EP3318650B1 - Alliage austénitique thermorésistant et structure soudée - Google Patents

Alliage austénitique thermorésistant et structure soudée Download PDF

Info

Publication number
EP3318650B1
EP3318650B1 EP16817632.9A EP16817632A EP3318650B1 EP 3318650 B1 EP3318650 B1 EP 3318650B1 EP 16817632 A EP16817632 A EP 16817632A EP 3318650 B1 EP3318650 B1 EP 3318650B1
Authority
EP
European Patent Office
Prior art keywords
content
contained
austenitic heat
upper limit
resistant alloy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP16817632.9A
Other languages
German (de)
English (en)
Other versions
EP3318650A4 (fr
EP3318650A1 (fr
Inventor
Hiroyuki Hirata
Hiroyuki Semba
Kana JOTOKU
Atsuro Iseda
Toshihide Ono
Katsuki Tanaka
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.)
Nippon Steel Corp
Original Assignee
Nippon Steel Corp
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 Nippon Steel Corp filed Critical Nippon Steel Corp
Publication of EP3318650A1 publication Critical patent/EP3318650A1/fr
Publication of EP3318650A4 publication Critical patent/EP3318650A4/fr
Application granted granted Critical
Publication of EP3318650B1 publication Critical patent/EP3318650B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/001—Austenite

Definitions

  • the present invention relates to an austenitic heat-resistant alloy and a welded structure including this alloy.
  • JP 2004-250783 A proposes an austenitic stainless steel with improved high-temperature strength and corrosion resistance, where the N content is 0.1 to 0.35 % and the Cr content is higher than 22 % and lower than 30 %, and a metallic microstructure is specified.
  • JP 2009-084606 A proposes an austenitic stainless steel with improved high-temperature strength and corrosion resistance, where the N content is 0.1 to 0.35 % and the Cr content is higher than 22 % and lower than 30 %, and impurity elements are specified.
  • JP 2012-1749 A discloses an austenitic heat-resistant steel with improved high-temperature strength and hot workability containing 0.09 to 0.30 % N and having large amounts of Mo and W in composite addition.
  • WO 2009/044796 A1 discloses a high-strength austenitic stainless steel containing 0.03 to 0.35 % N and one or more of Nb, V and Ti.
  • JP2013-044013 discloses a high strength austenitic heat resistant steel including, by mass%, C: 0.02-0.08%, Si: above 0.3-0.8%, Mn: 0.6-2.0%, P: ⁇ 0.04%, S: ⁇ 0.010%, Ni: above 15-26%, Cr: 18-23%, W: 1.8-4.2%, Mo: ⁇ 0.5%, Nb: 0.2-0.5%, Al: 0.001-0.040%, N: 0.07-0.13% with the balance being Fe and inevitable impurities, and which satisfies the following formulae (1) and (2).
  • JP2013-067843 discloses a high-strength austenitic heat-resistant steel containing, by mass%, 0.02-0.08% C, >0.3-0.8% Si, 0.6-2.0% Mn, ⁇ 0.040% P, ⁇ 0.005% S, >15-26% Ni, 18-23% Cr, 1.8-4.2% W, ⁇ 0.5% Mo, 0.2-0.5% Nb, 0.001-0.040% Al, 0.07-0.13% N, ⁇ 0.001% B and the balance Fe with inevitable impurities, and which satisfies the following three formulas: 0.05% ⁇ Nb-0.031(C+N) ⁇ 0.15%; 2.8% ⁇ W+2Mo ⁇ 4.2%; and 9.5% ⁇ Ni+27C+23N+0.2Mn+0.3Cu-1.2(Cr+Mo+0.5W)-0.5Si-0.3Nb+10%.
  • JPS63-183155 discloses an alloy having a composition which consists of, by weight, 0.02-0.2% C, 0.3-1.5% Si, 0.3-1.5% Mn, 18-30% Cr, 20-50% Ni, 0.5-5.0% Mo, 1.0-5.0% W, 0.05-0.4% Nb, 0.01-0.2% Ti,, 0.003-0.008% B, ⁇ 0.04% P, ⁇ 0.005% S, 0.02-0.3% N, and the balance Fe with inevitable impurities and in which Mo+W ⁇ 6.0% is satisfied is prepared.
  • JP H11-277292 discloses a steel containing, by weight, 0.03-0.13% C, 0.2-4% Mn, 1-5% Cu, 15/25% Ni, 15-25% Cr, 0.5-3% W, 0.15-1.5 Nb, 0.1-0.35% N, 0.001-0.01% B, ⁇ 0.01% Al, ⁇ 0.01% O, 0-1.5% Mo, 0-0.01 Ca, 0-0.01% Mg, 0-0.02% Zr, 0-0.02% Hf and 0.02% Ta.
  • Si and Nb satisfy the formula, Si ⁇ 0.2Nb+0.25, and also Ni, Cu and Cr satisfy the formula, 0.7 ⁇ (Ni+Cu)/Cr ⁇ 1.4.
  • WO 2009/044796 A1 discussed above states that limiting the amounts of the elements that cause embrittlement of the grain boundaries and the elements that strengthen the grain interiors to certain ranges prevents cracking that would occur during use for a prolonged period of time. Indeed, these materials prevent cracking under certain conditions.
  • austenitic heat-resistant alloys with large amounts of W, Mo etc. added thereto to further improve properties such as high-temperature strength has become widespread.
  • structure shapes and sizes for example, these austenitic heat-resistant alloys may not prevent cracking in a stable manner. More specifically, they may not prevent cracking in a stable manner for high welding heat inputs, heavy plate thicknesses or high use temperatures such as above 650 °C.
  • An object of the present invention is to provide an austenitic heat-resistant alloy that provides good crack resistance and high-temperature strength in a stable manner.
  • An austenitic heat-resistant alloy has a chemical composition of, in mass %: 0.04 to 0.14 % C; 0.05 to 1 % Si; 0.5 to 2.5 % Mn; up to 0.03 % P; less than 0.001 % S; 23 to 32 % Ni; 20 to 25 % Cr; 1 to 5 % W; 0.1 to 0.6 % Nb; 0.12 to 0.6 V; 0.1 to 0.3 % N; 0.0005 to 0.01 % B; 0.001 to 0.02 % Sn; up to 0.03 % Al; up to 0.02 % O; 0 to 0.5 % Ti; 0 to 2 % Co; 0 to 4 % Cu; 0 to 4 % Mo; 0 to 0.02 % Ca; 0 to 0.02 % Mg; 0 to 0.2 % REM; and the balance being Fe and impurities, the alloy having a microstructure with a grain size represented by a grain size number in accordance with ASTM E11
  • the present invention provides an austenitic heat-resistant alloy that provides good crack resistance and high-temperature strength in a stable manner.
  • FIG. 1 is a cross-sectional view of a bevel produced for the Examples, showing the shape of the groove thereof.
  • the present inventors conducted a detailed investigation to solve the above-discussed problems, and revealed the following findings.
  • the inventors thoroughly investigated SIPH cracks occurring, during use, in welded joints using austenitic heat-resistant alloys with high N contents. They found that (1) cracks developed along grain boundaries in weld-heat-affected zones with coarse grains near the fusion lines, and (2) clear concentrating of S was detected on the fractured surfaces of cracks. They further found that (3) large amounts of nitrides and carbonitrides had precipitated within grains near the cracks. This was particularly significant for high Nb contents. In addition, they found that (4) the larger the initial grain size of the used austenitic heat-resistant alloy, the larger the grain size in weld-heat-affected zones became and the more likely cracking occurred.
  • the inventors revealed that, in order to prevent SIPH cracking in an austenitic heat-resistant alloy containing 0.04 to 0.14 % C, 0.05 to 1 % Si, 0.5 to 2.5 % Mn, up to 0.03 % P, 23 to 32 % Ni, 20 to 25 % Cr, 1 to 5 % W, 0.1 to 0.3 % N, 0.0005 to 0.01 % B, up to 0.03 % Al, and up to 0.02 % O, it is effective to exactly control the Nb and S contents to be in the range of 0.1 to 0.6 % and below 0.001 %, respectively, and to have an initial grain size of the base material represented by a grain size number as defined by the American Society for Testing and Material (ASTM) of 2.0 or more.
  • ASTM American Society for Testing and Material
  • the inventors found that the grain size as represented by grain size number needs to be less than 7.0.
  • V which has a lower precipitation strengthening property than Nb, in a content of 0.12 to 0.6 % is necessary to achieve a predetermined creep strength without impairing SIPH crack resistance.
  • austenitic heat-resistant alloys are generally welded for assembly. When they are welded, a filler material is usually used. However, for small parts with thin wall thicknesses, or even for components with heavy wall thickness for root running or tack welding, gas shield-arc welding may be performed without using a filler material. If the penetration depth is insufficient at this time, unwelded abutting surfaces remain as weld defects, and the strength required of a welded joint cannot be obtained. While S reduces SIPH crack resistance, S has the effect of increasing the penetration depth. Thus, the inventors found that the problem of insufficient penetration depth tends to be apparent if the S content is exactly controlled to be below 0.001 % to address the issue of SIPH crack resistance.
  • welding heat input may be simply increased.
  • increasing welding heat input brings about grains coarsening in weld-heat-affected zones, and the inventors failed to prevent SIPH cracking even when the initial grain size of the base material had a grain size number of 2.0 or more.
  • the austenitic heat-resistant alloy according to the present embodiment has the chemical composition described below.
  • "%" in the content of an element means mass percent.
  • Carbon (C) stabilizes the austenite microstructure and forms fine carbide particles to improve creep strength during use at high temperatures. 0.04 % or more C needs to be contained in order that these effects are sufficiently present. However, if an excess amount of C is contained, large amounts of carbides precipitate, which reduces SIPH crack resistance. In view of this, the upper limit should be 0.14 %.
  • the lower limit of C content is preferably 0.05 %, and more preferably 0.06 %.
  • the upper limit of C content is preferably 0.13 %, and more preferably 0.12 %.
  • Silicon (Si) has a deoxidizing effect, and is effective in improving the corrosion resistance and oxidation resistance at high temperatures. 0.05 % or more Si needs to be contained in order that these effects are sufficiently present. However, if an excess amount of Si is contained, the stability of the microstructure decreases, which decreases toughness and creep strength. In view of this, the upper limit should be 1 %.
  • the lower limit of Si content is preferably 0.08 %, and more preferably 0.1 %.
  • the upper limit of Si content is preferably 0.6 %, and more preferably 0.5 %.
  • Mn manganese
  • the lower limit of Mn content is preferably 0.6 %, and more preferably 0.7 %.
  • the upper limit of Mn content is preferably 2 %, and more preferably 1.5 %.
  • Phosphorus (P) is contained in the alloy in the form of an impurity, and, during welding, segregates on grain boundaries in weld-heat-affected zones, thereby increasing liquation cracking susceptibility. P also decreases creep ductility after use for a prolonged period of time.
  • an upper limit should be set for P content, which should be 0.03 % or lower.
  • the upper limit of P content is preferably 0.028 %, and more preferably 0.025 %. It is preferable to minimize P content; however, reducing it excessively causes increased steel-manufacturing cost.
  • the lower limit of P content is preferably 0.0005 %, and more preferably 0.0008 %.
  • sulfur (S) is contained in the alloy in the form of an impurity, and, during welding, segregates on grain boundaries in weld-heat-affected zones, thereby increasing liquation cracking susceptibility. S also segregates on grain boundaries during use for a prolonged period of time and causes embrittlement, which significantly reduces SIPH crack resistance.
  • the S content needs to be less than 0.001 %.
  • the upper limit of S content is preferably 0.0008 %, and more preferably 0.0005 %. It is preferable to minimize S content; however, reducing it excessively causes increased steel-manufacturing cost.
  • the lower limit of S content is preferably 0.0001 %, and more preferably 0.0002 %.
  • Nickel (Ni) is an element indispensable for providing sufficient stability of the austenite phase during use for a prolonged period of time. 23 % or more Ni needs to be contained in order that this effect is sufficiently present within the limits of Cr and W contents of the present embodiment. However, Ni is an expensive element, and large amounts of Ni contained mean increased costs. In view of this, the upper limit should be 32 %.
  • the lower limit of Ni content is preferably 25 %, and more preferably 25.5 %.
  • the upper limit of Ni content is preferably 31.5 %, and more preferably 31 %.
  • Chromium (Cr) is an element indispensable for providing sufficient oxidation resistance and corrosion resistance at high temperatures. Cr also forms fine carbide particles to contribute to the provision of sufficient creep strength, too. 20 % or more Cr needs to be contained in order that these effects are sufficiently present within the limits of Ni content of the present embodiment. However, if an excessive amount of Cr is contained, the microstructure stability of the austenite phase at high temperatures deteriorates, which decreases creep strength. In view of this, the upper limit should be 25 %.
  • the lower limit of Cr content is preferably 20.5 %, and more preferably 21 %.
  • the upper limit of Cr content is preferably 24.5 %, and more preferably 24 %.
  • Tungsten (W) dissolves in the matrix, or forms fine intermetallic compounds to significantly contribute to the improvement of creep strength and tensile strength at high temperatures. 1 % or more W needs to be contained in order that these effects are sufficiently present. However, if an excess amount of W is contained, the deformation resistance with grains becomes high and SIPH crack resistance reduces, and creep strength may decrease. Further, W is an expensive element, and large amounts of W contained mean increased costs. In view of this, the upper limit should be 5 %.
  • the lower limit of W content is preferably 1.2 %, and more preferably 1.5 %.
  • the upper limit of W content is preferably 4.5 %, and more preferably 4 %.
  • Niobium (Nb) precipitates in the form of fine MX carbonitride particles, and, in addition, precipitates in the form of Z phase (CrNbN) within grains to significantly contribute to the improvement of creep strength and tensile strength at high temperatures.
  • 0.1 % or more Nb needs to be contained in order that these effects are sufficiently present. However, if an excess amount of Nb is contained, the strengthening property of these precipitates is too high, which reduces SIPH crack resistance and causes a decrease in creep ductility and toughness.
  • the upper limit should be 0.6 %.
  • the lower limit of Nb content is preferably 0.12 %, and more preferably 0.15 %.
  • the upper limit of Nb content is preferably 0.55 %, and more preferably 0.5 %.
  • Vanadium (V) precipitates in the form of fine MX carbonitride particles within the grains to contribute to the improvement of creep strength and tensile strength at high temperatures.
  • 0.1 % or more V needs to be contained in order that these effects are sufficiently present.
  • the upper limit should be 0.6 %.
  • the lower limit of V content is 0.12 %, and preferably 0.15 %.
  • the upper limit of V content is preferably 0.55 %, and more preferably 0.5 %.
  • N Nitrogen
  • the lower limit of N content is preferably 0.12 %, and more preferably 0.14 %.
  • the upper limit of N content is preferably 0.28 %, and more preferably 0.26 %.
  • B Boron
  • B provides fine dispersed grain-boundary carbide particles to improve creep strength, and segregates on grain boundaries to strengthen grain boundaries. 0.0005 % or more B needs to be contained in order that these effects are sufficiently present. However, if an excess amount of B is contained, the weld thermal cycle during welding causes a large amount of B to segregate in weld heat affected zones near melt boundaries to decrease the melting point of grain boundaries, thereby increasing liquation cracking susceptibility. In view of this, the upper limit should be 0.01 %.
  • the lower limit of B content is preferably 0.0008 %, and more preferably 0.001 %.
  • the upper limit of B content is preferably 0.008 %, and more preferably 0.006 %.
  • Tin (Sn) has the effect of increasing the penetration depth during welding by evaporating from the molten pool to increase the current density of the arc. 0.001 % or more Sn needs to be contained in order that these effects are sufficiently present. However, if an excess amount of Sn is contained, the liquation cracking susceptibility in weld-heat-affected zones during welding and the SIPH crack susceptibility during use become high. In view of this, the upper limit should be 0.02 %.
  • the lower limit of Sn content is preferably 0.0015 %, and more preferably 0.002 %.
  • the upper limit of Sn content is preferably 0.018 %, and more preferably 0.015 %.
  • Aluminum (Al) has a deoxidizing effect. However, if an excess amount of Al is contained, the cleanliness of the alloy deteriorates, which decreases hot workability. In view of this, the upper limit should be 0.03 %.
  • the upper limit of Al content is preferably 0.025 %, and more preferably 0.02 %. No lower limit needs to be set; still, it should be noted that decreasing Al excessively causes an increase in steel-manufacturing cost. In view of this, the lower limit of Al content is preferably 0.0005 %, and more preferably 0.001 %.
  • Al as used herein means acid-soluble Al (sol. Al).
  • Oxygen (O) is contained in the alloy in the form of an impurity, and has the effect of increasing the penetration depth during welding. However, if an excess amount of O is contained, hot workability decreases and toughness and ductility deteriorate.
  • the upper limit should be 0.02 %.
  • the upper limit of O content is preferably 0.018 %, and more preferably 0.015 %. No lower limit needs to be set; still, it should be noted that decreasing O excessively causes an increase in steel-manufacturing cost.
  • the lower limit of O content is preferably 0.0005 %, and more preferably 0.0008 %.
  • the balance of the chemical composition of the austenitic heat-resistant alloy in the present embodiment is Fe and impurities.
  • Impurity as used herein means an element originating from ore or scrap used as raw material for the heat-resistant alloy being manufactured on an industrial basis or an element that has entered from the environment or the like during the manufacturing process.
  • some of the Fe may be replaced by one or more elements selected from one of the first to third groups provided below. All of the elements listed below are optional elements. That is, none of the elements listed below may be contained in the austenitic heat-resistant alloy of the present embodiment. Or, only one or some of them may be contained.
  • only one group may be selected from among the first to third groups and one or more elements may be selected from this group. In this case, it is not necessary to select all the elements belonging to the selected group.
  • a plurality of groups may be selected from among the first to third groups and one or more elements may be selected from each of these groups. Again, it is not necessary to select all the elements belonging to the selected groups.
  • the element belonging to the first group is Ti.
  • Ti improves the creep strength of the alloy through precipitation strengthening.
  • Titanium (Ti) combines with carbon or nitrogen to form fine carbide or carbonitride particles, thereby contributing to the improvement of creep strength. These effects are present if a small amount of Ti is contained. On the other hand, if an excess amount of Ti is contained, large amounts of precipitates are produced, which reduces SIPH resistance and creep ductility.
  • the upper limit should be 0.5 %.
  • the lower limit of Ti content is preferably 0.01 %, and more preferably 0.03 %.
  • the upper limit of Ti content is preferably 0.45 %, and more preferably 0.4 %.
  • Second Group-Co 0 to 2 %, Cu: 0 to 4 %, Mo: 0 to 4 %
  • the elements belonging to the second group are Co, Cu, and Mo. These elements improve the creep strength of the alloy.
  • cobalt (Co) is an austenite-forming element, and increases the stability of the austenite microstructure to contribute to the improvement of creep strength. These effects are present if a small amount of Co is contained. However, Co is a very expensive element, and large amounts of Co contained mean increased costs. In view of this, the upper limit should be 2 %.
  • the lower limit of Co content is preferably 0.01 %, and more preferably 0.03 %.
  • the upper limit of Co content is preferably 1.8 %, and more preferably 1.5 %.
  • Cu copper
  • the upper limit should be 4 %.
  • the lower limit of Cu content is preferably 0.01 %, and more preferably 0.03 %.
  • the upper limit of Cu content is preferably 3.8 %, and more preferably 3.5 %.
  • Mo molybdenum
  • the lower limit of Mo content is preferably 0.01 %, and more preferably 0.03 %.
  • the upper limit of Mo content is preferably 3.8 %, and more preferably 3.5 %.
  • the elements belonging to the third group are Ca, Mg and REM. These elements improve hot workability of the alloy.
  • the upper limit should be 0.02 %.
  • the lower limit of Ca content is preferably 0.0005 %, and more preferably 0.001 %.
  • the upper limit of Ca content is preferably 0.01 %, and more preferably 0.005 %.
  • magnesium (Mg) improves hot workability during manufacture. This effect is present if a small amount of Mg is contained. On the other hand, if an excess amount of Mg is contained, it combines with oxygen to significantly decrease the cleanliness of the alloy, which decreases hot workability.
  • the upper limit is 0.02 %.
  • the lower limit of Mg content is preferably 0.0005 %, and more preferably 0.001 %.
  • the upper limit of Mg content is preferably 0.01 %, and more preferably 0.005 %.
  • rare-earth metals improve hot workability during manufacture. This effect is present if a small amount of REM is contained. On the other hand, if an excessive amount of REM is contained, it combines with oxygen to significantly decrease the cleanliness of the alloy, which decreases hot workability.
  • the upper limit should be 0.2 %.
  • the lower limit of REM content is preferably 0.0005 %, and more preferably 0.001 %.
  • the upper limit of REM content is preferably 0.15 %, and more preferably 0.1 %.
  • REM is a collective term for a total of 17 elements, i.e. Sc, Y and the lanthanoids, and "REM content” means the total content of one or more REM elements.
  • REMs are usually contained in mischmetal. Thus, for example, mischmetal may be added to the alloy such that the REM content is in the above-indicated range.
  • Nd has a strong affinity for S and P, and has the effect of reducing weld liquation cracking susceptibility by forming sulfides or phosphides, and thus it is more preferable to utilize Nd.
  • Grain Size Number 2.0 or more and less than 7.0
  • the austenitic heat-resistant alloy according to the present embodiment has a microstructure having a grain size represented by a grain size number in accordance with ASTM E112 of 2.0 or more and less than 7.0.
  • the grains of the microstructure before welding need to be fine grains, i.e. their size as represented by grain size number in accordance with ASTM E112 needs to be 2.0 or more, in order to prevent the grains in the weld-heat-affected zones from becoming excessively coarse even after being affected by the heat cycle from the welding.
  • the grain size number should be 2.0 or more and less than 7.0.
  • the microstructure having the above-specified grain size can be provided by performing a heat treatment on the alloy with the above-specified chemical composition under appropriate conditions.
  • This microstructure may be achieved by, for example, shaping the alloy of the above-specified chemical composition into a predetermined shape by hot working or cold working before performing a solution heat treatment in which it is held at temperatures of 900 to 1250 °C for 3 to 60 minutes before water cooling.
  • the solution heat treatment involves holding the alloy at temperatures of 1120 to 1220 °C for 3 to 45 minutes before water cooling, and yet more preferably holding the alloy at temperatures of 1140 to 1210 °C for 3 to 30 minutes before water cooling.
  • the austenitic heat-resistant alloy according to an embodiment of the present invention has been described.
  • the present embodiment provides an austenitic heat-resistant alloy providing good crack resistance and high-temperature strength in a stable manner.
  • the materials labeled A to J having the chemical compositions shown in Table 1 were melted in a laboratory and ingots were cast, which were subjected to hot forging and hot rolling in the temperature range of 1000 to 1150 °C to provide plates with a thickness of 20 mm. These plates were further subjected to cold rolling to the thickness of 16 mm.
  • the plates were subjected to a solution heat treatment in which they were held at 1200 °C for a predetermined period of time before water cooling. After the solution heat treatment, they were machined to plates with a thickness of 14 mm, a width of 50 mm and a length of 100 mm.
  • the groove shown in FIG. 1 was provided along the longitudinal direction of each plate produced as described above. With grooved plates abutting each other, two joints for each mark were subjected to butt welding using gas-tungsten arc welding to produce welded joints. The welding did not use filler material, and the amount of heat input was 5 kJ/cm.
  • Table 2 also shows the grain size number of the austenitic heat-resistant alloy for each mark.
  • Each of the welded joints using the austenitic heat-resistant alloys with Marks A-1 to A-4, B to D and I as the base material had an appropriate chemical composition, where the initial grain size of the base material had a grain size of 2.0 or more and less than 7.0.
  • Each of these welded joints had a back bead across the entire length after root running, and had good weldability in fabrication. Further, though the thickness of the base material was 14 mm, which is relatively large, no cracks were produced in weld-heat-affected zones even after aging, meaning good crack resistance. Further, the creep-rupture strength at high temperatures was sufficient.
  • the welded joint using the austenitic heat-resistant alloy with Mark A-6 as the base material had good crack resistance, but the creep-rupture time was below the target. This is presumably because the grain size of the austenitic heat-resistant alloy with Mark A-6 was too small.
  • the welded joint using the austenitic heat-resistant alloy with Mark F as the base material contained no Sn but a large amount of S such that a sufficient back bead was produced. However, cracks that are believed to be SIPH cracks were produced after aging.
  • the present invention can be suitably used as an austenitic heat-resistant alloy used as a high-temperature part such as a main steam tube or high-temperature reheating steam tube in a thermal power boiler.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Arc Welding In General (AREA)
  • Heat Treatment Of Steel (AREA)

Claims (3)

  1. Alliage austénitique résistant à la chaleur présentant une composition chimique de, en % massique :
    de 0,04 à 0,14 % de C ;
    de 0,05 à 1 % de Si ;
    de 0,5 à 2,5 % de Mn ;
    jusqu'à 0,03 % de P ;
    moins de 0,001 % de S ;
    de 23 à 32 % de Ni ;
    de 20 à 25 % de Cr ;
    de 1 à 5 % de W ;
    de 0,1 à 0,6 % de Nb ;
    de 0,12 à 0,6 % de V;
    de 0,1 à 0,3 % de N ;
    de 0,0005 à 0,01 % de B ;
    de 0,001 à 0,02 % de Sn ;
    jusqu'à 0,03 % d'Al sol. ;
    jusqu'à 0,02 % de O ;
    de 0 à 0,5 % de Ti ;
    de 0 à 2 % de Co ;
    de 0 à 4 % de Cu ;
    de 0 à 4 % de Mo ;
    de 0 à 0,02 % de Ca ;
    de 0 à 0,02 % de Mg ;
    de 0 à 0,2 % de métal de terres rares (REM) ; et
    le reste étant constitué de Fe et d'impuretés,
    l'alliage présentant une microstructure avec une granulométrie représentée par un numéro granulométrique conformément à ASTM E112 de 2,0 ou plus et moins de 7,0.
  2. Alliage austénitique résistant à la chaleur selon la revendication 1, dans lequel la composition chimique contient au moins un élément choisi parmi les premier au troisième groupes prévus ci-dessous, en % massique :
    premier groupe : de 0,01 à 0,5 % de Ti ;
    deuxième groupe : de 0,01 à 2 % de Co, de 0,01 à 4 % de Cu et de 0,01 à 4 % de Mo ; et
    troisième groupe : de 0,0005 à 0,02 % de Ca ; de 0,0005 à 0,02 % de Mg ; et de 0,0005 à 0,2 % de REM.
  3. Joint soudé à l'aide de l'alliage austénitique résistant à la chaleur selon la revendication 1 ou 2 en tant que matériau de base.
EP16817632.9A 2015-07-01 2016-06-02 Alliage austénitique thermorésistant et structure soudée Active EP3318650B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015132552 2015-07-01
PCT/JP2016/066458 WO2017002523A1 (fr) 2015-07-01 2016-06-02 Alliage austénitique thermorésistant et structure soudée

Publications (3)

Publication Number Publication Date
EP3318650A1 EP3318650A1 (fr) 2018-05-09
EP3318650A4 EP3318650A4 (fr) 2018-12-26
EP3318650B1 true EP3318650B1 (fr) 2019-10-09

Family

ID=57609569

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16817632.9A Active EP3318650B1 (fr) 2015-07-01 2016-06-02 Alliage austénitique thermorésistant et structure soudée

Country Status (8)

Country Link
US (1) US20180216215A1 (fr)
EP (1) EP3318650B1 (fr)
JP (1) JP6384610B2 (fr)
KR (1) KR102048479B1 (fr)
CN (1) CN107709595B (fr)
CA (1) CA2988556C (fr)
ES (1) ES2759543T3 (fr)
WO (1) WO2017002523A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190062488A (ko) * 2016-10-03 2019-06-05 닛폰세이테츠 가부시키가이샤 오스테나이트계 내열 합금 및 그것을 이용한 용접 이음매
CN111183239B (zh) * 2017-10-03 2022-04-29 日本制铁株式会社 奥氏体系不锈钢焊接金属以及焊接结构物
JP7167707B2 (ja) * 2018-12-27 2022-11-09 日本製鉄株式会社 オーステナイト系耐熱鋼
WO2021039266A1 (fr) * 2019-08-29 2021-03-04 日本製鉄株式会社 Acier austénitique résistant à la chaleur
CN110551932A (zh) * 2019-09-23 2019-12-10 广东鑫发精密金属科技有限公司 一种304薄带不锈钢电池加热片及其制备方法
US11618930B2 (en) * 2019-12-26 2023-04-04 Seiko Watch Kabushiki Kaisha Personal ornament and method for producing personal ornament
JP7187604B2 (ja) * 2021-04-14 2022-12-12 日鉄ステンレス株式会社 耐溶接高温割れ性に優れた高Ｎｉ合金
KR102569355B1 (ko) 2021-04-14 2023-08-22 닛테츠 스테인레스 가부시키가이샤 내용접 고온 균열성이 우수한 고Ni 합금
DE102021211652A1 (de) * 2021-10-15 2023-04-20 Siemens Energy Global GmbH & Co. KG Austenitlegierung, Rohteil und Bauteil sowie Verfahren

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0753898B2 (ja) * 1987-01-24 1995-06-07 新日本製鐵株式会社 高強度オ−ステナイト系耐熱合金
US5378427A (en) * 1991-03-13 1995-01-03 Sumitomo Metal Industries, Ltd. Corrosion-resistant alloy heat transfer tubes for heat-recovery boilers
JPH05195127A (ja) * 1992-01-22 1993-08-03 Sumitomo Metal Ind Ltd ボイラ伝熱管用高耐食合金
JPH09165655A (ja) * 1995-12-14 1997-06-24 Nkk Corp 高温機器用オーステナイトステンレス鋼およびその製造方法
JP3329261B2 (ja) * 1998-03-26 2002-09-30 住友金属工業株式会社 高温高強度鋼用溶接材料および溶接継手
JP4424471B2 (ja) * 2003-01-29 2010-03-03 住友金属工業株式会社 オーステナイト系ステンレス鋼およびその製造方法
CN100473730C (zh) * 2004-09-15 2009-04-01 住友金属工业株式会社 管内表面的鳞片的耐剥离性优良的钢管
JP4492805B2 (ja) * 2004-09-15 2010-06-30 住友金属工業株式会社 管内表面のスケールの耐剥離性に優れた鋼管
JP4946758B2 (ja) * 2007-09-28 2012-06-06 住友金属工業株式会社 長期使用後の加工性に優れた高温用オーステナイト系ステンレス鋼
KR20100059957A (ko) * 2007-10-03 2010-06-04 수미도모 메탈 인더스트리즈, 리미티드 오스테나이트계 스테인리스강
JP4258679B1 (ja) * 2007-10-04 2009-04-30 住友金属工業株式会社 オーステナイト系ステンレス鋼
EP2412841B1 (fr) * 2009-03-27 2018-11-14 Nippon Steel & Sumitomo Metal Corporation Acier inoxydable austénitique
JP5586279B2 (ja) * 2010-03-15 2014-09-10 新日鐵住金ステンレス株式会社 自動車排気系部材用フェライト系ステンレス鋼
BR112013025511B1 (pt) * 2011-06-24 2019-05-07 Nippon Steel & Sumitomo Metal Corporation Material metálico resistente à carburação
JP5661001B2 (ja) * 2011-08-23 2015-01-28 山陽特殊製鋼株式会社 時効後靭性に優れた高強度オーステナイト系耐熱鋼
JP5930635B2 (ja) * 2011-09-26 2016-06-08 山陽特殊製鋼株式会社 優れた高温強度を有するオーステナイト系耐熱鋼とその製造方法
US9347121B2 (en) * 2011-12-20 2016-05-24 Ati Properties, Inc. High strength, corrosion resistant austenitic alloys
JP5786830B2 (ja) * 2012-09-03 2015-09-30 新日鐵住金株式会社 高圧水素ガス用高強度オーステナイトステンレス鋼
CN103966528A (zh) * 2014-04-29 2014-08-06 宝钢不锈钢有限公司 一种含Sn奥氏体不锈钢及其制造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
CA2988556A1 (fr) 2017-01-05
US20180216215A1 (en) 2018-08-02
CN107709595A (zh) 2018-02-16
WO2017002523A1 (fr) 2017-01-05
CA2988556C (fr) 2020-04-21
KR20180012813A (ko) 2018-02-06
KR102048479B1 (ko) 2019-11-25
CN107709595B (zh) 2019-07-23
EP3318650A4 (fr) 2018-12-26
ES2759543T3 (es) 2020-05-11
JPWO2017002523A1 (ja) 2018-03-29
EP3318650A1 (fr) 2018-05-09
JP6384610B2 (ja) 2018-09-05

Similar Documents

Publication Publication Date Title
EP3318650B1 (fr) Alliage austénitique thermorésistant et structure soudée
EP3318651B1 (fr) Alliage austénitique résistant à la chaleur et joint soudé
EP2206796B1 (fr) Alliage austénitique résistant à la chaleur
EP2781612B1 (fr) Tube en alliage résistant à la chaleur en austénite sans soudure
US8801876B2 (en) Ni-based alloy product and producing method thereof
KR102031776B1 (ko) 오스테나이트계 내열합금 용접 조인트의 제조 방법 및 그것을 이용하여 얻어지는 용접 조인트
JP5170297B1 (ja) Ｎｉ基耐熱合金用溶接材料ならびにそれを用いてなる溶接金属および溶接継手
CN111344427B (zh) 奥氏体系耐热钢焊接金属、焊接接头、奥氏体系耐热钢用焊接材料以及焊接接头的制造方法
EP3693484A1 (fr) Métal soudé d'acier inoxydable à base d'austénite, et structure soudée
JP6623719B2 (ja) オーステナイト系ステンレス鋼
EP3693486B1 (fr) Métal soudé d'acier inoxydable à base d'austénite, et structure soudée
EP3693487A1 (fr) Acier inoxydable à base d'austénite
JP7368722B2 (ja) オーステナイト系耐熱鋼溶接金属、溶接継手、およびオーステナイト系耐熱鋼用溶接材料
JP6638552B2 (ja) オーステナイト系耐熱鋼用溶接材料
JP2021021130A (ja) オーステナイト系耐熱合金溶接継手
JP2021011610A (ja) オーステナイト系耐熱合金溶接継手
JP6638551B2 (ja) オーステナイト系耐熱鋼溶接金属およびそれを有する溶接継手
JP2019130591A (ja) 溶接継手
JP2019173122A (ja) 溶接継手
JP2021025096A (ja) オーステナイト系耐熱合金溶接継手
JP2021025095A (ja) オーステナイト系耐熱合金溶接継手

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: 20171128

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

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

Effective date: 20181128

RIC1 Information provided on ipc code assigned before grant

Ipc: C22C 38/48 20060101ALI20181123BHEP

Ipc: C22C 38/44 20060101ALI20181123BHEP

Ipc: C22C 38/54 20060101ALI20181123BHEP

Ipc: C22C 38/02 20060101ALI20181123BHEP

Ipc: C22C 38/52 20060101ALI20181123BHEP

Ipc: C22C 38/00 20060101AFI20181123BHEP

Ipc: C22C 38/46 20060101ALI20181123BHEP

Ipc: C22C 38/50 20060101ALI20181123BHEP

Ipc: C22C 38/42 20060101ALI20181123BHEP

Ipc: C22C 38/06 20060101ALI20181123BHEP

Ipc: C22C 38/04 20060101ALI20181123BHEP

Ipc: C22C 38/58 20060101ALI20181123BHEP

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: 20190606

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

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

Owner name: NIPPON STEEL CORPORATION

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

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: DE

Ref legal event code: R096

Ref document number: 602016022297

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1188898

Country of ref document: AT

Kind code of ref document: T

Effective date: 20191115

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20191009

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

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

Ref country code: 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: 20200109

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: 20191009

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: 20200110

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: 20191009

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: 20191009

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: 20200109

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: 20200210

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: 20191009

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: 20191009

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2759543

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20200511

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: 20200224

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: 20191009

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: 20191009

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: 20191009

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602016022297

Country of ref document: DE

PG2D Information on lapse in contracting state deleted

Ref country code: IS

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

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: 20191009

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: 20191009

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: 20191009

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: 20200209

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: 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: 20191009

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: 20191009

26N No opposition filed

Effective date: 20200710

REG Reference to a national code

Ref country code: AT

Ref legal event code: UEP

Ref document number: 1188898

Country of ref document: AT

Kind code of ref document: T

Effective date: 20191009

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: 20191009

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: 20191009

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: LU

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

Effective date: 20200602

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20200630

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: 20200602

Ref country code: CH

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

Effective date: 20200630

Ref country code: LI

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

Effective date: 20200630

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: 20200630

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: 20191009

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: 20191009

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: 20191009

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: 20191009

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

Ref country code: IT

Payment date: 20230510

Year of fee payment: 8

Ref country code: FR

Payment date: 20230510

Year of fee payment: 8

Ref country code: DE

Payment date: 20230502

Year of fee payment: 8

Ref country code: CZ

Payment date: 20230517

Year of fee payment: 8

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

Ref country code: SE

Payment date: 20230510

Year of fee payment: 8

Ref country code: AT

Payment date: 20230525

Year of fee payment: 8

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

Ref country code: GB

Payment date: 20230427

Year of fee payment: 8

Ref country code: ES

Payment date: 20230706

Year of fee payment: 8