc: C22C 38/58 20060101ALI20190801BHEP

Ipc: C22C 38/04 20060101ALI20190801BHEP

Ipc: C22C 38/38 20060101ALI20190801BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

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

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20191002

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

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

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTC Intention to grant announced (deleted)
INTG Intention to grant announced

Effective date: 20200204

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL 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 RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602016040209

Country of ref document: DE

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: 1291125

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200815

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1291125

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200715

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20200715

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

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: 20200715

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: 20201015

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: 20201015

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: 20201016

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: 20200715

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: 20200715

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: 20200715

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: 20200715

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: 20200715

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: 20201116

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: 20201115

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: 20200715

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: 20200715

Ref country code: RS

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: 20200715

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: 20200715

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602016040209

Country of ref document: DE

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

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: 20200715

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: 20200715

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: 20200715

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: 20200715

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: 20200715

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

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

Ref country code: AL

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: 20200715

26N No opposition filed

Effective date: 20210416

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

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: 20200715

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: 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: 20200715

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: 20200715

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20201231

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: 20201222

Ref country code: LU

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

Effective date: 20201222

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: 20201231

Ref country code: CH

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

Effective date: 20201231

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: 20200715

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: 20200715

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: 20200715

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: 20200715

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

Ref country code: BE

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

Effective date: 20201231

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602016040209

Country of ref document: DE

Owner name: POSCO CO., LTD, POHANG-SI, KR

Free format text: FORMER OWNER: POSCO, POHANG-SI, GYEONGSANGBUK-DO, KR

Ref country code: DE

Ref legal event code: R081

Ref document number: 602016040209

Country of ref document: DE

Owner name: POSCO CO., LTD, POHANG- SI, KR

Free format text: FORMER OWNER: POSCO, POHANG-SI, GYEONGSANGBUK-DO, KR

Ref country code: DE

Ref legal event code: R081

Ref document number: 602016040209

Country of ref document: DE

Owner name: POSCO HOLDINGS INC., KR

Free format text: FORMER OWNER: POSCO, POHANG-SI, GYEONGSANGBUK-DO, KR

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20221027 AND 20221102

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602016040209

Country of ref document: DE

Owner name: POSCO CO., LTD, POHANG-SI, KR

Free format text: FORMER OWNER: POSCO HOLDINGS INC., SEOUL, KR

Ref country code: DE

Ref legal event code: R081

Ref document number: 602016040209

Country of ref document: DE

Owner name: POSCO CO., LTD, POHANG- SI, KR

Free format text: FORMER OWNER: POSCO HOLDINGS INC., SEOUL, KR

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

Ref country code: DE

Payment date: 20251105

Year of fee payment: 10

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

Ref country code: GB

Payment date: 20251105

Year of fee payment: 10

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

Ref country code: IT

Payment date: 20251106

Year of fee payment: 10

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

Ref country code: FR

Payment date: 20251111

Year of fee payment: 10