WO2021125729A1 - 내마모성과 복합내식성이 우수한 강판 및 그 제조방법 - Google Patents

내마모성과 복합내식성이 우수한 강판 및 그 제조방법 Download PDF

Info

Publication number
WO2021125729A1
WO2021125729A1 PCT/KR2020/018284 KR2020018284W WO2021125729A1 WO 2021125729 A1 WO2021125729 A1 WO 2021125729A1 KR 2020018284 W KR2020018284 W KR 2020018284W WO 2021125729 A1 WO2021125729 A1 WO 2021125729A1
Authority
WO
WIPO (PCT)
Prior art keywords
steel sheet
corrosion
hot
equation
weight
Prior art date
Application number
PCT/KR2020/018284
Other languages
English (en)
French (fr)
Korean (ko)
Inventor
이병호
홍영광
Original Assignee
주식회사 포스코
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 주식회사 포스코 filed Critical 주식회사 포스코
Priority to CN202080097198.3A priority Critical patent/CN115135797B/zh
Priority to US17/785,846 priority patent/US20230033491A1/en
Priority to JP2022538262A priority patent/JP2023507661A/ja
Publication of WO2021125729A1 publication Critical patent/WO2021125729A1/ko

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
    • C22C38/60—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
    • 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
    • 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
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226—Hot rolling
    • 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
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0236—Cold rolling
    • 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
    • C21D8/0273—Final recrystallisation 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
    • 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
    • C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
    • 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
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • 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
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1277—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties involving a particular surface treatment
    • C21D8/1283—Application of a separating or insulating coating
    • 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
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • 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
    • C22C38/008—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
    • C22C38/04—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
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • 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
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing 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
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
    • 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
    • C21D2211/004—Dispersions; Precipitations

Definitions

  • the present invention relates to a steel sheet having excellent wear resistance and composite corrosion resistance and a method for manufacturing the same. More specifically, SO x , Cl, etc. present in the exhaust gas after combustion of fossil fuels have high strength and abrasion resistance as well as corrosion resistance against the corrosion of steel sheets due to sulfuric acid/hydrochloric acid complex condensate and sulfuric acid condensate generated as the flue gas temperature decreases.
  • the present invention relates to an excellent steel sheet and a method for manufacturing the same.
  • Fossil fuels contain various impurity elements such as S and Cl. Since these fossil fuels are used for combustion, there is always a problem in that pipes and equipment, which are passages through which combustion gases pass, deteriorate due to corrosion. This corrosion phenomenon is called condensate corrosion, and typical uses where piping and equipment are exposed to these corrosive environments are exhaust gas piping and environmental equipment of thermal power plants, and automobile exhaust systems. As the types of condensation corrosion, SO x is formed as S contained in the flue gas is burned. In particular, sulfuric acid condensate corrosion where SO 3 meets moisture in the flue gas to form sulfuric acid, and chlorine contained in the flue gas or industrial water is diverse.
  • Hydrochloric acid is generated through the reaction, corrosion by the generated hydrochloric acid condensate, and sulfuric acid/hydrochloric acid composite condensate corrosion occurring in a state in which sulfuric acid and hydrochloric acid are mixed.
  • the starting temperature of the acid condensation is related to the temperature of the flue-gas itself , the content of SO x , Cl and the water vapor content in the flue-gas.
  • GGH Gas Heater
  • EP electrostatic precipitator
  • An object of the present invention is to provide a steel sheet having excellent wear resistance and composite corrosion resistance and a method for manufacturing the same. More specifically, SO x , Cl, etc. present in the exhaust gas after combustion of fossil fuels have high strength and abrasion resistance as well as corrosion resistance against the corrosion of steel sheets due to sulfuric acid/hydrochloric acid complex condensate and sulfuric acid condensate generated as the flue gas temperature decreases. An object of the present invention is to provide an excellent steel sheet and a method for manufacturing the same.
  • Corrosion-resistant steel sheet by weight, carbon (C): 0.04 to 0.10%, silicon (Si): 0.1% or less (excluding 0%), copper (Cu): 0.20 to 0.35 %, nickel (Ni): 0.1 to 0.2%, antimony (Sb): 0.05 to 0.15%, tin (Sn): 0.07 to 0.22%, titanium (Ti): 0.05 to 0.15%, sulfur (S): 0.01% or less (excluding 0%), nitrogen (N): 0.005% or less (excluding 0%), the remainder including iron (Fe) and unavoidable impurities, and satisfies Formulas 1 and 2 below.
  • Equations 1 and 2 [Ni], [Cu], [Ti], [S], and [N] are the contents (wt%) of Ni, Cu, Ti, S, and N in the steel sheet, respectively. indicates.
  • the corrosion-resistant steel sheet includes TiC precipitates, and TiC precipitates and aggregates made of TiC precipitates may be included in an amount of 10 16 or more per 1 cm 3 .
  • the TiC precipitate may have a particle diameter of 1 to 10 nm.
  • the corrosion-resistant steel sheet may further satisfy the following formula (3).
  • Equation 3 [Sn], [Sb], and [Cu] represent the contents (weight %) of Sn, Sb, and Cu in the steel sheet, respectively.
  • a thickening layer may be formed on the surface of the steel sheet.
  • a thickening layer may be formed on the surface of the steel sheet.
  • the thickening layer may include Cu, Sb, and Sn.
  • the concentration of the thickening layer may be 15% by weight or more.
  • the concentration means the sum (weight %) of the content of the concentration elements Mo, Cu, Sb, and Sn holding the boundary point at which Fe and O are equal in weight %.
  • the thickening layer thickness may be 10 nm or more.
  • the recrystallization fraction after the annealing heat treatment of the steel sheet may be 80% or more.
  • the corrosion loss ratio is 1.0 mg/cm 2 /hr. may be below.
  • the corrosion loss ratio is 25 mg/cm 2 /hr. may be below.
  • the tensile strength of the hot-rolled steel sheet may be 550 MPa or more, and the surface hardness may be 85 or more based on HRB.
  • the tensile strength of the cold-rolled steel sheet may be 500 MPa or more, and the surface hardness may be 80 or more based on HRB.
  • the method of manufacturing a corrosion-resistant steel sheet according to an embodiment of the present invention in weight %, carbon (C): 0.04 to 0.10%, silicon (Si): 0.1% or less (excluding 0%), copper (Cu): 0.20 to 0.35%, nickel (Ni): 0.1 to 0.2%, antimony (Sb): 0.05 to 0.15%, tin (Sn): 0.07 to 0.22%, titanium (Ti): 0.05 to 0.15%, sulfur (S): 0.01% or less (excluding 0%), nitrogen (N): 0.005% or less (excluding 0%), remaining iron (Fe) and unavoidable impurities, and the steel slab satisfying the following formulas 1 and 2 preparing; heating the slab above 1,200 °C; and preparing a hot-rolled steel sheet by hot-rolling the heated slab to a finish rolling temperature of 850 to 1000 °C.
  • Equations 1 and 2 [Ni], [Cu], [Ti], [S], and [N] are the contents (wt%) of Ni, Cu, Ti, S, and N in the steel sheet, respectively. indicates.
  • manufacturing a hot-rolled steel sheet Thereafter, winding the hot-rolled steel sheet at 450 to 750 °C; manufacturing a cold rolled steel sheet by cold rolling the wound hot rolled steel sheet at a reduction ratio of 54 to 70%; and annealing and heat-treating the cold-rolled steel sheet at 750 to 880°C.
  • the step of heating the slab at 1,200 ° C. or higher; in, the re-route time may be 150 minutes or more.
  • the corrosion-resistant steel sheet according to an embodiment of the present invention can be effectively used as a raw material for piping through which exhaust gas passes after combustion of fossil fuels, hot-rolled products for fossil fuel combustion facilities, and cold-rolled products.
  • the corrosion-resistant steel sheet according to an embodiment of the present invention can be applied to the GGH facility. In this case, it can satisfy both wear resistance and complex corrosion resistance requirements despite the large environmental change.
  • Example 1 is a graph showing the element concentration of the surface portion of the steel sheet by measuring the element distribution from the surface to the inside through GDS measurement after immersing the steel sheet of Inventive Example 2 in a 50 wt% sulfuric acid solution for 24 hours.
  • first, second and third are used to describe, but are not limited to, various parts, components, regions, layers and/or sections. These terms are used only to distinguish one part, component, region, layer or section from another part, component, region, layer or section. Accordingly, a first part, component, region, layer or section described below may be referred to as a second part, component, region, layer or section without departing from the scope of the present invention.
  • the term “combination of these” included in the expression of the Markush form means one or more mixtures or combinations selected from the group consisting of the components described in the expression of the Markush form, and the components It means to include one or more selected from the group consisting of.
  • % means weight %, and 1 ppm is 0.0001 weight %.
  • the meaning of further including the additional element means that the remaining iron (Fe) is included by replacing the additional amount of the additional element.
  • the inventors of the present invention when adding an element capable of forming precipitates, such as Ti, to a normal medium to low carbon steel sheet, if appropriate manufacturing conditions are used in the manufacturing process, the intermediate material of the hot rolled material and the final material of the cold rolled material It was confirmed that hardness and strength can be significantly increased.
  • Corrosion-resistant steel sheet by weight, carbon (C): 0.04 to 0.10%, silicon (Si): 0.1% or less (excluding 0%), copper (Cu): 0.20 to 0.35 %, nickel (Ni): 0.1% to 0.2%, antimony (Sb): 0.05 to 0.15%, tin (Sn): 0.07 to 0.22%, titanium (Ti): 0.05 to 0.15%, sulfur (S): 0.01% or less (excluding 0%), nitrogen (N): 0.005% or less (excluding 0%), the remainder including iron (Fe) and unavoidable impurities, and satisfy the following formulas 1 and 2.
  • Equations 1 and 2 [Ni], [Cu], [Ti], [S], and [N] are the contents (wt%) of Ni, Cu, Ti, S, and N in the steel sheet, respectively. indicates.
  • the corrosion-resistant steel sheet may further satisfy the following formula (3).
  • Equation 3 [Sn], [Sb], and [Cu] represent the contents (weight %) of Sn, Sb, and Cu in the steel sheet, respectively.
  • the carbon content of the low-carbon steel sheet may be 0.04 to 0.10 wt%. If the content of carbon in the steel is too large, corrosion resistance may be deteriorated due to excessive TiC formation and carbide formation, in particular, deterioration of sulfuric acid/hydrochloric acid composite corrosion resistance may occur. Conversely, if the carbon content is too small, it may be impossible to secure the strength desired in the present invention. More specifically, it may be 0.042 to 0.10 wt%.
  • the silicon content of the low-carbon steel sheet may be 0.1 wt% or less. If the silicon content in the steel is too large, a large amount of scale may be induced on the surface due to the complex phase shape of SiO 2 and Fe oxide. Accordingly, the Si content may be within the above range for resolving surface defects. More specifically, it may be 0.05 wt% or less. More specifically, it may be 0.01 to 0.05 wt%.
  • Cu is a representative element that, when corroded in an acid immersion environment, is concentrated between the steel surface and corrosion products to prevent further corrosion. In order to exhibit the effect, an appropriate amount of Cu may be added. However, when too much is added, there is a possibility of causing cracks during manufacturing due to the low melting point of Cu.
  • Nickel (Ni) 0.1% to 0.2% by weight
  • Ni is added for the purpose of limiting the occurrence of cracks by raising the melting point by adding Ni.
  • the content of Ni is too small, it does not sufficiently serve to increase the melting point of Cu.
  • the content of Ni is too large, surface defects due to Ni may occur. More specifically, it may be 0.11 to 0.19 wt%.
  • Equation 1 For the same reason as adding Ni together with Cu, Ni and Cu may be added in the above ranges in order to properly increase the melting point and not cause surface defects due to Ni. If the value of Equation 1 is too high, surface defects may occur due to Ni, and if the value of Equation 1 is too low, the effect of increasing the melting point by Ni may be insignificant. In this case, in Equation 1, [Ni] and [Cu] represent Ni and Cu contents (weight %) in the steel sheet, respectively.
  • Sb like Cu
  • Sb is added to form a stable thickening layer on the surface.
  • a sufficient thickening layer may not be formed. Conversely, too much may cause surface cracks.
  • Sn like Cu and Sb, is added to form a stable thickening layer on the surface.
  • Sn was first dissolved in an acid immersion environment such as sulfuric acid, thereby greatly improving the corrosion resistance of steel grades. More specifically, although it is not clear, it is thought that Sn improves the corrosion resistance of steel grades by the following mechanism.
  • Sn dissolves out before Cu, Sn dissociates in solution. It is thought that the dissociated Sn lowers the corrosion potential of the solution, thereby partially delaying the corrosion phenomenon of the steel sheet.
  • the corrosion potential means a potential with respect to the combination electrode (Reference Electrode) of the metal corrosion is in progress.
  • a corrosion retardation layer may be formed in the process of re-fusion of Sn dissolved on the surface of the steel sheet, and it is believed that this corrosion retardation layer may delay corrosion of the steel sheet.
  • Sn is included too little, it may not be possible to form a sufficient thickening layer. If Sn is added too much, it can cause serious surface cracks in the production process. More specifically, it may be 0.073 to 0.22 wt%.
  • the Cu, Sb, and Sn are elements that form a concentrated layer on the surface of the steel sheet in a sulfuric acid/hydrochloric acid complex condensing atmosphere or a sulfuric acid condensing atmosphere, and may satisfy the relation of Equation 3 as well as an appropriate content of each element. If the value of Equation 3 is too small, there is a disadvantage that a sufficient thickening layer cannot be formed.
  • Equation 3 [Sn], [Sb], and [Cu] represent the contents (weight %) of Sn, Sb, and Cu in the steel sheet, respectively. More specifically, Equation 3 may be 15 to 26. More specifically, it may be 15.2 to 23.44.
  • Ti acts as an element for forming precipitates and is added to increase the strength and wear resistance of the steel sheet. That is, Ti combines with C to form TiC precipitates. TiC as a fine precipitate may improve the hardness and wear resistance of the steel sheet due to precipitation strengthening, and may also increase strength. In this regard, specific details of TiC will be described later.
  • Ti may include 0.05 to 0.145 wt%. More specifically, it may contain 0.052 to 0.145 wt%.
  • S may have an adverse effect of limiting the effective content of Ti in forming Ti carbides.
  • the reason is that, in the present invention, although the wear resistance is improved by precipitation hardening according to the formation of TiC precipitates, since TiS is formed first before TiC formation, a large amount of S interferes with the formation of TiC. Therefore, the range of the largest component can be made into said range. More specifically, it may be 0.0097 wt% or less. More specifically, it may be 0.001 to 0.0097 wt%.
  • N may have an adverse effect of limiting the effective content of Ti in forming Ti carbide.
  • the wear resistance is improved by precipitation hardening according to the formation of TiC precipitates, but since TiN is first formed before TiC formation, a large amount of N interferes with the formation of TiC.
  • Ti when Ti is formed as a precipitate, it is formed in the order of TiN, TiS, and TiC. Therefore, the range of the largest component can be made into said range. More specifically, it may be 0.004 wt% or less. More specifically, it may be 0.001 to 0.004 wt%.
  • the effective content of Ti(Ti * ) can be calculated by Equation 2. Even if the component ranges of S and N are satisfied, if the range of Equation 2 is not satisfied, sufficient TiC may not be formed, resulting in a decrease in strength. At this time, in Equation 2, [Ti], [S], and [N] represent the contents (weight %) of Ti, S, and N in the steel sheet, respectively. More specifically, the range of Equation 2 may be 0.04 to 0.12.
  • steel sheet may further include manganese (Mn) and aluminum (Al).
  • Mn plays a role in improving strength through solid solution strengthening in steel, but if the content is too large, coarse MnS is formed, which reduces strength. Therefore, the content of Mn in the present invention is preferably limited to 0.5 to 1.5% by weight.
  • Al is an element that is unavoidably added during the production of aluminum-killed steel, and is preferably added in an appropriate amount for the deoxidation effect.
  • the Al content exceeds 0.02% by weight, there is a problem that not only increases the possibility of causing surface defects of the steel sheet, but also deteriorates weldability. Therefore, in the present invention, it is preferable to limit the Al content to 0.02 to 0.05 wt%.
  • the present invention contains Fe and unavoidable impurities. Since unavoidable impurities are widely known in the art, a detailed description thereof will be omitted. In one embodiment of the present invention, the addition of effective components other than the above components is not excluded, and when additional components are further included, the remaining Fe is included.
  • the corrosion-resistant steel sheet according to an embodiment of the present invention has excellent wear resistance, and may include TiC precipitates in relation thereto.
  • TiC precipitates and the aggregate formed of the TiC precipitates may improve hardness and wear resistance of the steel sheet due to precipitation strengthening as fine precipitates, and may also increase strength.
  • TiC precipitates and aggregates made of a plurality of TiC precipitates may be included in an amount of 10 16 or more per 1 cm 3 . If the content of the precipitates is too small, there is a disadvantage in that the desired strength and wear resistance cannot be secured. More specifically, it may be 10 16 to 10 18 pieces per 1 cm 3 .
  • the TiC precipitate may be spherical.
  • the TiC precipitate may have a particle diameter of 1 to 10 nm.
  • the precipitates interfere with the movement of dislocations inside the steel and increase the strength by forming bands of dislocations. If the particle size of the precipitates is too small, the dislocations can easily move, so there is a disadvantage that there is no strength-increasing effect. If it is too large, dislocations cut and pass through the precipitates to facilitate movement, so there is a disadvantage that the effect of increasing the strength is also reduced. More specifically, it may be 2 to 10 nm. More specifically, it may be 2 to 8 nm.
  • the particle diameter means a diameter of the sphere, assuming a sphere having the same volume as the particle.
  • TiC precipitates may be uniformly distributed in the steel sheet.
  • Cu, Sb, and Sn form a thickening layer in a sulfuric acid/hydrochloric acid complex condensing atmosphere or a sulfuric acid condensing atmosphere, which suppresses additional corrosion. More specifically, when the steel sheet is immersed in a mixture of 28.5 wt% sulfuric acid solution and 0.5 wt% hydrochloric acid solution at 40 to 80° C., a thickening layer may be formed on the surface of the steel sheet. In addition, when the steel sheet is immersed in a 50 wt% sulfuric acid solution at 50 to 90°C, a thickening layer may be formed on the surface of the steel sheet. More specifically, when immersed for 4 to 8 hours, a thickening layer may be formed.
  • the thickening layer means a layer in which Cu, Sb, and Sn begin to be concentrated, and in other respects, it is similar to the point where oxidation generally starts.
  • the thickened layer in the present invention means a layer in which the sum of Cu, Sb, and Sn in the layer exceeds four times the sum of Cu, Sb, and Sn of the steel sheet.
  • the thickening layer may be an amorphous thickening layer.
  • the thickening layer is generated along with the formation of a corrosion layer when immersed in acid.
  • the corrosion layer means a layer in which Fe is oxidized by O.
  • Fe is oxidized before Cu and Sb, and when immersed in acid, Fe is dissociated into Fe ions and escapes into an acid solution, but Cu and Sb are stable in a solid state and remain on the surface. Therefore, even if the reduction of the Fe content on the surface of the steel sheet continues to occur due to the continued acid reaction, Cu and Sb remain on the surface to form a high-concentration layer. It is formed on the surface in the form of a thickening layer after a certain reaction time has passed, and the thickening layer prevents direct contact between the acid and the internal iron to suppress further corrosion.
  • the concentrating layer may include Cu, Sb, and Sn, and the concentrating amount of the concentrating layer may be 15% by weight or more.
  • the concentration means the sum (weight %) of the content of the concentration elements Mo, Cu, Sb, and Sn holding the boundary point at which Fe and O are equal in weight %. That is, the boundary point at which Fe and O contents (wt%) are equal, mean the sum (wt%) of the concentrations of Cu, Sb, and Sn concentrating elements at this time. If the amount of thickening is too small, the thickening layer may not be sufficiently formed, so that the corrosion reduction ratio increases. More specifically, it may be 15% to 22%.
  • each enriching element at the point where the content (wt%) of Fe and O in the enriched layer becomes the same is Cu: 10 to 15 wt%, Sb: 1 to 3 wt%, and Sn: 1 to 3 wt% can be
  • the thickening layer thickness may be 10 nm or more. More specifically, the thickening layer may be formed to a thickness of 10 to 500 nm. When the thickness of the thickening layer is too thin, it is difficult to prevent the above-mentioned corrosion. If the thickened layer is formed too thickly, cracks may occur inside the thickened layer, and acid may penetrate along the crack to cause corrosion. More specifically, the thickening layer may be formed to a thickness of 12 to 100 nm.
  • the corrosion-resistant steel sheet according to an embodiment of the present invention may be a hot-rolled steel sheet or a cold-rolled steel sheet.
  • the thickness of the steel sheet may be 2.5 to 5.5 mm. More specifically, it may be 3.5 to 5.5 mm.
  • the thickness of the steel sheet may be 1.0 to 2.5 mm. More specifically, it may be 1.0 to 2.0 mm.
  • the recrystallization fraction after the annealing heat treatment of the steel sheet may be 80% or more. More specifically, it may be 100%. If the recrystallization fraction is too low, the strength is increased, but the ductility is sharply decreased, so there is a disadvantage of forming defects during customer processing. In this case, the recrystallized fraction means the area of the recrystallized grain (grain) based on the total area of the steel sheet.
  • the corrosion loss ratio is 1.0 mg/cm 2 /hr. may be below.
  • the corrosion loss ratio is 25 mg/cm 2 /hr. may be below.
  • the corrosion-resistant steel sheet according to an embodiment of the present invention is a hot-rolled steel sheet
  • the tensile strength of the hot-rolled steel sheet may be 550 MPa or more
  • the surface hardness may be 85 or more based on HRB.
  • the tensile strength of the cold-rolled steel sheet may be 500 MPa or more, and the surface hardness may be 80 or more based on HRB.
  • the method of manufacturing a corrosion-resistant steel sheet according to an embodiment of the present invention in weight %, carbon (C): 0.04 to 0.10%, silicon (Si): 0.1% or less (excluding 0%), copper (Cu): 0.20 to 0.35%, nickel (Ni): 0.1 to 0.2%, antimony (Sb): 0.05 to 0.15%, tin (Sn): 0.07 to 0.22%, titanium (Ti): 0.05 to 0.15%, sulfur (S): 0.01% or less (excluding 0%), nitrogen (N): 0.005% or less (excluding 0%), remaining iron (Fe) and unavoidable impurities, and the steel slab satisfying the following formulas 1 and 2 preparing; heating the slab at 1,200° C. or higher; and preparing a hot-rolled steel sheet by hot-rolling the heated slab to a finish rolling temperature of 850 to 1000 °C.
  • Equations 1 and 2 [Ni], [Cu], [Ti], [S], and [N] are the contents (wt%) of Ni, Cu, Ti, S, and N in the steel sheet, respectively. indicates.
  • manufacturing a hot-rolled steel sheet Thereafter, winding the hot-rolled steel sheet at 450 to 750 °C; manufacturing a cold rolled steel sheet by cold rolling the wound hot rolled steel sheet at a reduction ratio of 54 to 70%; and annealing and heat-treating the cold-rolled steel sheet at 750 to 880°C.
  • the slab that satisfies the above-described composition is heated.
  • the reason for limiting the addition ratio of each composition in the slab is the same as the reason for limiting the composition of the steel sheet described above, and thus repeated description will be omitted. Since the composition of the slab does not substantially change in the manufacturing process of hot rolling, winding, pickling, cold rolling, annealing, etc. to be described later, the composition of the slab and the composition of the finally manufactured corrosion-resistant steel sheet are substantially the same.
  • heating may refer to reheating.
  • the slab heating temperature may be 1,200 °C or more. The reason why the heating temperature of the slab is in the above range is for sufficient Ti re-dissolution. This is because TiC precipitates are later precipitated only when Ti is sufficiently re-dissolved.
  • the ash furnace time at the time of heating the slab may be 150 minutes or more. If the time for ash is too short, the re-recruitment of Ti may not occur sufficiently.
  • a hot-rolled steel sheet is manufactured by hot rolling the heated slab.
  • the finish rolling temperature of the hot rolling may be 850 to 1000 °C. If the finish rolling temperature is too low, sufficient rolling ability may not be exhibited. On the other hand, if the finish rolling temperature is too high, it may be difficult to secure the strength of the steel sheet. In this case, the thickness of the hot-rolled sheet may be 2.5 to 5.5 mm.
  • the step of winding the hot-rolled steel sheet may be made at 450 to 750 °C. If the coiling temperature is too low, the final cold rolling may be difficult due to an increase in the initial strength of the hot rolled material. On the other hand, if the coiling temperature is too high, there may be problems of buckling and strength drop due to phase transformation in the winding section.
  • the step of pickling the wound hot-rolled steel sheet may include.
  • cold rolling the wound hot-rolled steel sheet at a reduction ratio of 54 to 70% to manufacture a cold-rolled steel sheet may include. If the reduction ratio is too low, it may be difficult to secure complete recrystallization during cold rolling, which may cause a decrease in the elongation of the material and may cause cracks during customer processing in the future. On the other hand, if the reduction ratio is too high, there may be a problem in that rolling is not performed due to a motor load during the rolling process.
  • annealing the cold-rolled steel sheet at 750 to 880 °C may include. If the annealing heat treatment temperature is too low, it may be difficult to secure complete recrystallization, which may cause a decrease in the elongation of the material, and may cause cracks during customer processing in the future. On the other hand, if the annealing heat treatment temperature is too high, there is a problem in that it is difficult to secure the strength of the steel sheet.
  • the slab was heated at 1250° C. for 200 minutes and then hot-rolled to a thickness of 3.5 mm to prepare a hot-rolled sheet.
  • the finish rolling temperature (FDT) was 920 °C, and the winding was performed at 650 °C.
  • an immersion test was performed by the method described in the standard of ASTM G31.
  • the immersion test was performed by preparing a 50% by weight aqueous solution of sulfuric acid and immersing it at 70° C. for 6 hours. After immersion, the weight loss per unit time and per unit surface area was measured by measuring the weight loss after washing through the method of cleaning the surface of the specimen in ASTM G1.
  • the hot-rolled sheet of each invention example and comparative example was immersed in a 50 wt% sulfuric acid solution at 70° C. for 24 hours, and then the specimen was distributed from the surface to the inside through GDS measurement. was measured.
  • Table 2 the thickness of the concentrating layer measured therefrom and the concentrating amount of the surface concentrating elements were measured and shown.
  • the thickening layer means a layer in which Cu, Sb, and Sn begin to be concentrated, and in other respects, it is similar to the point where oxidation generally starts.
  • the thickness of the thickening layer was measured as the thickness of the layer in which the sum of Cu, Sb, and Sn in the layer exceeds four times the sum of Cu, Sb, and Sn of the steel sheet.
  • Cu is maximally concentrated at the boundary point where the content (wt%) of Fe and O is equal to the weight%
  • the concentration is the point where the content (wt.%) of Fe and O is equal, and at this time
  • the thickening layer made of Sb, Sn, and Cu was present on the surface of steel and corrosion products at a level of about 20 wt%. It was found that the thickness and amount of the thickening layer determine the corrosion resistance during immersion.
  • FIG. 1 is a graph showing the element concentration of the surface portion of the steel sheet by measuring the element distribution from the surface to the inside through GDS measurement after immersing the steel sheet of Inventive Example 2 in a 50 wt% sulfuric acid solution for 24 hours.
  • the sum of the contents of Cu, Sb, and Sn of Invention Example 2 is (0.26+0.1+0.15), which is 0.51% by weight, and the sum of Cu, Sb, and Sn at a depth of 14nm exceeds 2.04% by weight, which is four times of 0.51% by weight. do. Therefore, the depth of 14 nm was set as the thickness of the thickening layer. (red dotted line)
  • the boundary point where Fe and O meet that is, the point where the content of Fe and O are equal is the layer corresponding to the blue dotted line (left) of FIG. 1, and the concentration amount, which is the sum of Cu, Sb, and Sn, in the layer is 17% by weight.
  • the concentration means the sum (weight %) of the contents of the enriched elements Cu, Sb, and Sn at the point at which the contents (weight %) of Fe and O are the same.
  • Comparative Example 1 having a low C content
  • the tensile strength of the hot rolled material was lower than 550 MPa and the surface hardness was low due to a decrease in the TiC precipitate content due to the low C content, so that strength and abrasion could not be secured.
  • the C content was excessively high as in Comparative Example 2, a phenomenon in which the composite corrosion resistance was decreased due to the increase of TiC precipitates was observed.
  • the content of Si was characteristically significantly lowered, because as in Comparative Example 3, the higher the Si content, the excessively the red scale occurred on the surface of the hot rolled material, and it was confirmed that this leads to cracks. to be.
  • Comparative Example 4 having a low Cu content resulted in a decrease in corrosion resistance of sulfuric acid alone, and in Comparative Example 5 having an excessively high Cu content, cracks in the cast slab due to Cu liquefaction during continuous casting were confirmed.
  • Comparative Example 8 with a low Sb content and Comparative Example 12 with a low Sn content, the corrosion resistance was greatly reduced, and Comparative Example 9 with an excessively high Sb content In the case of Comparative Example 13 having an excessively high Sn content, it was confirmed that surface defects and cracks of the hot rolled material were induced.
  • Ti was actively added to form precipitates to ensure strength and surface hardness.
  • the Ti content is low as in Comparative Example 10, it can be seen that the tensile strength and surface hardness of the hot rolled material are rapidly decreased.
  • Comparative Example 11 having a high Ti content, particularly 0.15 wt% or more nozzle clogging may be caused in the continuous casting process, and severe nozzle clogging was confirmed in the actual test process of Comparative Example.
  • Comparative Example 16 even if the content of S and N described in the invention example is within the effective Ti (Ti * ) content of Equation 2 is not 0.04 or more, it is difficult to obtain the effect of high strength and high wear resistance. On the other hand, in the case of Comparative Example 16 having a low effective Ti content, the TiC density was small and the TiC particle size was too small, so that the desired precipitation hardening effect could not be obtained.
  • Table 3 below shows the characteristics of the hot-rolled material and the cold-rolled material after manufacturing under different manufacturing conditions with the component system of Invention Example 4 in order to examine the influence of the manufacturing conditions on the production possibility and strength.
  • FIG. 2 shows (a) the tendency of cracks in the hot rolling edge part after hot rolling in Inventive Example 4 under condition 1 and (b) hot rolling edge after hot rolling in Inventive Example 4 under condition 2. This is a picture comparing the tendency of minor cracks.
  • condition 3 where the hot finish rolling temperature (FDT) was high at 1050 ° C, the target material could not be obtained due to the low tensile strength of the hot and cold rolled materials, which also occurred in condition 5 when the coiling temperature (CT) was high.
  • FDT hot finish rolling temperature
  • the steel grade of the present invention has a high recrystallization temperature after cold rolling due to high C and Ti content.
  • condition 6 where the cold rolling reduction ratio was 53%, the recrystallization fraction of the final cold rolled material was 70%, so complete recrystallization was not achieved.
  • condition 8 where the annealing temperature was as low as 740 °C, the recrystallization fraction was 65% and complete recrystallization was not achieved.
  • the reduction ratio is 54% or more, and the annealing temperature is limited to 750 ° C or more. do.

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)
  • Electromagnetism (AREA)
  • Manufacturing & Machinery (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
PCT/KR2020/018284 2019-12-19 2020-12-14 내마모성과 복합내식성이 우수한 강판 및 그 제조방법 WO2021125729A1 (ko)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN202080097198.3A CN115135797B (zh) 2019-12-19 2020-12-14 耐磨性和复合耐蚀性优异的钢板及其制造方法
US17/785,846 US20230033491A1 (en) 2019-12-19 2020-12-14 Steel plate having excellent wear resistance and composite corrosion resistance and method for manufacturing same
JP2022538262A JP2023507661A (ja) 2019-12-19 2020-12-14 耐摩耗性と複合耐食性に優れた鋼板およびその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020190170978A KR102326323B1 (ko) 2019-12-19 2019-12-19 내마모성과 복합내식성이 우수한 강판 및 그 제조방법
KR10-2019-0170978 2019-12-19

Publications (1)

Publication Number Publication Date
WO2021125729A1 true WO2021125729A1 (ko) 2021-06-24

Family

ID=76477759

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2020/018284 WO2021125729A1 (ko) 2019-12-19 2020-12-14 내마모성과 복합내식성이 우수한 강판 및 그 제조방법

Country Status (5)

Country Link
US (1) US20230033491A1 (zh)
JP (1) JP2023507661A (zh)
KR (1) KR102326323B1 (zh)
CN (1) CN115135797B (zh)
WO (1) WO2021125729A1 (zh)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130143375A (ko) * 2012-06-21 2013-12-31 주식회사 포스코 황산내식성 및 표면특성이 우수한 냉연강판 및 그 제조방법
JP2015113506A (ja) * 2013-12-12 2015-06-22 Ｊｆｅスチール株式会社 耐食性に優れる原油タンク用鋼材および原油タンク
KR101657787B1 (ko) * 2014-12-04 2016-09-20 주식회사 포스코 황산 내식성 및 법랑 밀착성이 우수한 강판 및 그 제조방법
WO2019003856A1 (ja) * 2017-06-30 2019-01-03 Ｊｆｅスチール株式会社 構造用鋼材および構造物
KR20190062480A (ko) * 2016-10-06 2019-06-05 제이에프이 스틸 가부시키가이샤 선박 밸러스트 탱크용 강재 및 선박

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3305936B1 (en) * 2015-05-28 2019-07-10 Posco Hot-rolled steel sheet having excellent composite corrosion resistance to sulfuric acid and hydrochloric acid and manufacturing method therefor
KR101746404B1 (ko) * 2015-12-23 2017-06-14 주식회사 포스코 내식성 및 가공성이 향상된 린 듀플렉스 스테인리스강 및 이의 제조 방법
CN109576591B (zh) * 2019-02-12 2020-03-31 鞍钢股份有限公司 一种700MPa级冷轧耐蚀双相钢及其制造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130143375A (ko) * 2012-06-21 2013-12-31 주식회사 포스코 황산내식성 및 표면특성이 우수한 냉연강판 및 그 제조방법
JP2015113506A (ja) * 2013-12-12 2015-06-22 Ｊｆｅスチール株式会社 耐食性に優れる原油タンク用鋼材および原油タンク
KR101657787B1 (ko) * 2014-12-04 2016-09-20 주식회사 포스코 황산 내식성 및 법랑 밀착성이 우수한 강판 및 그 제조방법
KR20190062480A (ko) * 2016-10-06 2019-06-05 제이에프이 스틸 가부시키가이샤 선박 밸러스트 탱크용 강재 및 선박
WO2019003856A1 (ja) * 2017-06-30 2019-01-03 Ｊｆｅスチール株式会社 構造用鋼材および構造物

Also Published As

Publication number Publication date
KR102326323B1 (ko) 2021-11-12
CN115135797A (zh) 2022-09-30
JP2023507661A (ja) 2023-02-24
KR20210078976A (ko) 2021-06-29
US20230033491A1 (en) 2023-02-02
CN115135797B (zh) 2023-09-22

Similar Documents

Publication Publication Date Title
WO2018117543A1 (ko) 충격특성이 우수한 열간성형용 도금강판, 열간성형 부재 및 그들의 제조방법
WO2015099221A1 (ko) 고강도 저비중 강판 및 그 제조방법
WO2017105064A1 (ko) 표면품질 및 점 용접성이 우수한 고강도 용융아연도금강판 및 그 제조방법
WO2019231023A1 (ko) Twb 용접 특성이 우수한 열간성형용 al-fe 합금화 도금강판, 열간성형 부재 및 그들의 제조방법
WO2019124688A1 (ko) 충돌특성 및 성형성이 우수한 고강도 강판 및 이의 제조방법
WO2017105026A1 (ko) 화성처리성 및 구멍확장성이 우수한 초고강도 강판 및 이의 제조방법
WO2013081422A1 (ko) 린 듀플렉스 스테인리스강 및 그 제조방법
WO2017105025A1 (ko) 화성처리성 및 굽힘가공성이 우수한 초고강도 강판 및 이의 제조방법
WO2018117724A1 (ko) 연속 생산성이 우수한 고강도 열연강판 및 냉연강판 그리고 표면 품질 및 도금 밀착성이 우수한 고강도 용융아연도금강판 및 이들의 제조방법
WO2017082621A1 (ko) 방향성 전기강판 및 그 제조방법
WO2018056792A1 (ko) 내식성 및 점용접성이 우수한 열간성형용 냉연강판, 열간성형부재 및 그들의 제조방법
WO2016104837A1 (ko) 표면품질이 우수한 고강도 아연도금강판용 열연강판 및 이의 제조방법
WO2018110906A1 (ko) 표면품질이 우수한 고탄소 열연강판 및 이의 제조방법
WO2019124781A1 (ko) 상온내시효성 및 소부경화성이 우수한 아연계 도금강판 및 그 제조방법
WO2020226301A1 (ko) 전단가공성이 우수한 초고강도 강판 및 그 제조방법
WO2021125729A1 (ko) 내마모성과 복합내식성이 우수한 강판 및 그 제조방법
WO2021125730A2 (ko) 내마모성과 복합내식성이 우수한 강판 및 그 제조방법
WO2020130675A1 (ko) 굽힘 가공성이 우수한 고강도 냉연강판 및 그 제조방법
WO2020060051A1 (ko) 충격 인성이 우수한 페라이트계 스테인리스 열연 무소둔 강판 및 그 제조방법
WO2016104838A1 (ko) 표면품질이 우수한 고강도 아연도금강판용 열연강판 및 이의 제조방법
WO2022097965A1 (ko) 내수소취성 및 내충돌성이 우수한 열간성형용 도금강판, 열간성형 부재 및 이들의 제조방법
WO2022086050A1 (ko) 연성이 우수한 초고강도 강판 및 그 제조방법
WO2018117539A1 (ko) 용접성 및 연성이 우수한 고강도 열연강판 및 이의 제조방법
WO2020085888A1 (ko) 황화물 응력부식 균열 저항성이 우수한 고강도 강재 및 이의 제조방법
WO2021020787A1 (ko) 고강도 강판 및 이의 제조방법

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20901957

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022538262

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20901957

Country of ref document: EP

Kind code of ref document: A1