EP3396006A1 - Microcrack-reduced, hot press-formed article, and method for manufacturing same - Google Patents
Microcrack-reduced, hot press-formed article, and method for manufacturing same Download PDFInfo
- Publication number
- EP3396006A1 EP3396006A1 EP16879309.9A EP16879309A EP3396006A1 EP 3396006 A1 EP3396006 A1 EP 3396006A1 EP 16879309 A EP16879309 A EP 16879309A EP 3396006 A1 EP3396006 A1 EP 3396006A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zinc
- steel sheet
- plated layer
- based plated
- hot press
- 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
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000011701 zinc Substances 0.000 claims abstract description 74
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 68
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000010959 steel Substances 0.000 claims abstract description 68
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 68
- 229910052718 tin Inorganic materials 0.000 claims abstract description 30
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 26
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 25
- 238000005275 alloying Methods 0.000 claims abstract description 13
- 229910001335 Galvanized steel Inorganic materials 0.000 claims abstract description 11
- 239000008397 galvanized steel Substances 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 26
- 238000000465 moulding Methods 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 62
- 238000007747 plating Methods 0.000 description 22
- 239000011777 magnesium Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000005204 segregation Methods 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910001566 austenite Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- ZNEMGFATAVGQSF-UHFFFAOYSA-N 1-(2-amino-6,7-dihydro-4H-[1,3]thiazolo[4,5-c]pyridin-5-yl)-2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound NC=1SC2=C(CN(CC2)C(CC=2OC(=NN=2)C=2C=NC(=NC=2)NC2CC3=CC=CC=C3C2)=O)N=1 ZNEMGFATAVGQSF-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 239000010731 rolling oil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
- B21D22/02—Stamping using rigid devices or tools
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
- B21D22/20—Deep-drawing
-
- 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
- C21D1/62—Quenching devices
- C21D1/673—Quenching devices for die quenching
-
- 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
- C21D8/005—Modifying the physical properties by deformation combined with, or followed by, heat treatment of ferrous alloys
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
- C23C2/261—After-treatment in a gas atmosphere, e.g. inert or reducing atmosphere
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
- C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
- C23C2/29—Cooling or quenching
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
- B21D22/02—Stamping using rigid devices or tools
- B21D22/022—Stamping using rigid devices or tools by heating the blank or stamping associated with heat treatment
Definitions
- the present disclosure relates to a microcrack reduced hot press-formed article and a method for manufacturing the same.
- HPF hot press forming
- Hot press forming is a method of machining a steel sheet to have a complicated shape at high temperatures by utilizing the properties of the steel sheet, soft-nitrides, having high ductility at high temperature. More specifically, in a state in which a steel sheet is heated to an austenite region or greater, the steel sheet is machined and rapidly quenched simultaneously to transform the structure of the steel sheet into martensite, thus producing a product having high strength and a precise shape.
- plated steel materials having a zinc-based or aluminum-based plated layer formed on a surface thereof are commonly used as materials for hot press forming.
- a galvanized steel sheet having a zinc-based plated layer is a steel material having corrosion resistance improved using the self-sacrificial corrosion resistance of zinc.
- Patent document 1 U.S. Patent Publication No. 6296805 proposes a technique of performing Al-based plating on a surface of a steel sheet.
- Al-based plating As Al-based plating is performed, an oxidation reaction on a surface of the steel sheet is suppressed, while the plated layer is maintained in a heating furnace, and formation of a passivation film of Al is used to increase corrosion resistance, but corrosion resistance of the Al plated steel sheet is drastically lowered.
- microcracks are formed even in a surface of the base steel sheet, due to a high temperature working environment in which a temperature of the plated steel exceeds 900°C and stress caused by friction between a Zn-Fe alloyed layer alloyed during hot press forming and a dice.
- Such microcracks may act as a starting point for the propagation of cracks in the base steel sheet or cause fatigue cracks, which may decrease durability of parts.
- An aspect of the present disclosure is to provide a microcrack reduced hot press-formed article and a method for manufacturing the same.
- a hot press-formed article manufactured by hot press forming a galvanized steel sheet including a base steel sheet and a zinc-based plated layer formed on a surface of the base steel sheet, wherein the zinc-based plated layer includes at least one element selected from the group consisting of Sb, Sn, and Bi in a total amount of 0.05 to 2.0 wt%, a balance of Zn, and inevitable impurities, and at least 70 wt% of the at least one element selected from the group consisting of Sb, Sn, Bi is concentrated in a region 3 ⁇ m or less away from a surface of an alloyed zinc-based plated layer, formed by alloying the zinc-based plated layer, of the hot press-formed article.
- a method for manufacturing a hot press-formed article includes: preparing a zinc-based plated steel sheet; primarily heating the zinc-based plated steel sheet to a temperature of 640 to 680°C at a rate of 3.5 to 4.2°C/sec; secondarily heating the primarily-heated zinc-based plated steel sheet to a temperature of 900 to 930°C at a rate of 1.1 to 1.6°C/sec; maintaining the secondarily-heated zinc-based plated steel sheet at a constant temperature for 1 to 5 minutes; and molding the zinc-based plated steel sheet maintained at the constant temperature with a die and simultaneously quenching the steel sheet, wherein the zinc-based plated steel sheet includes a base steel sheet and a zinc-based plated layer formed on a surface of the base steel sheet and including at least one element selected from the group consisting of Sb, Sn, and Bi in a total amount of 0.05 to 2.0 wt%.
- microcracks in a plated layer caused during hot press forming is effectively restrained from propagating to the base steel sheet, obtaining excellent durability.
- FIG. 1 shows observed microcracks of Comparative Example 1
- FIG. 2 shows observed microcracks of Inventive Example 1
- FIG. 3 shows observed microcracks of Inventive Example 3
- FIG. 4 shows observed microcracks of Comparative Example 4
- FIG. 5 shows observed microcracks of Inventive Example 5.
- FIG. 6 (a) is GDS data obtained by analyzing contents of Al, Mg, and Sn according to depths of a plated layer in Inventive Example 1
- FIG. 6 (b) is GDS data obtained by analyzing contents of Al, Mg, and Sn according to depths of a plated layer in Inventive Example 3
- FIG. 6 (c) is GDS data obtained by analyzing contents of Al, Mg, and Sn according to depths of a plated layer in Inventive Example 5.
- the inventors of the present application have conducted research in depth to provide a hot press formed article with suppressed microcracks and resultantly discovered that propagation of microcracks in a plated layer to a base steel sheet could be effectively blocked by using a galvanized steel sheet having a zinc-based plated layer containing a proper amount of grain, a boundary segregation element as a material for hot press forming and concentrating the boundary segregation element on a surface layer of a plated layer by appropriately controlling heating conditions during the hot press forming, thus completing the present disclosure.
- the hot press formed article as one aspect of the present disclosure is manufactured by hot press forming a galvanized steel sheet including a base steel sheet and a zinc-based plated layer formed on a surface of the base steel sheet to hot press molding.
- the kind of the base steel sheet is not limited and may be, for example, a hot-rolled steel sheet or a cold-rolled steel sheet used as a base of a general galvanized steel sheet.
- a hot-rolled steel sheet a large amount of oxide scale is present on a surface thereof. Such an oxide scale lowers plating adhesion to deteriorate quality of plating, and thus, a hot-rolled steel sheet whose oxide scale has previously been removed by an acid solution may be used as a base.
- the zinc-based plated layer is formed on one side or both sides of the base steel sheet, and the zinc-based plated layer is alloyed at the time of heat treatment for hot press forming to change into an alloyed zinc-based plated layer.
- the zinc-based plated layer may include at least one element selected from the group consisting of Sb, Sn, and Bi in a total amount of 0.05% to 2.0% by weight, a balanced amount of Zn, and inevitable impurities.
- Sb, Sn, and Bi are grain boundary segregation elements serving to inhibit formation of an internal oxide due to penetration of oxygen into the grain boundary in a high-temperature working environment.
- the sum of the contents of the above elements is preferably 0.05 wt% or greater, and more preferably 0.3 wt% or greater.
- the sum of the contents of the above elements is preferably 2.0 wt% or less, more preferably 1.5 wt% or less.
- the zinc-based plated layer may further contain 0.1 to 5.0 wt% of Mg and 0.1 to 7.5 wt% of Al.
- Mg is an element serving to improve corrosion resistance of a hot press-formed article.
- the Mg content is preferably 0.1 wt% or greater, and more preferably 1 wt% or greater.
- an upper limit of the magnesium content is preferably 5.0 wt%, more preferably 4.0 wt%, and even more preferably 3.0 wt%.
- Al serves to suppress Mg oxide dross. If the Al content is too low, the effect of preventing Mg oxidation in the plating bath may be insignificant. Therefore, a lower limit of the aluminum content is preferably 0.1 wt%, and more preferably 1.5 wt%. However, if the Al content is too excessive, a temperature of the plating bath must be increased. If the temperature of the plating bath is high, the plating facility may be eroded. Therefore, an upper limit of the aluminum content is preferably 7.5 wt%, and more preferably 7.2 wt%.
- a degree of alloying of Fe of the alloyed zinc-based plated layer formed by alloying the zinc-based plated layer is preferably 30 to 85%, more preferably 45 to 78%, and even more preferably 50 to 75%.
- the degree of alloying of Fe satisfies the above range, surface cracking during hot pressing may be effectively prevented and corrosion resistance characteristics based on sacrificial corrosion prevention is excellent.
- the degree of alloying of Fe is less than 30%, a region of the plated layer in which a part of Zn is concentrated may exist in a liquid phase, causing a liquid embrittlement cracks during processing. Meanwhile, if the degree of alloying of Fe degree exceeds 85%, corrosion resistance may be lowered.
- the hot pressed-formed article of the present disclosure features that at least 70 wt% of at least one element selected from the group consisting of Sb, Sn, and Bi is concentrated in a region 3 ⁇ m or less away from a surface of the alloyed zinc-based plated layer.
- Sb, Sn and Bi When Sb, Sn and Bi are concentrated in a large amount on the surface of the alloyed zinc-based plated layer as described above, Sb, Sn and Bi may settle on the surface of the plated layer before oxygen penetrates from the surface of the plated layer to cause grain boundary segregation to restrain formation of internal oxide to prevent formation of boundary cracks in the plated layer, thus blocking propagation of microcracks to the base member. Furthermore, microcracks are mainly formed in a location where friction between the mold and the plated layer is severe. The oxide of Sb, Sn, and Bi concentrated on the surface may reduce a coefficient of friction between the mold and the plated layer to reduce formation of microcracks, thus improving durability of the hot press-formed article.
- a specific method of measuring the content of at least one element selected from the group consisting of Sb, Sn, and Bi concentrated in a region 3 ⁇ m or less away from the surface of the alloyed zinc-based plated layer is not particularly limited, but the following method may be used.
- a distribution of at least one element selected from the group consisting of Sb, Sn, and Bi in the cross-section of the plated layer may be measured using a glow discharge emission spectrometry (GDS), and an area thereof is integrated in a graph related to the content of at least one element selected from the group consisting of Sb, Sn, and Bi relative to the depth from the surface of the plated layer, whereby the content of at least one element selected from the group consisting of Sb, Sn, and Bi concentrated in the region 3 ⁇ m or less away from the surface of the alloyed zinc-based plated layer may be measured.
- GDS glow discharge emission spectrometry
- the hot press-formed article of the present disclosure described above may be manufactured by various methods, and the manufacturing method is not particularly limited. However, the hot press-formed article may be manufactured by the following method as one embodiment.
- a galvanized steel sheet having the above-described alloy composition is prepared.
- a specific method for preparing a zinc-based plated steel sheet is not particularly limited.
- the galvanized steel sheet may be manufactured by a general method of manufacturing a hot dip galvanized steel sheet.
- a base steel sheet may be dipped in a zinc-based plating bath having the above-described composition and subsequently cooled to prepare the galvanized steel sheet.
- the inert gas may be one or more selected from the group consisting of nitrogen (N 2 ), argon (Ar), and helium (He).
- Performing bubbling in the zinc-based plating bath prior to performing the plating as described above may help uniformly distribute Sb, Sn, and Bi in the zinc-based plating bath, help evenly distribute Sb, Sn, and Bi in the zinc-based plated layer obtained by a plating operation (to be described hereinafter), and help concentrate Sb, Sn, and Bi on the surface of the alloyed zinc-based plated layer of the hot press-formed article which is resultantly obtained. This is because as the distribution of Sb, Sn, and Bi in the plated layer prior to heating for hot press forming is uniform, Sb, Si, and Bi may be easily concentrated on the surface.
- supply of the inert gas is preferably maintained for 1 hour or greater, and more preferably for 3 hours or greater. Meanwhile, an increase in the supply time of the inert gas may be advantageous to evenly distribute the components in the plating bath, and thus, an upper limit is not particularly limited.
- the zinc-based plated steel sheet is primarily-heated to be processed into an article. This operation is performed in order to sufficiently impart the zinc content of the plated layer in a follow-up heating process by increasing a melting point by performing alloying with iron before zinc of the plated layer is oxidized in the atmosphere
- an average heating rate is preferably 3.5 to 4.2°C/sec. If the average heating rate is lower than 3.5°C/sec, a rise time may be prolonged to delay the effect of the increase in the melting point due to alloying to cause excessive oxidation of zinc. Meanwhile, if the average heating rate exceeds 4.2°C/sec, zinc on the surface may be first melted earlier than alloying of the material to increase oxidation of the surface of the plated layer.
- a primary heating end temperature is preferably 640 to 680°C. If the temperature is lower than 650°C, a diffusion coefficient in the plated layer may be too low due to the low temperature so the plated layer may not be uniformly alloyed. Meanwhile, if the temperature exceeds 680°C, the plated layer may be liquefied beyond the melting point of zinc delta and zinc may be vaporized to cause loss of the plated layer.
- the primarily-heated zinc-based plated steel sheet is secondarily-heated. This operation is performed so that added internal oxidation inhibiting materials are first segregated to the grain boundary to prevent grain boundary oxidation due to oxygen to suppress microcracks, while stably changing the plated layer, sufficiently changed into delta phase, into Fe-alpha phase.
- an average heating rate is preferably 1.1 to 1.6°C/sec. If the average heating rate is less than 1.1°C/sec, an alloying time to the Fe-alpha phase may be prolonged to cause a possibility of grain boundary oxidation based on oxygen, rather than the grain boundary segregation element. Meanwhile, if the average heating rate exceeds 1.6°C/sec, partial plated layer liquefaction may occur on the surface of the plated layer at high temperatures to deteriorate quality due to a non-uniform surface.
- a secondary heating end temperature is preferably 900 to 930°C. If the temperature is lower than 900°C, sufficient austenite transformation of the material may not be achieved, making it difficult to secure strength of a final product. If the temperature exceeds 930°C, the plated layer may be entirely liquefied to degrade the microcrack suppressing effect based on the added grain boundary oxidation element.
- the secondarily-heated zinc-based plated steel sheet is kept at the secondary heating end temperature for 1 to 5 minutes. If the holding time is less than 1 minute, it may be difficult to secure a sufficient time for the austenite transformation of the material due to the shortage of the total heating time. Meanwhile, if the holding time exceeds 5 minutes, the plated layer may be excessively alloyed to lower the zinc content in the plated layer to degrade corrosion resistance.
- the secondarily-heated zinc-based plated steel sheet is molded by a die and quenched at the same time.
- the molding and quenching by the die may be sufficient by the general hot press forming method, and therefore, it is not limited in the present disclosure.
- each of the cooled plated steel materials was heated under the conditions shown in Table 2 below and hot press-formed to obtain a hot press-formed article.
- FIG. 1 shows observed microcracks of Comparative Example 1
- FIG. 2 shows observed microcracks of Inventive Example 1
- FIG. 3 shows observed microcracks of Inventive Example 3
- FIG. 4 shows observed microcracks of Comparative Example 4
- FIG. 5 shows observed microcracks of Inventive Example 5.
- FIG. 6A is GDS data obtained by analyzing contents of Al, Mg, and Sn according to depths of a plated layer in Inventive Example 1
- FIG. 6B is GDS data obtained by analyzing contents of Al, Mg, and Sn according to depths of a plated layer in Inventive Example 3
- FIG. 6C is GDS data obtained by analyzing contents of Al, Mg, and Sn according to depths of a plated layer in Inventive Example 5.
Abstract
Description
- The present disclosure relates to a microcrack reduced hot press-formed article and a method for manufacturing the same.
- In recent years, the use of high-strength steel has increased to reduce the weight of automobiles, but such high-strength steel is easily worn or fractured at room temperature. In addition, the occurrence of a spring back phenomenon during machining makes precise dimension work difficult, which makes it difficult to form complex products. Thus, hot press forming (HPF) has been used as a desirable method for machining high strength steel.
- Hot press forming (HPF) is a method of machining a steel sheet to have a complicated shape at high temperatures by utilizing the properties of the steel sheet, soft-nitrides, having high ductility at high temperature. More specifically, in a state in which a steel sheet is heated to an austenite region or greater, the steel sheet is machined and rapidly quenched simultaneously to transform the structure of the steel sheet into martensite, thus producing a product having high strength and a precise shape.
- However, when a steel material is heated to high temperatures, a phenomenon such as corrosion or decarbonization may occur on a surface of the steel material. To prevent this, plated steel materials having a zinc-based or aluminum-based plated layer formed on a surface thereof are commonly used as materials for hot press forming. In particular, a galvanized steel sheet having a zinc-based plated layer is a steel material having corrosion resistance improved using the self-sacrificial corrosion resistance of zinc.
- However, when such a plated steel material is subjected to hot press forming, cracks are formed in the plated layer of a seam-processed part where surface friction is severe due to direct contact between a mold and the plated layer, and microcracks are formed even on a surface of the base steel sheet along the cracks formed in the plated layer.
- In order to solve the problem, Patent document 1 (
U.S. Patent Publication No. 6296805 ) proposes a technique of performing Al-based plating on a surface of a steel sheet. As proposed inPatent document 1, as Al-based plating is performed, an oxidation reaction on a surface of the steel sheet is suppressed, while the plated layer is maintained in a heating furnace, and formation of a passivation film of Al is used to increase corrosion resistance, but corrosion resistance of the Al plated steel sheet is drastically lowered. - In order to solve the problem, research into Zn-plated hot-pressed steel sheets has been conducted and reviewed, but there is a problem that microcracks are formed even in a surface of the base steel sheet, due to a high temperature working environment in which a temperature of the plated steel exceeds 900°C and stress caused by friction between a Zn-Fe alloyed layer alloyed during hot press forming and a dice. Such microcracks may act as a starting point for the propagation of cracks in the base steel sheet or cause fatigue cracks, which may decrease durability of parts.
- An aspect of the present disclosure is to provide a microcrack reduced hot press-formed article and a method for manufacturing the same.
- According to an aspect of the present disclosure, there is provided a hot press-formed article manufactured by hot press forming a galvanized steel sheet including a base steel sheet and a zinc-based plated layer formed on a surface of the base steel sheet, wherein the zinc-based plated layer includes at least one element selected from the group consisting of Sb, Sn, and Bi in a total amount of 0.05 to 2.0 wt%, a balance of Zn, and inevitable impurities, and at least 70 wt% of the at least one element selected from the group consisting of Sb, Sn, Bi is concentrated in a
region 3 µm or less away from a surface of an alloyed zinc-based plated layer, formed by alloying the zinc-based plated layer, of the hot press-formed article. - According to another aspect of the present disclosure, a method for manufacturing a hot press-formed article includes: preparing a zinc-based plated steel sheet; primarily heating the zinc-based plated steel sheet to a temperature of 640 to 680°C at a rate of 3.5 to 4.2°C/sec; secondarily heating the primarily-heated zinc-based plated steel sheet to a temperature of 900 to 930°C at a rate of 1.1 to 1.6°C/sec; maintaining the secondarily-heated zinc-based plated steel sheet at a constant temperature for 1 to 5 minutes; and molding the zinc-based plated steel sheet maintained at the constant temperature with a die and simultaneously quenching the steel sheet, wherein the zinc-based plated steel sheet includes a base steel sheet and a zinc-based plated layer formed on a surface of the base steel sheet and including at least one element selected from the group consisting of Sb, Sn, and Bi in a total amount of 0.05 to 2.0 wt%.
- As set forth above, in the hot press-formed article according to an exemplary embodiment in the present disclosure, microcracks in a plated layer caused during hot press forming is effectively restrained from propagating to the base steel sheet, obtaining excellent durability.
- Various and advantageous advantages and effects of the present inventive concept are not limited to those described above and may be more easily understood in the course of describing the specific example embodiment of the present inventive concept.
-
FIG. 1 shows observed microcracks of Comparative Example 1,FIG. 2 shows observed microcracks of Inventive Example 1,FIG. 3 shows observed microcracks of Inventive Example 3,FIG. 4 shows observed microcracks of Comparative Example 4, andFIG. 5 shows observed microcracks of Inventive Example 5. -
FIG. 6 (a) is GDS data obtained by analyzing contents of Al, Mg, and Sn according to depths of a plated layer in Inventive Example 1,FIG. 6 (b) is GDS data obtained by analyzing contents of Al, Mg, and Sn according to depths of a plated layer in Inventive Example 3, andFIG. 6 (c) is GDS data obtained by analyzing contents of Al, Mg, and Sn according to depths of a plated layer in Inventive Example 5. - The inventors of the present application have conducted research in depth to provide a hot press formed article with suppressed microcracks and resultantly discovered that propagation of microcracks in a plated layer to a base steel sheet could be effectively blocked by using a galvanized steel sheet having a zinc-based plated layer containing a proper amount of grain, a boundary segregation element as a material for hot press forming and concentrating the boundary segregation element on a surface layer of a plated layer by appropriately controlling heating conditions during the hot press forming, thus completing the present disclosure.
- Hereinafter, a hot press-formed article according to an aspect of the present disclosure will be described in detail.
- The hot press formed article as one aspect of the present disclosure is manufactured by hot press forming a galvanized steel sheet including a base steel sheet and a zinc-based plated layer formed on a surface of the base steel sheet to hot press molding.
- In the present disclosure, the kind of the base steel sheet is not limited and may be, for example, a hot-rolled steel sheet or a cold-rolled steel sheet used as a base of a general galvanized steel sheet. However, in the case of a hot-rolled steel sheet, a large amount of oxide scale is present on a surface thereof. Such an oxide scale lowers plating adhesion to deteriorate quality of plating, and thus, a hot-rolled steel sheet whose oxide scale has previously been removed by an acid solution may be used as a base.
- Meanwhile, the zinc-based plated layer is formed on one side or both sides of the base steel sheet, and the zinc-based plated layer is alloyed at the time of heat treatment for hot press forming to change into an alloyed zinc-based plated layer.
- The zinc-based plated layer may include at least one element selected from the group consisting of Sb, Sn, and Bi in a total amount of 0.05% to 2.0% by weight, a balanced amount of Zn, and inevitable impurities.
- Sb, Sn, and Bi are grain boundary segregation elements serving to inhibit formation of an internal oxide due to penetration of oxygen into the grain boundary in a high-temperature working environment. In order to exhibit such effects in the present disclosure, the sum of the contents of the above elements is preferably 0.05 wt% or greater, and more preferably 0.3 wt% or greater. However, if the content is excessive, formation of an aluminum oxide film on the surface of the plated layer may be hindered to impair a barrier function of aluminum and an effect is low relative to the increase in the content, lowering economic efficiency. Therefore, the sum of the contents of the above elements is preferably 2.0 wt% or less, more preferably 1.5 wt% or less.
- According to an example, the zinc-based plated layer may further contain 0.1 to 5.0 wt% of Mg and 0.1 to 7.5 wt% of Al.
- Mg is an element serving to improve corrosion resistance of a hot press-formed article. In order to exhibit such an effect in the present disclosure, the Mg content is preferably 0.1 wt% or greater, and more preferably 1 wt% or greater. However, if the Mg content is excessive, dross of a plating bath may be generated due to Mg oxidation in the plating bath. Therefore, an upper limit of the magnesium content is preferably 5.0 wt%, more preferably 4.0 wt%, and even more preferably 3.0 wt%.
- Al serves to suppress Mg oxide dross. If the Al content is too low, the effect of preventing Mg oxidation in the plating bath may be insignificant. Therefore, a lower limit of the aluminum content is preferably 0.1 wt%, and more preferably 1.5 wt%. However, if the Al content is too excessive, a temperature of the plating bath must be increased. If the temperature of the plating bath is high, the plating facility may be eroded. Therefore, an upper limit of the aluminum content is preferably 7.5 wt%, and more preferably 7.2 wt%.
- According to an example, a degree of alloying of Fe of the alloyed zinc-based plated layer formed by alloying the zinc-based plated layer is preferably 30 to 85%, more preferably 45 to 78%, and even more preferably 50 to 75%. When the degree of alloying of Fe satisfies the above range, surface cracking during hot pressing may be effectively prevented and corrosion resistance characteristics based on sacrificial corrosion prevention is excellent. If the degree of alloying of Fe is less than 30%, a region of the plated layer in which a part of Zn is concentrated may exist in a liquid phase, causing a liquid embrittlement cracks during processing. Meanwhile, if the degree of alloying of Fe degree exceeds 85%, corrosion resistance may be lowered.
- The hot pressed-formed article of the present disclosure features that at least 70 wt% of at least one element selected from the group consisting of Sb, Sn, and Bi is concentrated in a
region 3 µm or less away from a surface of the alloyed zinc-based plated layer. - When Sb, Sn and Bi are concentrated in a large amount on the surface of the alloyed zinc-based plated layer as described above, Sb, Sn and Bi may settle on the surface of the plated layer before oxygen penetrates from the surface of the plated layer to cause grain boundary segregation to restrain formation of internal oxide to prevent formation of boundary cracks in the plated layer, thus blocking propagation of microcracks to the base member. Furthermore, microcracks are mainly formed in a location where friction between the mold and the plated layer is severe. The oxide of Sb, Sn, and Bi concentrated on the surface may reduce a coefficient of friction between the mold and the plated layer to reduce formation of microcracks, thus improving durability of the hot press-formed article.
- Meanwhile, in the present disclosure, a specific method of measuring the content of at least one element selected from the group consisting of Sb, Sn, and Bi concentrated in a
region 3 µm or less away from the surface of the alloyed zinc-based plated layer is not particularly limited, but the following method may be used. That is, after the hot press-formed article may be cut vertically, a distribution of at least one element selected from the group consisting of Sb, Sn, and Bi in the cross-section of the plated layer may be measured using a glow discharge emission spectrometry (GDS), and an area thereof is integrated in a graph related to the content of at least one element selected from the group consisting of Sb, Sn, and Bi relative to the depth from the surface of the plated layer, whereby the content of at least one element selected from the group consisting of Sb, Sn, and Bi concentrated in theregion 3 µm or less away from the surface of the alloyed zinc-based plated layer may be measured. - The hot press-formed article of the present disclosure described above may be manufactured by various methods, and the manufacturing method is not particularly limited. However, the hot press-formed article may be manufactured by the following method as one embodiment.
- Hereinafter, a method for manufacturing a hot press-formed article having excellent durability, which is another aspect of the present disclosure, will be described in detail.
- First, a galvanized steel sheet having the above-described alloy composition is prepared. In the present disclosure, a specific method for preparing a zinc-based plated steel sheet is not particularly limited. The galvanized steel sheet may be manufactured by a general method of manufacturing a hot dip galvanized steel sheet. For example, a base steel sheet may be dipped in a zinc-based plating bath having the above-described composition and subsequently cooled to prepare the galvanized steel sheet.
- However, in order to further maximize the intended effect of the present disclosure, it is preferable to perform bubbling by supplying an inert gas in advance in the zinc-based plating bath before dipping the base steel sheet in the zinc-based plating bath. Here, the inert gas may be one or more selected from the group consisting of nitrogen (N2), argon (Ar), and helium (He).
- Performing bubbling in the zinc-based plating bath prior to performing the plating as described above may help uniformly distribute Sb, Sn, and Bi in the zinc-based plating bath, help evenly distribute Sb, Sn, and Bi in the zinc-based plated layer obtained by a plating operation (to be described hereinafter), and help concentrate Sb, Sn, and Bi on the surface of the alloyed zinc-based plated layer of the hot press-formed article which is resultantly obtained. This is because as the distribution of Sb, Sn, and Bi in the plated layer prior to heating for hot press forming is uniform, Sb, Si, and Bi may be easily concentrated on the surface.
- Meanwhile, in order to obtain the above effect, supply of the inert gas is preferably maintained for 1 hour or greater, and more preferably for 3 hours or greater. Meanwhile, an increase in the supply time of the inert gas may be advantageous to evenly distribute the components in the plating bath, and thus, an upper limit is not particularly limited.
- Next, the zinc-based plated steel sheet is primarily-heated to be processed into an article. This operation is performed in order to sufficiently impart the zinc content of the plated layer in a follow-up heating process by increasing a melting point by performing alloying with iron before zinc of the plated layer is oxidized in the atmosphere
- During the primary heating, an average heating rate is preferably 3.5 to 4.2°C/sec. If the average heating rate is lower than 3.5°C/sec, a rise time may be prolonged to delay the effect of the increase in the melting point due to alloying to cause excessive oxidation of zinc. Meanwhile, if the average heating rate exceeds 4.2°C/sec, zinc on the surface may be first melted earlier than alloying of the material to increase oxidation of the surface of the plated layer.
- During the primary heating, a primary heating end temperature is preferably 640 to 680°C. If the temperature is lower than 650°C, a diffusion coefficient in the plated layer may be too low due to the low temperature so the plated layer may not be uniformly alloyed. Meanwhile, if the temperature exceeds 680°C, the plated layer may be liquefied beyond the melting point of zinc delta and zinc may be vaporized to cause loss of the plated layer.
- Next, the primarily-heated zinc-based plated steel sheet is secondarily-heated. This operation is performed so that added internal oxidation inhibiting materials are first segregated to the grain boundary to prevent grain boundary oxidation due to oxygen to suppress microcracks, while stably changing the plated layer, sufficiently changed into delta phase, into Fe-alpha phase.
- During the secondary heating, an average heating rate is preferably 1.1 to 1.6°C/sec. If the average heating rate is less than 1.1°C/sec, an alloying time to the Fe-alpha phase may be prolonged to cause a possibility of grain boundary oxidation based on oxygen, rather than the grain boundary segregation element. Meanwhile, if the average heating rate exceeds 1.6°C/sec, partial plated layer liquefaction may occur on the surface of the plated layer at high temperatures to deteriorate quality due to a non-uniform surface.
- During the secondary heating, a secondary heating end temperature is preferably 900 to 930°C. If the temperature is lower than 900°C, sufficient austenite transformation of the material may not be achieved, making it difficult to secure strength of a final product. If the temperature exceeds 930°C, the plated layer may be entirely liquefied to degrade the microcrack suppressing effect based on the added grain boundary oxidation element.
- Next, the secondarily-heated zinc-based plated steel sheet is kept at the secondary heating end temperature for 1 to 5 minutes. If the holding time is less than 1 minute, it may be difficult to secure a sufficient time for the austenite transformation of the material due to the shortage of the total heating time. Meanwhile, if the holding time exceeds 5 minutes, the plated layer may be excessively alloyed to lower the zinc content in the plated layer to degrade corrosion resistance.
- Thereafter, the secondarily-heated zinc-based plated steel sheet is molded by a die and quenched at the same time. Here, the molding and quenching by the die may be sufficient by the general hot press forming method, and therefore, it is not limited in the present disclosure.
- Hereinafter, the present disclosure will be described more specifically by way of examples. It should be noted, however, that the following embodiments are intended to illustrate and specify the present disclosure and do not to limit the scope of the present disclosure. The scope of the present disclosure is determined by the matters described in the claims and the matters reasonably deduced therefrom.
- A low carbon cold-rolled steel sheet having a thickness of 0.8 mm, a width of 100 mm, and a length of 200 mm, as a base steel sheet, was prepared as a test sample for plating, dipped in acetone, and ultrasonically cleaned to remove foreign substances such as rolling oil present on the surface thereof. Thereafter, the steel sheet was subjected to a heat treatment in a reducing atmosphere at 750°C to secure the mechanical properties of the steel sheet at the general hotdip plating site and subsequently dipped in a zinc-based plating bath having the composition shown in Table 1 below to manufacture a plated steel sheet. Thereafter, each of the manufactured plated steel materials was gas-wiped to adjust the coating weight to 70g/m2 per side and cooled at a rate of 12°C/sec.
- Thereafter, each of the cooled plated steel materials was heated under the conditions shown in Table 2 below and hot press-formed to obtain a hot press-formed article.
- Thereafter, each of the hot press-formed articles was cut vertically, and a distribution of grain boundary segregation elements in the plated layer was measured by a GDS analysis. The results are shown in Table 2 below. A specific measurement method is as described above.
- Thereafter, a maximum depth of microcracks at a portion where tension and surface friction were most severe during molding, and the results are shown in Table 2 below.
[Table 1] Bath type Plating bath composition (wt%) (* balance is Zn) Sb Sn Bi Al Mg Bath 1 - - - 0.21 - Bath 2 - 0.7 - 1.50 1.0 Bath 3 - 0.4 - 2.5 1.0 Bath 4 - - - 2.5 1.0 Bath 5 - 0.3 - 7.0 3.0 Bath 6 0.3 - - 1.5 1.0 Bath 7 - - 0.5 2.5 1.0 [Table 2] No Bath type Primary heating Secondary heating Main tain ① Maximum depth of microc rack Remark Rate (°C /s) End temperature (°C) Rate (°C /s) End temperature (°C) Time (min .) 1 Bath 1 3.8 640 1.2 900 5 - 32.0 Comparative Example 1 2 Bath 1 4.2 670 1.6 910 5 - 29.0 Comparative Example 2 3 Bath 2 3.5 650 1.2 900 5 78 2.5 Inventive Example 1 4 Bath 2 3.9 670 1.4 910 5 85 3.8 Inventive Example 2 5 Bath 3 3.7 650 1.3 910 5 99 3.0 Inventive Example 3 6 Bath 3 4.0 660 1.1 900 5 92 3.7 Inventive Example 4 7 Bath 4 4.0 660 1.3 900 5 - 28.0 Comparative Example 3 8 Bath 4 3.9 660 1.5 915 5 - 26.0 Comparative Example 4 9 Bath 5 3.7 650 1.2 910 5 77 7.0 Inventive Example 5 10 Bath 5 3.8 640 1.4 910 5 79 7.3 Inventive Example 6 11 Bath 6 4.0 650 1.5 900 5 83 5.2 Inventive Example 7 12 Bath 6 4.1 640 1.3 920 5 82 6.0 Inventive Example 8 13 Bath 7 3.9 650 1.3 910 5 89 8.0 Inventive Example 9 14 Bath 7 3.5 640 1.2 930 5 91 7.8 Inventive Example 10 Here, ① indicates the content (wt%) of at least one element selected from the group consisting of Sb, Sn, and Bi concentrated a region 3µm or less away from the surface of the alloyed zinc-based plated layer - Referring to Table 2, it can be seen that the maximum depth of microcracks in Inventive Examples 1 to 10 satisfying all the conditions of the present disclosure was suppressed to 10 µm or less.
-
FIG. 1 shows observed microcracks of Comparative Example 1,FIG. 2 shows observed microcracks of Inventive Example 1,FIG. 3 shows observed microcracks of Inventive Example 3,FIG. 4 shows observed microcracks of Comparative Example 4, andFIG. 5 shows observed microcracks of Inventive Example 5. Referring toFIGS. 1 to 5 , it can be seen that in the case of Inventive Examples, propagation of microcracks in the plated layer to the base steel sheet was effectively blocked. -
FIG. 6A is GDS data obtained by analyzing contents of Al, Mg, and Sn according to depths of a plated layer in Inventive Example 1,FIG. 6B is GDS data obtained by analyzing contents of Al, Mg, and Sn according to depths of a plated layer in Inventive Example 3, andFIG. 6C is GDS data obtained by analyzing contents of Al, Mg, and Sn according to depths of a plated layer in Inventive Example 5.
Claims (7)
- A hot press-formed article manufactured by hot press forming a galvanized steel sheet including a base steel sheet and a zinc-based plated layer formed on a surface of the base steel sheet,
wherein the zinc-based plated layer includes at least one element selected from the group consisting of Sb, Sn, and Bi in a total amount of 0.05 to 2.0 wt%, a balance of Zn, and inevitable impurities, and
at least 70 wt% of the at least one element selected from the group consisting of Sb, Sn, Bi is concentrated in a region 3 µm or less away from a surface of an alloyed zinc-based plated layer, formed by alloying the zinc-based plated layer, of the hot press-formed article. - The hot press-formed article of claim 1,
Wherein the zinc-based plated layer includes at least one element selected from the group consisting of Sb, Sn, and Bi in a total amount of 0.3 to 1.5 wt%. - The hot press-formed article of claim 1,
Wherein the zinc-based plated layer further includes 0.1 to 5.0 wt% of Al and 0.1 to 5.0 wt% of Mg. - The hot press-formed article of claim 1,
wherein a degree of alloying of Fe of the alloyed zinc-based plated layer is 30 to 85%. - A method for manufacturing a hot press-formed article, the method comprising:preparing a zinc-based plated steel sheet;primarily heating the zinc-based plated steel sheet to a temperature of 640 to 680°C at a rate of 3.5 to 4.2°C/sec;secondarily heating the primarily-heated zinc-based plated steel sheet to a temperature of 900 to 930°C at a rate of 1.1 to 1.6°C/sec;maintaining the secondarily-heated zinc-based plated steel sheet at a constant temperature for 1 to 5 minutes; andmolding the zinc-based plated steel sheet maintained at the constant temperature with a die and simultaneously quenching the steel sheet,wherein the zinc-based plated steel sheet includes a base steel sheet and a zinc-based plated layer formed on a surface of the base steel sheet and including at least one element selected from the group consisting of Sb, Sn, and Bi in a total amount of 0.05 to 2.0 wt%.
- The method of claim 1,
Wherein the zinc-based plated layer includes at least one element selected from the group consisting of Sb, Sn, and Bi in a total amount of 0.3 to 1.5 wt%. - The method of claim 1,
Wherein the zinc-based plated layer further includes 0.1 to 5.0 wt% of Al and 0.1 to 5.0 wt% of Mg.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020150186107A KR101726094B1 (en) | 2015-12-24 | 2015-12-24 | Hot pressed part with reduced microcrack and method for manufacturing same |
PCT/KR2016/014963 WO2017111442A1 (en) | 2015-12-24 | 2016-12-21 | Microcrack-reduced, hot press-formed article, and method for manufacturing same |
Publications (3)
Publication Number | Publication Date |
---|---|
EP3396006A1 true EP3396006A1 (en) | 2018-10-31 |
EP3396006A4 EP3396006A4 (en) | 2018-11-07 |
EP3396006B1 EP3396006B1 (en) | 2019-11-20 |
Family
ID=58580256
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP16879309.9A Active EP3396006B1 (en) | 2015-12-24 | 2016-12-21 | Microcrack-reduced, hot press-formed article, and method for manufacturing same |
Country Status (6)
Country | Link |
---|---|
US (2) | US20190003031A1 (en) |
EP (1) | EP3396006B1 (en) |
JP (1) | JP6661772B2 (en) |
KR (1) | KR101726094B1 (en) |
CN (1) | CN108431286B (en) |
WO (1) | WO2017111442A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108950160A (en) * | 2018-08-25 | 2018-12-07 | 马鞍山钢铁股份有限公司 | A kind of Zn-based plating layer hot forming steel and preparation method thereof based on CSP process |
CN113564507B (en) * | 2021-07-28 | 2022-08-09 | 东北大学 | Hot galvanizing low-temperature plating solution and preparation method and application thereof |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6055590B2 (en) * | 1980-07-18 | 1985-12-05 | 新日本製鐵株式会社 | Zero-spangle galvanized steel sheet with excellent peeling resistance over time, method for producing the same, and hot-dip galvanizing coating bath |
FR2780984B1 (en) | 1998-07-09 | 2001-06-22 | Lorraine Laminage | COATED HOT AND COLD STEEL SHEET HAVING VERY HIGH RESISTANCE AFTER HEAT TREATMENT |
EP1354970B1 (en) * | 2000-12-29 | 2011-02-16 | Nippon Steel Corporation | High-strength molten-zinc-plated steel plate excellent in deposit adhesion and suitability for press forming and process for producing the same |
JP2004124207A (en) * | 2002-10-04 | 2004-04-22 | Nippon Steel Corp | Zn-PLATED STEEL SHEET FOR HOT-PRESS, AND CAR COMPONENTS WITH HIGH STRENGTH USING IT |
KR20080060981A (en) * | 2006-12-27 | 2008-07-02 | 주식회사 포스코 | Zn-coated steel sheet having excellent surface quality and the method for manufacturing the same |
KR100928788B1 (en) * | 2007-12-28 | 2009-11-25 | 주식회사 포스코 | High strength steel sheet with excellent weldability and manufacturing method |
KR101143072B1 (en) * | 2009-08-07 | 2012-05-08 | 주식회사 포스코 | Ultra-high strength galvinized steel sheet having excellent coatability and bending-workability and method for manufacturing the same |
EP2520693B1 (en) * | 2009-12-28 | 2017-01-25 | Nippon Steel & Sumitomo Metal Corporation | Method for manufacturing a hot press-molded member |
DE202011107125U1 (en) * | 2011-04-13 | 2011-11-30 | Tata Steel Ijmuiden Bv | Thermoformable strip, sheet or blank and thermoformed product |
EP2728032A4 (en) * | 2011-06-28 | 2015-03-11 | Posco | Plated steel sheet having plated layer with excellent stability for hot press molding |
JP5488735B2 (en) * | 2012-07-31 | 2014-05-14 | Jfeスチール株式会社 | Method for producing hot-dip galvanized steel pipe |
CN104520464B (en) * | 2012-08-07 | 2016-08-24 | 新日铁住金株式会社 | Hot forming electrogalvanized steel plate |
KR101528010B1 (en) * | 2012-12-21 | 2015-06-10 | 주식회사 포스코 | High manganese hot dip galvanized steel sheet with superior weldability and method for manufacturing the same |
ES2891582T3 (en) * | 2013-04-10 | 2022-01-28 | Tata Steel Ijmuiden Bv | Formed product by hot forming metal-coated steel sheet, method for forming the product, and steel strip |
CN103350539A (en) * | 2013-07-23 | 2013-10-16 | 江苏克罗德科技有限公司 | High temperature resistant anti-corrosion Al-Zn alloy coated steel sheet and preparation method thereof |
-
2015
- 2015-12-24 KR KR1020150186107A patent/KR101726094B1/en active IP Right Grant
-
2016
- 2016-12-21 CN CN201680075864.7A patent/CN108431286B/en active Active
- 2016-12-21 US US16/064,785 patent/US20190003031A1/en not_active Abandoned
- 2016-12-21 WO PCT/KR2016/014963 patent/WO2017111442A1/en active Application Filing
- 2016-12-21 JP JP2018532709A patent/JP6661772B2/en active Active
- 2016-12-21 EP EP16879309.9A patent/EP3396006B1/en active Active
-
2023
- 2023-10-30 US US18/385,162 patent/US20240082902A1/en active Pending
Also Published As
Publication number | Publication date |
---|---|
CN108431286A (en) | 2018-08-21 |
CN108431286B (en) | 2020-03-20 |
JP2019508575A (en) | 2019-03-28 |
EP3396006A4 (en) | 2018-11-07 |
EP3396006B1 (en) | 2019-11-20 |
WO2017111442A1 (en) | 2017-06-29 |
US20240082902A1 (en) | 2024-03-14 |
US20190003031A1 (en) | 2019-01-03 |
KR101726094B1 (en) | 2017-04-12 |
JP6661772B2 (en) | 2020-03-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5614496B2 (en) | Hot stamped high strength parts with excellent post-painting corrosion resistance and manufacturing method thereof | |
US20240082902A1 (en) | Microcrack-reduced, hot press-formed article, and method for manufacturing same | |
EP3632587B1 (en) | Steel sheet for hot press formed member having excellent painting adhesion and post-painting corrosion resistance, and method for manufacturing same | |
EP2687620A1 (en) | Steel sheet for hot-stamped member and process for producing same | |
KR20190078438A (en) | Plated steel for hot press forming, forming part by using the same and manufacturing method thereof | |
EP2728032A2 (en) | Plated steel sheet having plated layer with excellent stability for hot press molding | |
EP3017892A1 (en) | Method of manufacturing hot press member | |
KR20160057418A (en) | Method for producing a steel component having a metal coating protecting it against corrosion, and steel component | |
KR102031465B1 (en) | Zinc alloy coated steel having excellent corrosion resistance after forming, and method for manufacturing the same | |
JP4837604B2 (en) | Alloy hot-dip galvanized steel sheet | |
CN108430662B (en) | Hot press molded article having excellent corrosion resistance and method for producing same | |
KR20150073531A (en) | Steel sheet for hot press forming with excellent corrosion resistance and weldability, forming part and method for manufacturing thereof | |
JP5023871B2 (en) | Manufacturing method of hot pressed steel plate member | |
EP3919645A1 (en) | Hot-pressed member, cold-rolled steel sheet for hot-pressed member, and methods respectively for producing these products | |
KR101304621B1 (en) | Method for manufacturing hot press forming parts having different strengths by area | |
JP4889212B2 (en) | High-strength galvannealed steel sheet and method for producing the same | |
US11898252B2 (en) | Aluminum-based alloy-plated steel sheet having excellent workability and corrosion resistance, and manufacturing method therefor | |
EP4079928A2 (en) | Aluminum alloy-plated steel sheet having excellent workability and corrosion resistance and method for manufacturing same | |
CN105408523A (en) | Hot-pressed member and production method for same | |
KR102311503B1 (en) | Aluminium alloy plate steel sheet having excellent formability and corrosion resistance and method for manufacturing the same | |
CN113166910B (en) | Thermoforming part and method for producing same | |
KR101289198B1 (en) | Plated steel sheet for hot press forming having superior stability of plating layer | |
EP3889313A1 (en) | Aluminum-based plated steel plate for hot press having excellent resistance against hydrogen delayed fracture and spot weldability, and method for manufacturing same | |
KR101271802B1 (en) | Manufacturing method for hot press formed material having less crack | |
KR102031458B1 (en) | Hot press formed part having improved resistance for corrosion and crack propagation and method for manufacturing the same |
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 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R079 Ref document number: 602016024892 Country of ref document: DE Free format text: PREVIOUS MAIN CLASS: C23C0002060000 Ipc: C21D0001673000 |
|
17P | Request for examination filed |
Effective date: 20180720 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
A4 | Supplementary search report drawn up and despatched |
Effective date: 20181009 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: C23C 2/40 20060101ALI20181002BHEP Ipc: C21D 1/673 20060101AFI20181002BHEP Ipc: C23C 2/06 20060101ALI20181002BHEP |
|
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: 20190604 |
|
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 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602016024892 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1204255 Country of ref document: AT Kind code of ref document: T Effective date: 20191215 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20191120 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20191120 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200220 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: 20200220 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: 20191120 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: 20200221 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: 20191120 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: 20191120 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: 20191120 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20191120 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: 20191120 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: 20200320 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20191120 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20191120 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: 20191120 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: 20200412 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: 20191120 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: 20191120 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: 20191120 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1204255 Country of ref document: AT Kind code of ref document: T Effective date: 20191120 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602016024892 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20191231 |
|
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: 20191120 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: 20191120 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: 20191120 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20200821 |
|
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: 20191221 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20191221 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20191231 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: 20191120 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20191231 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: 20191120 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: 20191120 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20191231 |
|
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: 20191120 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20191120 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20161221 Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20191120 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20201221 |
|
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: 20201221 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20191120 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20191120 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R081 Ref document number: 602016024892 Country of ref document: DE Owner name: POSCO CO., LTD, POHANG-SI, KR Free format text: FORMER OWNER: POSCO, POHANG-SI, GYEONGSANGBUK-DO, KR Ref country code: DE Ref legal event code: R081 Ref document number: 602016024892 Country of ref document: DE Owner name: POSCO CO., LTD, POHANG- SI, KR Free format text: FORMER OWNER: POSCO, POHANG-SI, GYEONGSANGBUK-DO, KR Ref country code: DE Ref legal event code: R081 Ref document number: 602016024892 Country of ref document: DE Owner name: POSCO HOLDINGS INC., KR Free format text: FORMER OWNER: POSCO, POHANG-SI, GYEONGSANGBUK-DO, KR |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R081 Ref document number: 602016024892 Country of ref document: DE Owner name: POSCO CO., LTD, POHANG-SI, KR Free format text: FORMER OWNER: POSCO HOLDINGS INC., SEOUL, KR Ref country code: DE Ref legal event code: R081 Ref document number: 602016024892 Country of ref document: DE Owner name: POSCO CO., LTD, POHANG- SI, KR Free format text: FORMER OWNER: POSCO HOLDINGS INC., SEOUL, KR |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20230922 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20230920 Year of fee payment: 8 |