EP3822384A1 - Austenitic stainless steel having improved strength - Google Patents
Austenitic stainless steel having improved strength Download PDFInfo
- Publication number
- EP3822384A1 EP3822384A1 EP19849274.6A EP19849274A EP3822384A1 EP 3822384 A1 EP3822384 A1 EP 3822384A1 EP 19849274 A EP19849274 A EP 19849274A EP 3822384 A1 EP3822384 A1 EP 3822384A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- stainless steel
- austenitic stainless
- content
- less
- phase
- 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
Links
- 229910000963 austenitic stainless steel Inorganic materials 0.000 title claims abstract description 35
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 28
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 23
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 23
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 48
- 229910001566 austenite Inorganic materials 0.000 description 39
- 239000011572 manganese Substances 0.000 description 37
- 229910001220 stainless steel Inorganic materials 0.000 description 30
- 239000010935 stainless steel Substances 0.000 description 28
- 239000011651 chromium Substances 0.000 description 25
- 230000007797 corrosion Effects 0.000 description 25
- 238000005260 corrosion Methods 0.000 description 25
- 239000000463 material Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 229910000734 martensite Inorganic materials 0.000 description 17
- 239000010949 copper Substances 0.000 description 16
- 238000000137 annealing Methods 0.000 description 15
- 229910000859 α-Fe Inorganic materials 0.000 description 13
- 229910000831 Steel Inorganic materials 0.000 description 12
- 229910045601 alloy Inorganic materials 0.000 description 12
- 239000000956 alloy Substances 0.000 description 12
- 230000000087 stabilizing effect Effects 0.000 description 12
- 239000010959 steel Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 238000004364 calculation method Methods 0.000 description 8
- 238000009628 steelmaking Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 239000011575 calcium Substances 0.000 description 6
- 229910001039 duplex stainless steel Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000009466 transformation Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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
- 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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
-
- 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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0263—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—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
- C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
-
- 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 disclosure relates to austenitic stainless steel, in particular, to austenitic stainless steel with improved strength while securing elongation and corrosion resistance.
- Stainless steel refers to steel that has strong corrosion resistance by suppressing corrosion, a weak point of carbon steel.
- stainless steel is classified according to its chemical composition or metal structure. According to the metal structure, stainless steel can be classified into austenite, ferrite, martensite and dual phase.
- austenitic stainless steel is a steel containing a large amount of chromium (Cr) and nickel (Ni), and is most commonly used.
- 316L stainless steel has a component based on 16 ⁇ 18% Cr, 10 ⁇ 14% Ni, and 2 ⁇ 3% molybdenum (Mo), is applied in various industrial fields by securing corrosion resistance and molding properties.
- 216 stainless steel is basically a steel containing a large amount of Mn of 7% or more in order to reduce the material price by reducing the Ni content to a certain amount or less, and to secure the stability of the austenite phase according to the amount of Ni reduction. It contains 17.5 ⁇ 22% Cr, 5 ⁇ 7% Ni, 7.5 ⁇ 9% Mn and 2 ⁇ 3% Mo in percent (%) by weight.
- 216 stainless steel can secure a level of corrosion resistance similar to that of 316L stainless steel, but due to the generation of a large amount of Mn fume during the steel making process due to the addition of a large amount of Mn, not only environmental improvement is required, but also the production of steel making inclusions (MnS) results in a decrease in productivity in the manufacturing process and a decrease in the surface quality of the final material.
- MnS steel making inclusions
- duplex stainless steel is a substitute for 316L stainless steel.
- Duplex stainless steel is a stainless steel having a microstructure in which austenite phase and ferrite phase are mixed. Specifically, the austenite phase and the ferrite phase each exist in a volume fraction of about 35 to 65%, showing the characteristics of both austenitic stainless steel and ferritic stainless steel.
- Duplex stainless steel secures corrosion resistance equivalent to 316L stainless steel, and has low Ni content, making it economical and easy to secure high strength. Therefore, it is in the spotlight as a steel for industrial facilities such as desalination facilities, pulp, paper, and chemical facilities that require corrosion resistance.
- Embodiments of the present disclosure are intended to provide an austenitic stainless steel with improved strength while securing elongation and corrosion resistance of the existing 316L stainless steel level.
- an austenitic stainless steel with improved strength includes, in percent (%) by weight of the entire composition, C: 0.02 to 0.14%, Si: 0.2 to 0.6%, S: less than 0.01%, Mn: 2.0 to 4.5%, Ni: 2.5 to 5.0%, Cr: 19.0 to 22.0%, Cu: 1.0 to 3.0%, Mo: less than 1.0%, N: 0.25 to 0.40%, the remainder of iron (Fe) and other inevitable impurities, and the Solubility of Nitrogen in Liquid (SNL) value represented by the following equation (1) is equal to or greater than the content of N.
- SNL ⁇ 0.188 ⁇ 0.0423 ⁇ C ⁇ 0.0517 ⁇ Si + 0.012 ⁇ Mn + 0.0048 ⁇ Ni + 0.0252 ⁇ Cr ⁇ 0.00906 ⁇ Cu + 0.00021 ⁇ Mo
- C, Si, Mn, Ni, Cr, Cu, and Mo mean the content (% by weight) of each element.
- the C+N is 0.5% or less (excluding 0).
- the austenitic stainless steel may further include: one or more of B: 0.001 to 0.005% and Ca: 0.001 to 0.003%.
- the Md 30 value represented by the following equation (2) may satisfy -50 or less.
- Md 30 551 ⁇ 462 ⁇ C + N ⁇ 9.2 ⁇ Si ⁇ 8.1 ⁇ Mn ⁇ 13.7 ⁇ Cr ⁇ 29 ⁇ Ni + Cu ⁇ 8.5 ⁇ Mo
- C, N, Si, Mn, Cr, Ni, Cu, and Mo mean the content (% by weight) of each element.
- the austenitic stainless steel may satisfy the following equation (3). Creq / Nieq ⁇ 1.8
- PREN The Pitting Resistance Equivalent Number (PREN) represented by the following equation (4) may satisfy 22 or more.
- PREN 16 + 3.3 Mo + 16 N ⁇ 0.5 Mn
- Mo, N, and Mn mean the content (% by weight) of each element.
- the yield strength (0.2 off-set) may be 400 to 450 MPa and the tensile strength may be 700 to 850 MPa.
- the elongation may be 35% or more.
- FIG. 1 is a graph for illustrating a correlation between Thermocalc. calculation result and a regression equation applied value for deriving Solubility of Nitrogen in Liquid (SNL) value of austenitic stainless steel according to an embodiment of the present disclosure.
- An austenitic stainless steel includes, in percent (%) by weight of the entire composition, C: 0.02 to 0.14%, Si: 0.2 to 0.6%, P: less than 0.1%, S: less than 0.01%, Mn: 2.0 to 4.5%, Ni: 2.5 to 5.0%, Cr: 19.0 to 22.0%, Cu: 1.0 To 3.0%, Mo: less than 1.0%, N: 0.25 to 0.40%, the remainder of iron (Fe) and other inevitable impurities.
- the content of C is 0.02 to 0.14%.
- Carbon (C) is an element effective in stabilizing the austenite phase, but when the content is low, 0.02% or more may be added as additional austenite stabilizing elements are required. However, if the content is excessive, workability may be lowered due to the solid solution strengthening effect. In addition, if the content is excessive, it may adversely affect the ductility, toughness, corrosion resistance, etc. by inducing grain boundary precipitation of Cr carbide due to latent heat after hot-rolled coiling and the heat-affected zone of the weld, so the upper limit may be limited to 0.14%.
- the content of Si is 0.2 to 0.6%.
- Si serves as a deoxidizing agent during the steelmaking process and is an effective element to improve corrosion resistance and can be added by 0.2% or more.
- Si is an element that is effective in stabilizing the ferrite phase, and when excessively added, it promotes the formation of delta ferrite in the casting slab, thereby reducing hot workability.
- the ductility/toughness of the steel material due to the solid solution strengthening effect may be lowered, and thus the upper limit thereof may be limited to 0.6%.
- the content of Mn is 2.0 to 4.5%.
- Manganese (Mn) is an austenite phase stabilizing element that is added instead of nickel (Ni) in the present disclosure. It is effective in improving cold rolling properties by suppressing the generation of strain-induced martensite, and is an element that increases the solubility of nitrogen (N) during a steelmaking process to be described later, and may be added by 2.0% or more. However, if the content is excessive, Mn may reduce the ductility, toughness, and corrosion resistance of steel materials as it causes an increase in S-based inclusions (MnS), and thus the upper limit thereof may be limited to 4.5%.
- the content of Ni is 2.5 to 5.0%.
- Nickel (Ni) is a strong austenite phase stabilizing element and is essential to secure good hot workability and cold workability. In particular, even when a certain amount of Mn is added, it is essential to add 2.5% or more. However, since Ni is an expensive element, it causes an increase in raw material cost when a large amount is added. Accordingly, the upper limit can be limited to 5.0% in consideration of both cost and efficiency of the steel.
- the content of Cr is 19 to 22%.
- chromium (Cr) is a ferrite stabilizing element, it is effective in suppressing the formation of martensite phase, and is a basic element that secures corrosion resistance required for stainless steel.
- 19% or more may be added as an element that increases the solubility of nitrogen (N) during a steelmaking process to be described later.
- N solubility of nitrogen
- ⁇ delta
- austenite stabilizing elements such as Ni and Mn
- the content of P is less than 0.1%.
- phosphorus (P) lowers corrosion resistance or hot workability, its upper limit may be limited to 0.1%.
- the content of S is less than 0.01 %.
- sulfur (S) lowers corrosion resistance or hot workability, its upper limit may be limited to 0.01%.
- the content of Cu is 1.0 to 3.0%.
- Copper (Cu) is an austenite phase stabilizing element added instead of nickel (Ni) in the present disclosure, and improves formability by improving corrosion resistance in a reducing environment and reducing Stacking Fault Energy (SFE). 1.0% or more may be added to sufficiently express such an effect. However, if the content is excessive, the upper limit may be limited to 3.0% because it may increase the material cost as well as lower the hot workability.
- the content of Mo is less than 1.0%.
- Molybdenum (Mo) is an effective element in improving the corrosion resistance of stainless steel by modifying the passive film.
- Mo is an expensive element, when a large amount of Mo is added, it causes an increase in raw material cost and has a problem of deteriorating hot workability. Accordingly, in consideration of the cost-efficiency and hot workability of the steel, the upper limit can be limited to 1.0%.
- the content of N is 0.25 to 0.40%.
- Nitrogen (N) is an element that is effective in improving corrosion resistance and is a strong austenite stabilizing element. Therefore, nitrogen alloying can reduce material cost by enabling lower use of Ni, Cu, and Mn. 0.25% or more may be added to sufficiently express this effect. However, if the content is excessive, since workability and moldability may be deteriorated due to the solid solution strengthening effect, the upper limit may be limited to 0.40%.
- the content of C+N is 0.5% or less.
- C and N are elements that are effective for improving strength, but when the content is excessive, there is a problem of lowering the workability, and the upper limit of the total may be limited to 0.5%.
- the austenitic stainless steel with improved strength according to an embodiment of the present disclosure may further include one or more of B: 0.001 to 0.005 and Ca: 0.001 to 0.003%.
- the content of B is 0.001 to 0.005%.
- Boron (B) is an element effective in securing good surface quality by suppressing the occurrence of cracks during casting, and can be added by 0.001% or more. However, if the content is excessive, nitride (BN) may be formed on the product surface during the annealing/pickling process, thereby reducing the surface quality. Therefore, the upper limit can be limited to 0.005%.
- the content of Ca is 0.001 to 0.003%.
- Calcium (Ca) is an element that improves product cleanliness by suppressing the formation of MnS steel-making inclusions generated at grain boundaries when high Mn is contained, and can be added by 0.001 % or more. However, if the content is excessive, it may cause a decrease in hot workability and a decrease in product surface quality due to formation of Ca-based inclusions, and the upper limit may be limited to 0.003%.
- the remaining component of the present disclosure is iron (Fe).
- Fe iron
- unintended impurities from the raw material or the surrounding environment may inevitably be mixed in the normal manufacturing process, this cannot be excluded. Since these impurities are known to anyone of ordinary skill in the manufacturing process, all the contents are not specifically mentioned in the present specification.
- the content of N that can be dissolved in the molten metal temperature at 1150°C is derived according to the amount of each alloy element (C, Si, Mn, Ni, Cr, Cu, Mo) added.
- FIG. 1 is a graph for illustrating a correlation between Thermocalc. calculation result and a regression equation applied value for deriving Solubility of Nitrogen in Liquid (SNL) value of austenitic stainless steel according to an embodiment of the present disclosure.
- N solubility limit (The.)
- SNL Solubility of Nitrogen in Liquid regression equation of Equation (1) was derived based on the calculated value of Thermocalc. according to the component change.
- SNL ⁇ 0.188 ⁇ 0.0423 ⁇ C ⁇ 0.0517 ⁇ Si + 0.012 ⁇ Mn + 0.0048 ⁇ Ni + 0.0252 ⁇ Cr ⁇ 0.00906 ⁇ Cu + 0.00021 ⁇ Mo
- the SNL value is greater than or equal to N content. In this way, when the SNL value was set higher than the N content to increase the nitrogen solubility limit, it was confirmed that the steelmaking operation of the target alloy component was performed satisfactorily.
- austenitic stainless steel In the case of austenitic stainless steel, it is applied to products that require a beautiful surface. For products that require a beautiful surface, it is common to perform a bright annealing on cold-rolled materials.
- This bright annealing is a heat treatment technology that keeps the surface bright and beautiful without changing the color and properties of the surface by preventing reoxidation occurring during the heat treatment process of the stainless steel cold rolled material by performing heat treatment on the stainless steel cold rolled material in a reducing atmosphere (Dew point -40 ⁇ -60°C) using nitrogen (N 2 ), hydrogen (H 2 ), etc.
- Bright annealing using hydrogen as the atmosphere gas used for bright annealing is the most common, because it is most widely used for suppressing discoloration of the surface as well as high heat capacity.
- the hydrogen atoms penetrating into the surface layer are naturally bake-out after a certain period of time at room temperature for ferrite or martensite phase, which are general BCC and BCT structures, and do not significantly affect the physical properties.
- This hydrogen atom is known as a factor causing hydrogen embrittlement. Hydrogen atoms trapped in the material due to some processing or deformation change to the state of hydrogen molecules (gas), and when a certain pressure is reached, it acts as a starting point of cracks under a certain load, causing a decrease in elongation.
- the beautiful surface quality and workability can be secured through bright annealing only by controlling the amount of martensite phase formed on the surface by work hardening together with the alloy component.
- the Md30 value expressed by the following equation (2) satisfies the range of -50°C or less.
- Md 30 551 ⁇ 462 ⁇ C + N ⁇ 9.2 ⁇ Si ⁇ 8.1 ⁇ Mn ⁇ 13.7 ⁇ Cr ⁇ 29 ⁇ Ni + Cu ⁇ 8.5 ⁇ Mo
- martensitic transformation occurs by plastic working at a temperature of the martensitic transformation initiation temperature (Ms) or more.
- the upper limit temperature that causes phase transformation by such processing is represented by the Md value, and is a criterion of the degree to which phase transformation occurs by processing.
- the temperature (°C) at which 50% phase transformation to martensite occurs when 30% strain is applied is defined as Md 30 .
- Md 30 value is used as an index to determine the austenite stability of austenitic stainless steel, and can be calculated through the Nohara regression equation expressed by the equation (2).
- Creq Cr +Mo +1.5xSi
- Nieq Ni +0.5 ⁇ Mn +30x(C +N) +0.5 ⁇ Cu.
- PREN Pitting Resistance Equivalent Number
- PREN is generally used to influence Cr, Mo, and N, but for steel grades with relatively high Mn content, since it is necessary to consider the influence of Mn as well, the following equation (4) was derived from the present disclosure.
- a slab having a thickness of 200 mm was prepared by melting an ingot, heated at 1,240°C for 2 hours, and then hot-rolled to prepare a hot-rolled steel sheet having a thickness of 3 mm.
- comparative example 1 which corresponds to the composition of general 316L stainless steel, it represents the tissue composed of the austenite phase, and it can be seen that the PREN value is 22 or higher.
- the mechanical property evaluation result showed a yield strength of 220 MPa and a tensile strength of 540 MPa.
- This corresponds to the physical properties of generally widely used soft austenitic stainless steel, and thus has a problem that is difficult to apply to materials requiring high strength.
- the Md 30 value is -5°C, and hydrogen embrittlement is likely to occur when producing bright annealing materials with beautiful surfaces in the future.
- the N solubility limit which is greatly affected by the Cr content, is low, the amount of N added is 0.21%, and the nitrogen factor of the PREN value cannot be maximized, making it difficult to secure pitting resistance of 316L level.
- the C+N content is 0.5%, exceeding 0.5%, which is the upper limit of the present disclosure, indicating hard mechanical properties and elongation of less than 35%.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Heat Treatment Of Sheet Steel (AREA)
- Heat Treatment Of Steel (AREA)
- Materials For Medical Uses (AREA)
Abstract
Description
- The present disclosure relates to austenitic stainless steel, in particular, to austenitic stainless steel with improved strength while securing elongation and corrosion resistance.
- Stainless steel refers to steel that has strong corrosion resistance by suppressing corrosion, a weak point of carbon steel. In general, stainless steel is classified according to its chemical composition or metal structure. According to the metal structure, stainless steel can be classified into austenite, ferrite, martensite and dual phase.
- Among them, austenitic stainless steel is a steel containing a large amount of chromium (Cr) and nickel (Ni), and is most commonly used. For example, 316L stainless steel has a component based on 16∼18% Cr, 10∼14% Ni, and 2∼3% molybdenum (Mo), is applied in various industrial fields by securing corrosion resistance and molding properties.
- However, in the case of Ni and Mo, there is a problem in terms of price competitiveness due to high material prices, and raw material supply and demand are unstable due to extreme fluctuations in material prices, and it is difficult to secure supply price stability.
- Therefore, research has been conducted to reduce the content of Ni and Mo while securing corrosion resistance and formability of the conventional 316L stainless steel level. As a substitute for such 316L stainless steel, 200 series stainless steel, for example, 216 steel, which reduced Ni and increased the content of Mn was developed.
- 216 stainless steel is basically a steel containing a large amount of Mn of 7% or more in order to reduce the material price by reducing the Ni content to a certain amount or less, and to secure the stability of the austenite phase according to the amount of Ni reduction. It contains 17.5∼22% Cr, 5∼7% Ni, 7.5∼9% Mn and 2∼3% Mo in percent (%) by weight.
- By this component-based design, 216 stainless steel can secure a level of corrosion resistance similar to that of 316L stainless steel, but due to the generation of a large amount of Mn fume during the steel making process due to the addition of a large amount of Mn, not only environmental improvement is required, but also the production of steel making inclusions (MnS) results in a decrease in productivity in the manufacturing process and a decrease in the surface quality of the final material.
- Meanwhile, the duplex stainless steel is a substitute for 316L stainless steel.
- Duplex stainless steel is a stainless steel having a microstructure in which austenite phase and ferrite phase are mixed. Specifically, the austenite phase and the ferrite phase each exist in a volume fraction of about 35 to 65%, showing the characteristics of both austenitic stainless steel and ferritic stainless steel.
- Duplex stainless steel secures corrosion resistance equivalent to 316L stainless steel, and has low Ni content, making it economical and easy to secure high strength. Therefore, it is in the spotlight as a steel for industrial facilities such as desalination facilities, pulp, paper, and chemical facilities that require corrosion resistance.
- In particular, among duplex stainless steels, research on Lean Duplex stainless steel limited to 19∼23% Cr, 1.8∼3.5% Ni, 0∼2% Mn and 0.5-1.0% Mo by reducing expensive alloying elements such as Ni and Mo and, which further highlights the advantages of low alloy cost through the addition of 0.16∼0.3% high nitrogen, is being actively conducted.
- However, in the case of lean duplex stainless steel, there is a problem in that the formability and elongation are inferior due to the formation of an phase interface between austenite and ferrite. Therefore, it is required to develop austenitic stainless steel with improved strength while securing elongation and corrosion resistance while reducing Ni and Mo.
- Embodiments of the present disclosure are intended to provide an austenitic stainless steel with improved strength while securing elongation and corrosion resistance of the existing 316L stainless steel level.
- In accordance with an aspect of the present disclosure, an austenitic stainless steel with improved strength includes, in percent (%) by weight of the entire composition, C: 0.02 to 0.14%, Si: 0.2 to 0.6%, S: less than 0.01%, Mn: 2.0 to 4.5%, Ni: 2.5 to 5.0%, Cr: 19.0 to 22.0%, Cu: 1.0 to 3.0%, Mo: less than 1.0%, N: 0.25 to 0.40%, the remainder of iron (Fe) and other inevitable impurities, and the Solubility of Nitrogen in Liquid (SNL) value represented by the following equation (1) is equal to or greater than the content of N.
- (Here, C, Si, Mn, Ni, Cr, Cu, and Mo mean the content (% by weight) of each element.)
- The C+N is 0.5% or less (excluding 0).
- The austenitic stainless steel may further include: one or more of B: 0.001 to 0.005% and Ca: 0.001 to 0.003%.
-
- (Here, C, N, Si, Mn, Cr, Ni, Cu, and Mo mean the content (% by weight) of each element.)
-
- (Here, Creq = Cr +Mo +1.5 × Si, Nieq = Ni +0.5 × Mn +30 × (C +N) +0.5 × Cu.)
-
- (Here, Mo, N, and Mn mean the content (% by weight) of each element.)
- The yield strength (0.2 off-set) may be 400 to 450 MPa and the tensile strength may be 700 to 850 MPa.
- The elongation may be 35% or more.
- According to an embodiment of the present disclosure, it is possible to provide austenitic stainless steel with improved strength while securing elongation and corrosion resistance of the existing 316L stainless steel level.
-
FIG. 1 is a graph for illustrating a correlation between Thermocalc. calculation result and a regression equation applied value for deriving Solubility of Nitrogen in Liquid (SNL) value of austenitic stainless steel according to an embodiment of the present disclosure. - Hereinafter, the embodiments of the present disclosure will be described in detail with reference to the accompanying drawings. The following embodiments are provided to transfer the technical concepts of the present disclosure to one of ordinary skill in the art. However, the present disclosure is not limited to these embodiments, and may be embodied in another form. In the drawings, parts that are irrelevant to the descriptions may be not shown in order to clarify the present disclosure, and also, for easy understanding, the sizes of components are more or less exaggeratedly shown.
- Throughout the specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless specifically stated to the contrary.
- Expressions in the singular number include expressions in the plural unless the context clearly has exceptions.
- Hereinafter, embodiments according to the present disclosure will be described in detail with reference to the accompanying drawings.
- An austenitic stainless steel according to an aspect of present disclosure includes, in percent (%) by weight of the entire composition, C: 0.02 to 0.14%, Si: 0.2 to 0.6%, P: less than 0.1%, S: less than 0.01%, Mn: 2.0 to 4.5%, Ni: 2.5 to 5.0%, Cr: 19.0 to 22.0%, Cu: 1.0 To 3.0%, Mo: less than 1.0%, N: 0.25 to 0.40%, the remainder of iron (Fe) and other inevitable impurities.
- Hereinafter, the reason for limiting the numerical value of the content of the alloying component in the embodiment of the present disclosure will be described. Hereinafter, unless otherwise specified, the unit is % by weight.
- The content of C is 0.02 to 0.14%.
- Carbon (C) is an element effective in stabilizing the austenite phase, but when the content is low, 0.02% or more may be added as additional austenite stabilizing elements are required. However, if the content is excessive, workability may be lowered due to the solid solution strengthening effect. In addition, if the content is excessive, it may adversely affect the ductility, toughness, corrosion resistance, etc. by inducing grain boundary precipitation of Cr carbide due to latent heat after hot-rolled coiling and the heat-affected zone of the weld, so the upper limit may be limited to 0.14%.
- The content of Si is 0.2 to 0.6%.
- Silicon (Si) serves as a deoxidizing agent during the steelmaking process and is an effective element to improve corrosion resistance and can be added by 0.2% or more. However, Si is an element that is effective in stabilizing the ferrite phase, and when excessively added, it promotes the formation of delta ferrite in the casting slab, thereby reducing hot workability. In addition, when excessively added, the ductility/toughness of the steel material due to the solid solution strengthening effect may be lowered, and thus the upper limit thereof may be limited to 0.6%.
- The content of Mn is 2.0 to 4.5%.
- Manganese (Mn) is an austenite phase stabilizing element that is added instead of nickel (Ni) in the present disclosure. It is effective in improving cold rolling properties by suppressing the generation of strain-induced martensite, and is an element that increases the solubility of nitrogen (N) during a steelmaking process to be described later, and may be added by 2.0% or more. However, if the content is excessive, Mn may reduce the ductility, toughness, and corrosion resistance of steel materials as it causes an increase in S-based inclusions (MnS), and thus the upper limit thereof may be limited to 4.5%.
- The content of Ni is 2.5 to 5.0%.
- Nickel (Ni) is a strong austenite phase stabilizing element and is essential to secure good hot workability and cold workability. In particular, even when a certain amount of Mn is added, it is essential to add 2.5% or more. However, since Ni is an expensive element, it causes an increase in raw material cost when a large amount is added. Accordingly, the upper limit can be limited to 5.0% in consideration of both cost and efficiency of the steel.
- The content of Cr is 19 to 22%.
- Although chromium (Cr) is a ferrite stabilizing element, it is effective in suppressing the formation of martensite phase, and is a basic element that secures corrosion resistance required for stainless steel. In addition, 19% or more may be added as an element that increases the solubility of nitrogen (N) during a steelmaking process to be described later. However, if the content is excessive, the manufacturing cost increases, and the formation of delta (δ) ferrite in the slab leads to a decrease in hot workability. Accordingly, there is a problem that additional addition of austenite stabilizing elements such as Ni and Mn is required, and the upper limit thereof can be limited to 22%.
- The content of P is less than 0.1%.
- As phosphorus (P) lowers corrosion resistance or hot workability, its upper limit may be limited to 0.1%.
- The content of S is less than 0.01 %.
- As sulfur (S) lowers corrosion resistance or hot workability, its upper limit may be limited to 0.01%.
- The content of Cu is 1.0 to 3.0%.
- Copper (Cu) is an austenite phase stabilizing element added instead of nickel (Ni) in the present disclosure, and improves formability by improving corrosion resistance in a reducing environment and reducing Stacking Fault Energy (SFE). 1.0% or more may be added to sufficiently express such an effect. However, if the content is excessive, the upper limit may be limited to 3.0% because it may increase the material cost as well as lower the hot workability.
- The content of Mo is less than 1.0%.
- Molybdenum (Mo) is an effective element in improving the corrosion resistance of stainless steel by modifying the passive film. However, since Mo is an expensive element, when a large amount of Mo is added, it causes an increase in raw material cost and has a problem of deteriorating hot workability. Accordingly, in consideration of the cost-efficiency and hot workability of the steel, the upper limit can be limited to 1.0%.
- The content of N is 0.25 to 0.40%.
- Nitrogen (N) is an element that is effective in improving corrosion resistance and is a strong austenite stabilizing element. Therefore, nitrogen alloying can reduce material cost by enabling lower use of Ni, Cu, and Mn. 0.25% or more may be added to sufficiently express this effect. However, if the content is excessive, since workability and moldability may be deteriorated due to the solid solution strengthening effect, the upper limit may be limited to 0.40%.
- The content of C+N is 0.5% or less.
- C and N are elements that are effective for improving strength, but when the content is excessive, there is a problem of lowering the workability, and the upper limit of the total may be limited to 0.5%.
- In addition, the austenitic stainless steel with improved strength according to an embodiment of the present disclosure may further include one or more of B: 0.001 to 0.005 and Ca: 0.001 to 0.003%.
- The content of B is 0.001 to 0.005%.
- Boron (B) is an element effective in securing good surface quality by suppressing the occurrence of cracks during casting, and can be added by 0.001% or more. However, if the content is excessive, nitride (BN) may be formed on the product surface during the annealing/pickling process, thereby reducing the surface quality. Therefore, the upper limit can be limited to 0.005%.
- The content of Ca is 0.001 to 0.003%.
- Calcium (Ca) is an element that improves product cleanliness by suppressing the formation of MnS steel-making inclusions generated at grain boundaries when high Mn is contained, and can be added by 0.001 % or more. However, if the content is excessive, it may cause a decrease in hot workability and a decrease in product surface quality due to formation of Ca-based inclusions, and the upper limit may be limited to 0.003%.
- The remaining component of the present disclosure is iron (Fe). However, since unintended impurities from the raw material or the surrounding environment may inevitably be mixed in the normal manufacturing process, this cannot be excluded. Since these impurities are known to anyone of ordinary skill in the manufacturing process, all the contents are not specifically mentioned in the present specification.
- In order to secure price competitiveness of austenite stainless steel, it is necessary to reduce the content of expensive austenite stabilizing elements such as Ni and Mn, and it is required to predict the amount of N added that can compensate for this. To this end, it is necessary to set the optimal N content through calculation of the solubility limit of N in consideration of each alloy component.
- Thus, using the state diagram prediction program Thermocalc., the content of N that can be dissolved in the molten metal temperature at 1150°C is derived according to the amount of each alloy element (C, Si, Mn, Ni, Cr, Cu, Mo) added.
-
FIG. 1 is a graph for illustrating a correlation between Thermocalc. calculation result and a regression equation applied value for deriving Solubility of Nitrogen in Liquid (SNL) value of austenitic stainless steel according to an embodiment of the present disclosure. - Referring to
FIG. 1 , the limit value at which nitrogen is dissolved in the molten metal is calculated and expressed as "N solubility limit (The.)". -
- When applying the derived regression equation, it was confirmed that the R(sq) value corresponds to a high correlation of 100%. In addition, it was confirmed that it is possible to secure suitability in the relationship between the calculation result of the thermocalc for each component to derive SNL, which is N melting limit value, and the regression equation.
- In the austenitic stainless steel with improved strength according to an embodiment of the present disclosure, the SNL value is greater than or equal to N content. In this way, when the SNL value was set higher than the N content to increase the nitrogen solubility limit, it was confirmed that the steelmaking operation of the target alloy component was performed satisfactorily.
- In the case of austenitic stainless steel, it is applied to products that require a beautiful surface. For products that require a beautiful surface, it is common to perform a bright annealing on cold-rolled materials. This bright annealing is a heat treatment technology that keeps the surface bright and beautiful without changing the color and properties of the surface by preventing reoxidation occurring during the heat treatment process of the stainless steel cold rolled material by performing heat treatment on the stainless steel cold rolled material in a reducing atmosphere (Dew point -40 ∼ -60°C) using nitrogen (N2), hydrogen (H2), etc. Bright annealing using hydrogen as the atmosphere gas used for bright annealing is the most common, because it is most widely used for suppressing discoloration of the surface as well as high heat capacity.
- Compared to general austenitic stainless steel, in stainless steel that has reduced austenite stabilizing elements such as Ni and Mn as in the present disclosure, there is a point to be considered when applying bright annealing in a hydrogen atmosphere.
- During bright annealing, there is a high possibility of inferior workability due to hydrogen embrittlement defects in the final material due to the penetration of hydrogen. In the case of stainless steel with reduced austenite stabilizing elements such as Ni and Mn, during cold rolling before final bright annealing, stress-induced martensite or strain-induced martensite is formed around the surface layer. The martensite phase formed on the surface layer is in contact with hydrogen atoms, which are inert gases, before being transformed into an austenite phase by heat treatment during bright annealing. Some of these hydrogen atoms penetrate into the martensite phase. As the existing stress-induced martensite or strain-induced martensite is phase-transformed into the austenite phase by bright annealing, hydrogen atoms that have penetrated inside cannot be discharged to the outside and are trapped in the atomic state at the surface.
- The hydrogen atoms penetrating into the surface layer are naturally bake-out after a certain period of time at room temperature for ferrite or martensite phase, which are general BCC and BCT structures, and do not significantly affect the physical properties.
- On the other hand, when the martensite phase of the surface layer is transformed into an austenite phase by bright annealing, that is, when hydrogen atoms are present in the lattice structure of FCC, even after a considerable amount of time has passed at room temperature, the natural bakeout of hydrogen atoms is not smooth and remains in the material for a long time.
- This hydrogen atom is known as a factor causing hydrogen embrittlement. Hydrogen atoms trapped in the material due to some processing or deformation change to the state of hydrogen molecules (gas), and when a certain pressure is reached, it acts as a starting point of cracks under a certain load, causing a decrease in elongation.
- Therefore, for austenitic stainless steel with relatively low Ni and Mn, the beautiful surface quality and workability can be secured through bright annealing only by controlling the amount of martensite phase formed on the surface by work hardening together with the alloy component.
-
- In austenitic stainless steel, martensitic transformation occurs by plastic working at a temperature of the martensitic transformation initiation temperature (Ms) or more. The upper limit temperature that causes phase transformation by such processing is represented by the Md value, and is a criterion of the degree to which phase transformation occurs by processing.
- In particular, the temperature (°C) at which 50% phase transformation to martensite occurs when 30% strain is applied is defined as Md30. When the Md30 value is high, it is easy to form the strain-induced martensite phase, whereas when the Md30 value is low, the strain-induced martensite phase is relatively difficult to form. In general, the Md30 value is used as an index to determine the austenite stability of austenitic stainless steel, and can be calculated through the Nohara regression equation expressed by the equation (2).
- The reason why various kinds of phases are formed by the difference in alloy component content is because the effect of each added alloy component on the phase balance is different.
-
- Here, Creq = Cr +Mo +1.5xSi, Nieq = Ni +0.5×Mn +30x(C +N) +0.5×Cu.
- That is, when the Creq/Nieq ratio is low, austenite single phase can be formed at room temperature due to relatively high austenite stability. When the Creq/Nieq ratio is high, the austenite stability is low and the ferrite phase is likely to be formed locally.
- As a result of reviewing by applying the Creq/Nieq ratio to various alloy components, present inventor confirmed that the formation of austenite single-phase matrix structure was possible when the Creq/Nieq ratio was 1.8 or less.
- Various methods are used as a criterion for evaluating the corrosion resistance of stainless steel, but the use of the Pitting Resistance Equivalent Number (PREN) is a simple method of examining the discrimination power of alloy components.
- PREN is generally used to influence Cr, Mo, and N, but for steel grades with relatively high Mn content, since it is necessary to consider the influence of Mn as well, the following equation (4) was derived from the present disclosure.
- When the generally used high corrosion resistance 316L stainless steel alloy composition is applied to the following equation, it shows a value of about 22. Therefore, in the present disclosure, the PREN value was set to 22 or higher in order to secure corrosion resistance equal to or higher than that of 316L stainless steel.
- Hereinafter, the present disclosure will be described in more detail through examples.
- For various alloy component ranges shown in Table 1 below, a slab having a thickness of 200 mm was prepared by melting an ingot, heated at 1,240°C for 2 hours, and then hot-rolled to prepare a hot-rolled steel sheet having a thickness of 3 mm.
[Table 1] C Si Mn S Ni Cr Cu Mo N C+N inventive example 1 0.104 0.48 2.91 0.005 3.53 20.8 2.1 0.52 0.3 0.404 inventive example 2 0.103 0.49 3.4 0.005 3.35 19.6 1.16 0.39 0.27 0.373 inventive example 3 0.088 0.31 3.41 0.004 3.7 21.7 2.51 0.10 0.34 0.428 inventive example 4 0.035 0.31 3.8 0.006 4.2 21 2.48 0.20 0.33 0.365 comparative example 1 0.02 0.52 1.4 0.004 10.4 16.6 0.39 2.00 0.018 0.038 comparative example 2 0.014 0.55 2.4 0.006 2.4 20.3 0.1 1.30 0.2 0.166 comparative example 3 0.1 0.38 3.8 0.006 3.4 17.2 1.45 0.10 0.21 0.310 comparative example 4 0.15 0.46 3.8 0.004 3.6 21.6 2.04 0.32 0.35 0.500 - After performing a solution treatment at 1,150°C for 1 minute, microstructure observation and evaluation of various mechanical properties were performed.
- Mechanical properties were measured using a No. 5 test piece specified in Japanese Industrial Standard JIS Z 2201. Specifically, a tensile test was conducted using JIS Z 2201, and the measured yield strength, tensile strength, and elongation were described in Table 2 below.
- In addition, SNL calculation results, Md30 calculation results, Creq/Nieq ratio calculation results, and PREN calculation results for 4 inventive examples and 4 comparative examples in Table 1 are shown in Table 2 below.
[Table 2] Steel grade N solubility limit (The.) N solubility limit (Reg.) Md30 (°C) Creq/Nieq PREN Phase analysis Mechanical properties YS (MPa) TS (MPa) EI (%) inventive example 1 0.3238 0.3244 -121 1.2140 25.861 Austenite 490 780 44% inventive example 2 0.3067 0.3080 -60 1.2322 23.507 Austenite 460 760 50% inventive example 3 0.3582 0.3590 -170 1.0914 25.765 Austenite 510 800 44% inventive example 4 0.3472 0.3488 -136 1.1845 25.04 Austenite 470 750 42% comparative example 1 0.2205 0.2204 -60 1.5585 22.788 Austenite 220 540 58% comparative example 2 0.3230 0.3233 76 2.6076 25.822 Duplex 480 700 45% comparative example 3 0.2552 0.2556 -5 1.1661 18.99 Austenite 380 720 54% comparative example 4 0.3544 0.3550 -180 1.0507 26.356 Austenite 530 830 32% - In the case of comparative example 1, which corresponds to the composition of general 316L stainless steel, it represents the tissue composed of the austenite phase, and it can be seen that the PREN value is 22 or higher. However, less than 0.25% of nitrogen was added, and the mechanical property evaluation result showed a yield strength of 220 MPa and a tensile strength of 540 MPa. This corresponds to the physical properties of generally widely used soft austenitic stainless steel, and thus has a problem that is difficult to apply to materials requiring high strength.
- In the case of comparative example 2 in which the Creq/Nieq ratio exceeds 1.8, as Mo is added above a certain level, the PREN value is about 26, indicating excellent pitting resistance. In addition, it can be seen that the mechanical property evaluation results showed a yield strength of 480 MPa, a tensile strength of 700 MPa, and an elongation of 45%.
- However, as an alloy component in which both Ni and N are relatively low, when observing the microstructure at room temperature, it was confirmed that the austenite phase and the ferrite phase formed a duplex structure with about 5:5. This is because the stabilization of ferrite in the phase balance is relatively higher than that of 316L stainless steel. In the duplex structure, cracks may occur at the interface between the austenite phase and the ferrite phase, so there is a problem that it is difficult to apply to materials requiring molding such as bending.
- In the case of comparative example 3, in which the content of Ni and Mn was slightly increased compared to comparative example 2 and the Creq/Nieq ratio was set to 1.8 or less, when the microstructure was observed, a structure composed of austenite phase was formed, and the mechanical properties were harder than 316L of comparative example 1, and softer than the duplex stainless steel of comparative example 2.
- However, the Md30 value is -5°C, and hydrogen embrittlement is likely to occur when producing bright annealing materials with beautiful surfaces in the future. In addition, since the N solubility limit, which is greatly affected by the Cr content, is low, the amount of N added is 0.21%, and the nitrogen factor of the PREN value cannot be maximized, making it difficult to secure pitting resistance of 316L level.
- In the case of comparative example 4, in which the contents of N, C, and Cr were increased compared to comparative example 3, it is suitable for manufacturing bright annealing materials as it shows the Md30 value at the level of -180°C, and by setting the Creq/Nieq ratio to 1.8 or less, it can be seen that austenite single-phase structure can be secured.
- However, it can be seen that the C+N content is 0.5%, exceeding 0.5%, which is the upper limit of the present disclosure, indicating hard mechanical properties and elongation of less than 35%.
- Referring to Table 2, in the case of inventive examples 1 to 4 of the present disclosure, it is possible to secure Md30 value below -50°C, so the possibility of hydrogen embrittlement is low during bright annealing. In addition, the ratio of the nickel equivalent (Nieq) and the chromium equivalent (Creq) (Creq/Nieq) satisfies the range of 1.8 or less, so that the austenite single-phase structure can be formed at room temperature.
- In addition, it was confirmed that the content of Ni and Mo is relatively low, and while securing price competitiveness, it has a PREN value of 22 or more. As a result of mechanical property evaluation, it was confirmed that it was possible to realize high-strength characteristics compared to 316L and secure good elongation of 35% or more.
- From the above results, for austenitic stainless steel including, in percent (%) by weight of the entire composition, C: 0.02 to 0.14%, Si: 0.2 to 0.6%, P: less than 0.1%, S: less than 0.01%, Mn: 2.0 to 4.5%, Ni: 2.5 to 5.0%, Cr: 19.0 to 22.0%, Cu: 1.0 to 3.0%, Mo: less than 1.0%, N: 0.25 to 0.40%, the remainder of iron (Fe) and other inevitable impurities, it can secure the processability and corrosion resistance of the existing 316L stainless steel level through SNL value control for securing price competitiveness and ease of steel making newly proposed by the present disclosure, Md30 value control for securing austenite phase stability, Creq/Nieq ratio control for forming austenite phase in microstructure, and PREN control for securing corrosion resistance. In addition, it can be seen that stainless steel that can improve price competitiveness and strength can be manufactured.
- In the foregoing, exemplary inventive examples of the present disclosure have been described, but the present disclosure is not limited thereto, and a person with ordinary knowledge in the relevant technical field does not depart from the concept and scope of the following claims. It will be appreciated that various changes and modifications are possible in.
Claims (8)
- An austenitic stainless steel with improved strength comprising, in percent (%) by weight of the entire composition, C: 0.02 to 0.14%, Si: 0.2 to 0.6%, S: less than 0.01%, Mn: 2.0 to 4.5%, Ni: 2.5 to 5.0%, Cr: 19.0 to 22.0%, Cu: 1.0 to 3.0%, Mo: less than 1.0%, N: 0.25 to 0.40%, the remainder of iron (Fe) and other inevitable impurities, and
wherein the Solubility of Nitrogen in Liquid (SNL) value represented by the following equation (1) is equal to or greater than the content of N. - The austenitic stainless steel of claim 1, wherein the C+N is 0.5% or less (excluding 0).
- The austenitic stainless steel of claim 1, further comprising: one or more of B: 0.001 to 0.005% and Ca: 0.001 to 0.003%.
- The austenitic stainless steel of claim 1, wherein the yield strength (0.2 off-set) is 400 to 450 MPa and the tensile strength is 700 to 850 MPa.
- The austenitic stainless steel of claim 1, wherein the elongation is 35% or more.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020180094523A KR102160735B1 (en) | 2018-08-13 | 2018-08-13 | Austenitic stainless steel with improved strength |
PCT/KR2019/009977 WO2020036370A1 (en) | 2018-08-13 | 2019-08-08 | Austenitic stainless steel having improved strength |
Publications (4)
Publication Number | Publication Date |
---|---|
EP3822384A1 true EP3822384A1 (en) | 2021-05-19 |
EP3822384A4 EP3822384A4 (en) | 2021-09-01 |
EP3822384B1 EP3822384B1 (en) | 2023-01-18 |
EP3822384B8 EP3822384B8 (en) | 2023-02-22 |
Family
ID=69525604
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19849274.6A Active EP3822384B8 (en) | 2018-08-13 | 2019-08-08 | Austenitic stainless steel having improved strength |
Country Status (6)
Country | Link |
---|---|
US (1) | US20210292877A1 (en) |
EP (1) | EP3822384B8 (en) |
KR (1) | KR102160735B1 (en) |
CN (1) | CN112789365B (en) |
FI (1) | FI3822384T3 (en) |
WO (1) | WO2020036370A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7462439B2 (en) * | 2020-03-12 | 2024-04-05 | 日鉄ステンレス株式会社 | Austenitic stainless steel and calculation method for upper limit of N |
CN113151736A (en) * | 2021-01-28 | 2021-07-23 | 中航上大高温合金材料有限公司 | Corrosion-resistant duplex stainless steel and preparation method thereof |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000026428A1 (en) * | 1998-11-02 | 2000-05-11 | Crs Holdings, Inc. | Cr-mn-ni-cu austenitic stainless steel |
JP3696552B2 (en) * | 2001-04-12 | 2005-09-21 | 日新製鋼株式会社 | Soft stainless steel plate with excellent workability and cold forgeability |
KR20090005252A (en) * | 2004-01-29 | 2009-01-12 | 제이에프이 스틸 가부시키가이샤 | Austenitic-ferritic stainless steel |
US8337749B2 (en) * | 2007-12-20 | 2012-12-25 | Ati Properties, Inc. | Lean austenitic stainless steel |
MX2010005668A (en) * | 2007-12-20 | 2010-06-03 | Ati Properties Inc | Corrosion resistant lean austenitic stainless steel. |
KR101056235B1 (en) * | 2008-11-25 | 2011-08-11 | 주식회사 포스코 | Prediction of Material Properties of Austenitic Stainless Steel Cold Rolled Products |
SE533635C2 (en) * | 2009-01-30 | 2010-11-16 | Sandvik Intellectual Property | Austenitic stainless steel alloy with low nickel content, and article thereof |
KR20120132691A (en) * | 2010-04-29 | 2012-12-07 | 오또꿈뿌 오와이제이 | Method for manufacturing and utilizing ferritic-austenitic stainless steel with high formability |
TWI460293B (en) * | 2011-10-21 | 2014-11-11 | Nippon Steel & Sumikin Sst | Duplex stainless steel, duplex stainless steel slab, and duplex stainless steel material |
ES2885758T3 (en) * | 2012-01-20 | 2021-12-15 | Solu Stainless Oy | Procedure for the manufacture of an austenitic stainless steel product |
JP2014001422A (en) * | 2012-06-18 | 2014-01-09 | Nippon Steel & Sumitomo Metal | Austenitic stainless steel plate and manufacturing method for the same |
CN103627970A (en) * | 2013-10-30 | 2014-03-12 | 振石集团东方特钢股份有限公司 | Vanadium-containing austenitic stainless steel |
FI125105B (en) * | 2013-11-04 | 2015-06-15 | Outokumpu Oy | Austenitic stainless steel with grain boundary corrosion and method of manufacture |
KR20150074697A (en) * | 2013-12-24 | 2015-07-02 | 주식회사 포스코 | Low-nickel containing stainless steels |
JP6438253B2 (en) * | 2014-09-26 | 2018-12-12 | エア・ウォーターNv株式会社 | GAME STEEL BALL AND MANUFACTURING METHOD THEREOF |
JP6763759B2 (en) * | 2015-11-20 | 2020-09-30 | 日本精線株式会社 | Duplex stainless steel wire with excellent magnetic properties, and magnetic wire mesh products for sieves, net conveyors, or filters |
KR101952808B1 (en) * | 2017-08-22 | 2019-02-28 | 주식회사포스코 | Low nickel austenitic stainless steel having excellent hot workability and hydrogen embrittlement resistance |
-
2018
- 2018-08-13 KR KR1020180094523A patent/KR102160735B1/en active IP Right Grant
-
2019
- 2019-08-08 WO PCT/KR2019/009977 patent/WO2020036370A1/en unknown
- 2019-08-08 EP EP19849274.6A patent/EP3822384B8/en active Active
- 2019-08-08 FI FIEP19849274.6T patent/FI3822384T3/en active
- 2019-08-08 CN CN201980065501.9A patent/CN112789365B/en active Active
- 2019-08-08 US US17/266,011 patent/US20210292877A1/en active Pending
Also Published As
Publication number | Publication date |
---|---|
KR20200018995A (en) | 2020-02-21 |
CN112789365A (en) | 2021-05-11 |
CN112789365B (en) | 2022-09-27 |
FI3822384T3 (en) | 2023-03-20 |
EP3822384A4 (en) | 2021-09-01 |
EP3822384B1 (en) | 2023-01-18 |
WO2020036370A1 (en) | 2020-02-20 |
KR102160735B1 (en) | 2020-09-28 |
US20210292877A1 (en) | 2021-09-23 |
EP3822384B8 (en) | 2023-02-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20190226068A1 (en) | Process for manufacturing hot-rolled plate, strip or coil made of duplex stainless steel | |
EP2540854B1 (en) | Super-high strength cold-rolled steel sheet having excellent bending properties | |
EP2804962B1 (en) | Method for manufacturing an austenitic stainless steel product | |
KR100263365B1 (en) | Ferritic stainless steel sheet having less planar anisotropy and excellent anti ridging characteristics and process for producing same | |
EP3722448B1 (en) | High-mn steel and method for manufacturing same | |
JP5195413B2 (en) | High-strength hot-rolled steel sheet excellent in bending workability and toughness anisotropy and method for producing the same | |
EP3631032A1 (en) | High-strength, hot rolled abrasive wear resistant steel strip | |
EP3674434A1 (en) | Low-ni austenitic stainless steel with excellent hot workability and hydrogen embrittlement resistance | |
WO2021124094A1 (en) | Hot rolled and steel sheet and a method of manufacturing thereof | |
KR102634503B1 (en) | Hot rolled steel and its manufacturing method | |
EP3822384B1 (en) | Austenitic stainless steel having improved strength | |
KR101718757B1 (en) | Ferritic stainless steel sheet with excellent formability | |
US20210301378A1 (en) | HIGH-Mn STEEL AND METHOD OF PRODUCING SAME | |
JP6411881B2 (en) | Ferritic stainless steel and manufacturing method thereof | |
KR20190044689A (en) | Steel plate | |
EP3978643A2 (en) | Austenitic stainless steel having improved strength, and method for manufacturing same | |
JP4606113B2 (en) | Austenitic stainless steel with high proportional limit stress and manufacturing method | |
EP3699314A1 (en) | Utility ferritic stainless steel having excellent hot workability, and manufacturing method therefor | |
JP3858647B2 (en) | High strength steel excellent in low temperature joint toughness and SSC resistance and method for producing the same | |
KR102463485B1 (en) | Ferritic stainless steel sheet, manufacturing method thereof, and ferritic stainless steel member | |
JP4854924B2 (en) | High-strength cold-rolled steel sheet excellent in press formability and manufacturing method thereof | |
US20230287549A1 (en) | Austenitic stainless steel with improved deep drawing | |
JP4830318B2 (en) | Method for producing non-tempered high-tensile steel with excellent surface properties | |
JP2022167288A (en) | Thick steel plate for square steel pipe | |
KR20240019756A (en) | High-strength cold-rolled steel sheet for automobiles with excellent overall formability and bending properties |
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: 20210210 |
|
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 |
|
A4 | Supplementary search report drawn up and despatched |
Effective date: 20210802 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: C22C 38/58 20060101AFI20210727BHEP Ipc: C22C 38/42 20060101ALI20210727BHEP Ipc: C22C 38/44 20060101ALI20210727BHEP Ipc: C22C 38/02 20060101ALI20210727BHEP Ipc: C22C 38/00 20060101ALI20210727BHEP Ipc: C21D 1/26 20060101ALI20210727BHEP Ipc: C22C 38/18 20060101ALI20210727BHEP Ipc: C22C 38/20 20060101ALI20210727BHEP Ipc: C22C 38/22 20060101ALI20210727BHEP Ipc: C22C 38/32 20060101ALI20210727BHEP Ipc: C22C 38/38 20060101ALI20210727BHEP Ipc: C22C 38/40 20060101ALI20210727BHEP Ipc: C22C 38/54 20060101ALI20210727BHEP |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
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: 20220829 |
|
RAP3 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: POSCO HOLDINGS INC. |
|
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: DE Ref legal event code: R081 Ref document number: 602019024644 Country of ref document: DE Owner name: POSCO CO., LTD, POHANG-SI, KR Free format text: FORMER OWNER: POSCO HOLDINGS INC., SEOUL, KR |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PK Free format text: BERICHTIGUNG B8 Ref country code: CH Ref legal event code: EP |
|
RAP2 | Party data changed (patent owner data changed or rights of a patent transferred) |
Owner name: POSCO CO., LTD |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1544730 Country of ref document: AT Kind code of ref document: T Effective date: 20230215 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: 602019024644 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG9D |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20230118 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1544730 Country of ref document: AT Kind code of ref document: T Effective date: 20230118 |
|
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: 20230118 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20230118 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: 20230518 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: 20230418 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: 20230118 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: 20230118 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: 20230118 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: 20230118 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: 20230118 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20230118 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: 20230118 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: 20230518 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: 20230419 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602019024644 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230118 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: 20230118 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: 20230118 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: 20230118 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: 20230118 |
|
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: 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: 20230118 |
|
26N | No opposition filed |
Effective date: 20231019 |
|
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: 20230118 |
|
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: 20230118 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230118 |
|
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: 20230808 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20230808 |
|
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: 20230808 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230831 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20230831 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230118 |
|
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: 20230808 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230808 |
|
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: 20230808 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230808 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20240624 Year of fee payment: 6 Ref country code: FI Payment date: 20240620 Year of fee payment: 6 |
|
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: 20230831 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20240620 Year of fee payment: 6 |