EP3807435A1 - Couche de séparation pour formage à chaud - Google Patents
Couche de séparation pour formage à chaudInfo
- Publication number
- EP3807435A1 EP3807435A1 EP19733973.2A EP19733973A EP3807435A1 EP 3807435 A1 EP3807435 A1 EP 3807435A1 EP 19733973 A EP19733973 A EP 19733973A EP 3807435 A1 EP3807435 A1 EP 3807435A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cover layer
- flat steel
- steel product
- coating
- product according
- 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.)
- Pending
Links
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 97
- 239000010959 steel Substances 0.000 claims abstract description 97
- 238000000576 coating method Methods 0.000 claims abstract description 48
- 239000011248 coating agent Substances 0.000 claims abstract description 44
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000005260 corrosion Methods 0.000 claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 239000011701 zinc Substances 0.000 claims abstract description 28
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims description 57
- 230000007797 corrosion Effects 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 14
- 239000011253 protective coating Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- -1 alkaline earth metal sulfates Chemical class 0.000 claims description 10
- 238000005520 cutting process Methods 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 6
- 229910052936 alkali metal sulfate Inorganic materials 0.000 claims description 5
- 150000003008 phosphonic acid esters Chemical class 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 238000003618 dip coating Methods 0.000 claims description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 3
- 229910000385 transition metal sulfate Inorganic materials 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 238000005096 rolling process Methods 0.000 description 11
- 239000012535 impurity Substances 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000007493 shaping process Methods 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 description 3
- 235000011151 potassium sulphates Nutrition 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910000734 martensite Inorganic materials 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001563 bainite Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000003698 laser cutting Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910001562 pearlite Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- VCPQWWKLNIMKND-UHFFFAOYSA-L zinc hydroxy sulfate Chemical compound [Zn++].OOS([O-])(=O)=O.OOS([O-])(=O)=O VCPQWWKLNIMKND-UHFFFAOYSA-L 0.000 description 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical class [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C23C2/12—Aluminium or alloys based thereon
-
- 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
- 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
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/02—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions
- C23C22/03—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions containing phosphorus compounds
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/167—Phosphorus-containing compounds
- C23F11/1676—Phosphonic acids
Definitions
- the present invention relates to a flat steel product which is suitable for shaping into a component by hot press molding and which has a steel substrate, a coating which is based on aluminum and / or zinc and which protects against corrosion being applied to at least one side of the steel substrate the coating protecting against corrosion is provided with a covering layer, the covering layer having a thickness of less than 100 nm, a method for producing this flat steel product comprising at least the following steps (A) providing a coating with a protective coating against corrosion on at least one side Aluminum and / or zinc based, provided steel substrate, (B) applying a cover layer to at least one side of the steel substrate provided with a protective coating against corrosion by applying a solution of the components contained in the cover layer, and (C) Setting the thickness of the deck ski and a method for producing a hot-pressed component, comprising at least the following steps (D) providing a flat steel product, (E) cutting a blank from the flat steel product from step (D), (F) heating the blank on a Temperature above 700 ° C, and
- Processes for the production of flat steel products which are suitable for the production of components by hot press molding are known per se to the person skilled in the art.
- the components manufactured in this way are characterized by very good mechanical properties.
- the material thicknesses for applications in the automotive sector can be selected to be thinner, so that a weight reduction can be achieved.
- a corrosion-protective coating based on aluminum and / or zinc must be applied to the flat steel products.
- the correspondingly coated flat steel products have to be rolled during processing, for example, blanks have to be cut from them and the blanks have to be formed in a hot-forming process, for which the surface finish applied has to be suitable.
- WO 2012/1 19973 A1 discloses a method in which the corrosion-protecting coating of a flat steel product is provided with a cover layer which contains an oxide, nitride, sulfide, carbide, hydrate or phosphate compound of a base metal.
- the compounds mentioned are in particle form in the top layer.
- the cover layer is 100 to 5000 nm thick.
- the object of the present invention is therefore to provide a flat steel product and a method for its production, which avoids the night parts of the prior art.
- a flat steel product which is suitable for shaping into a component by hot press molding and which has a steel substrate, a coating protecting against corrosion being applied to aluminum and... On at least one side of the steel substrate / or zinc, and there is a cover layer on the corrosion-protecting coating, the cover layer having a thickness of less than 100 nm.
- a flat steel product is generally understood to be a sheet, a plate or a steel strip.
- a steel strip is preferably understood as a flat steel product.
- the flat steel product can be a hot strip or a cold strip.
- the suitability of the flat steel product according to the invention to be formed into a component by hot press molding is generally demonstrated by the fact that when the flat steel product is heated, a predominantly austenitic structure develops due to the steel composition. forms, so that easy forming is ensured and that a predominantly martensitic structure with high strength is formed by rapid cooling.
- the flat steel product according to the invention has a coating which is based on aluminum and / or zinc and protects against corrosion.
- the coating is preferably on one side of the flat steel product. In a further embodiment, the coating is present on both sides of the flat steel product.
- the coating protecting against corrosion is present, for example, with a coating weight of 20 to 200 g / m 2 , preferably 30 to 150 g / m 2 , particularly preferably 40 to 100 g / m 2, in each case on each side.
- Coatings based on zinc and / or aluminum, in particular aluminum, can contain, in addition to zinc and / or aluminum, for example silicon, iron, magnesium, strontium and / or calcium.
- a particularly preferred coating protecting against corrosion contains 0.01 to 1.5% by weight of aluminum and 0.01 to 3% of magnesium, the rest zinc and unavoidable impurities or 3-15% by weight of silicon (Si), preferably 9 to 10% by weight .-% Si, up to 3.5 wt .-% iron, balance aluminum and unavoidable impurities.
- the coating protecting against corrosion can generally be applied in all ways known to the person skilled in the art.
- the existing coatings can be applied, for example, by hot dipping, electrolytic processes, CVD, physical vapor deposition such as by means of steam spraying and / or plating.
- the flat steel product according to the invention has a thickness of, for example, 0.6 to 3.5 mm, preferably 0.8 to 3.0 mm, particularly preferably 0.8 to 2.75 mm.
- the cover layer there is a cover layer on the coating based on zinc and / or aluminum and protecting against corrosion, the cover layer having a thickness of less than 100 nm.
- the cover layer has a thickness of at least 3 nm, more preferably at least 10 nm.
- the present invention therefore relates to the flat steel product according to the invention, the cover layer having a thickness of at least 3 nm, more preferably at least 10 nm.
- the thickness of the cover layer present is preferably 20 to 95 nm, more preferably 40 to 95 nm.
- the cover layer thicknesses mentioned correspond to a cover layer coverage of 0.01 to 5 g / m 2 , preferably 0.05 to 1 g / m 3 .
- the existing cover layer is preferably distributed heterogeneously, i.e. that the same amount of cover layer is not present at all points of the flat steel product, but that the indicated thicknesses of the cover layer are average values over the flat steel product.
- the top layer according to the invention preferably contains at least one compound selected from the group consisting of phosphoric acid esters, phosphonic acid esters, sulfates and aluminum (Al (NO 3 ) 3 - and zinc nitrates (Zn (NO 3 ) 2 and mixtures thereof.
- the sulfate contained in the top layer is selected from the group consisting of ammonium sulfate ((NH 4) 2 S0 4), alkali metal sulfates such as Na 2 S0 4, K 2 S0 4, alkaline earth metal, such as MgS0 4, CaS0 4 , transition metal sulfates, for example CuS0 4 , ZnS0 4 and mixtures thereof.
- a particularly preferred phosphonic acid ester according to the invention is octadecylphosphonic acid ester.
- a particularly preferred alkali metal sulfate according to the invention is K 2 S0 4 .
- the flat steel product according to the invention is particularly suitable for use in the production of components by hot press molding.
- the present invention therefore also relates to the method for producing a flat steel product according to the invention, comprising at least the following steps:
- Step (A) of the method according to the invention comprises the provision of a steel substrate provided on at least one side with a coating protecting against corrosion, which is based on aluminum and / or zinc.
- the steel substrate provided in step (A) of the method according to the invention preferably has the following alloy components (all data in% by weight, remainder Fe and unavoidable impurities):
- 0 to 0.05 particularly preferably 0 to 0.03, S, 0.001 to 0.050, particularly preferably 0.050 to 0.030, AI,
- the steel substrate provided according to the invention has a coating which is based on aluminum and / or zinc and protects against corrosion.
- the coating is preferably present on one side of the steel substrate. In a further embodiment, the coating is on both sides of the steel substrate provided in step (A).
- the coating protecting against corrosion is present, for example, with a coating weight of 20 to 200 g / m 2 , preferably 30 to 150 g / m 2 , particularly preferably 40 to 100 g / m 2, in each case on each side.
- Coatings based on zinc and / or aluminum, in particular aluminum, can contain, in addition to zinc and / or aluminum, for example silicon, iron, magnesium, strontium and / or calcium.
- the coating protecting against corrosion can generally be applied in all ways known to the person skilled in the art.
- the existing coatings can be applied, for example, by hot dipping, electrolytic processes, CVD, PVD and / or plating.
- a coating based on aluminum which protects against corrosion is further preferably used. This is preferably applied by hot dipping.
- the present invention therefore preferably relates to the method according to the invention, wherein in step (A) a steel substrate is provided which has a coating based on zinc which has been applied electrolytically.
- the present invention preferably relates to the method according to the invention, a steel substrate being provided in step (A) which Has layering based on aluminum, which has been applied by hot dip coating.
- the steel substrate provided according to the invention has a thickness of, for example, 0.6 to 3.5 mm, preferably 0.8 to 3.0 mm, particularly preferably 0.8 to 2.75 mm.
- Step (B) of the method according to the invention comprises the application of a cover layer to at least one side of the steel substrate provided with a protective coating against corrosion by application of a solution of the components contained in the cover layer.
- Suitable compounds or reagents which are used in step (B) of the process according to the invention are in particular selected from the group consisting of phosphoric acid esters, phosphonic acid esters, sulfates, nitrates and mixtures thereof.
- a sulfate is particularly preferably selected from the group consisting of ammonium sulfate ((NH 4 ) 2 S0 4 ), alkali metal sulfates, for example Na 2 S0, K 2 S0, alkaline earth metal sulfates, for example MgS0 4 , CaS0 4 , transition metal sulfates , for example CuS0 4 , Zn-S0 4 and mixtures thereof.
- ammonium sulfate (NH 4 ) 2 S0 4 )
- alkali metal sulfates for example Na 2 S0, K 2 S0
- alkaline earth metal sulfates for example MgS0 4 , CaS0 4
- transition metal sulfates for example CuS0 4 , Zn-S0 4 and mixtures thereof.
- a particularly preferred phosphonic acid ester according to the invention is octadecylphosphonic acid ester.
- a particularly preferred alkali metal sulfate according to the invention is K 2 S0 4 .
- step (B) of the process according to the invention solutions or dispersions of the reagents mentioned are preferably used, particularly preferably aqueous solutions are used.
- alcoholic solvents such as ethanol, isopropanol, methanol or mixtures thereof can also be used.
- the present invention preferably relates to the method according to the invention, an aqueous or alcoholic solution being used in step (B).
- Solutions in particular aqueous solutions, with a concentration of the reagent to be applied of 10 to 100 g / L, more preferably 20 to 80 g / L, are preferably used.
- Step (B) of the method according to the invention can generally be carried out using all methods known to the person skilled in the art, for example spraying on, dipping, for example in a coater or a rinsing unit, and combinations thereof.
- step (B) of the method according to the invention so much reagent or solution or dispersion of the reagent is generally applied that a cover layer with a thickness of less than 100 nm forms therefrom in the further course of the method.
- the reagent or solution or dispersion thereof is applied in step (B) in an amount of 0.01 to 5 g / m 2 , preferably 0.05 to 1 g / m 2 , each per Side, angry.
- step (C) comprises adjusting the thickness of the cover layer
- step (C) of the process according to the invention can be carried out using any of the methods known to those skilled in the art, for example by squeezing through a pair of rollers.
- step (C) of the process according to the invention further process steps known to the person skilled in the art can take place, for example drying the applied cover layer at belt temperatures between 20 to 250 ° C., preferably 20 to 120 ° C., particularly preferably 50 to 120 ° C.
- step (C) or an optional drying are, for example, rolling up the steel strip obtained, trimming and / or blank cutting.
- Appropriate methods are known per se to the person skilled in the art.
- the steel strip is not dried after application of the cover layer, but is rolled up directly.
- a flat steel product in particular a steel strip, which has a coating based on aluminum and / or zinc and has a cover layer explained above.
- the flat steel product thus obtained is preferably used in step (D) of the method according to the invention for the production of a hot-pressed component.
- the present invention therefore also relates to a method for producing a hot-pressed component, comprising at least the following steps:
- step (E) cutting a blank from the flat steel product from step (D), (F) heating the board to a temperature above 700 ° C, and
- step (G) Forming the heated blank from step (F) in a forming tool to obtain the hot-pressed component.
- Step (D) of the method according to the invention comprises providing a flat steel product according to the invention.
- This flat steel product is preferably produced by the process steps (A), (B) and (C) described above.
- the flat steel product produced according to the invention is preferably provided as a roll and is therefore preferably rolled off and optionally smoothed before step (E).
- the flat steel product provided in step (D) of the method according to the invention can be subjected to flexible rolling before step (E) of the method according to the invention.
- variable sheet thicknesses are produced in almost any sequence in the rolling direction by a process known per se to the person skilled in the art by rolling with adjustable rolling forces which are set by means of a variable roll gap. Due to the flexible rolling, thickness differences of up to 70% are possible within one component.
- Step (E) of the method according to the invention comprises cutting a blank from the flat steel product from step (D).
- Methods with which step (E) of the method according to the invention can be carried out are known per se to the person skilled in the art, for example punching, laser cutting and combinations thereof.
- Step (F) of the method according to the invention comprises heating the circuit board to a temperature above 700 ° C.
- the circuit board is heated in step (F) to a temperature of 700 to 1000 ° C, particularly preferably 800 to 980 ° C; particularly preferably 850 to 940 ° C.
- the circuit board is heated to the above-mentioned temperature in step (F) preferably for a time of 5 to 900 s, particularly preferably 5 to 600 s, particularly preferably 120 to 600 s, most preferably 150 to 450 s.
- the circuit board is heated to the above-mentioned temperature in step (F) preferably at a heating rate of 1 to 200 ° C./s, particularly preferably 1 to 30 ° C./s, most preferably 3 to 20 ° C / s.
- the heating can take place with a uniform heating rate.
- step (F) of the method according to the invention can also be carried out using at least two different heating rates, the first average heating rate being particularly preferably 3 to 50 ° C./s, particularly preferably 6 to 20 ° C./s, in particular 8 to 16 ° C / s and the second heating rate is 1 to 10 ° C / s, particularly preferably 2 to 5 ° C / s.
- the circuit board in step (F) can generally be heated in any atmosphere which appears to be suitable to the person skilled in the art, for example in an atmosphere having an oxygen content of 16 to 25% by volume, nitrogen content of 75 to 84% by volume, Noble gases and other impurities with a content of less than 3% by volume and dew points between -15 ° C and +25 ° C.
- Step (F) of the method according to the invention can generally be carried out in any device or type of heating which appears to be suitable to the person skilled in the art, in particular in a roller hearth furnace, batch furnace and also by means of induction or conduction.
- the flat steel product used preferably has a structure containing ferrite, bainite, pearlite.
- the flat steel product After the flat steel product has been heated in step (F) of the method according to the invention as described above, it preferably has a structure containing austenite and ferrite.
- Step (G) of the method according to the invention comprises the shaping of the heated blank from step (F) in a shaping tool in order to obtain the hot-pressed component.
- Suitable forming tools are known per se to the person skilled in the art.
- the shaping is known per se to the person skilled in the art and is described for example in EP 2 993 248 A1.
- the transfer time i.e. the time from leaving the furnace in step (F) of the method according to the invention until the heated blank is introduced into the forming tool, 1 to 20 s, particularly preferably 3 to 12 s.
- the present invention preferably relates to the method according to the invention, it having the following step (H) after step (G):
- step (H) cooling the component from step (G) in order to obtain a hardness structure in the component.
- step (H) the formed blank is cooled. This is preferably done at a cooling rate of 20 to 1000 ° C / s.
- the formed component is obtained.
- This preferably has a structure containing martensite, austenite and ferrite.
- the present invention also relates to the use of a flat steel product according to the invention in the manufacture of motor vehicle parts, crash-relevant components such as e.g. B-pillars, sills, bumpers, tunnel systems and others.
- crash-relevant components such as e.g. B-pillars, sills, bumpers, tunnel systems and others.
- Example 1 (according to the invention):
- a steel strip with the composition given in Table 1 is coated on both sides with a protective coating of 9% by weight Si, 2.5% by weight Fe, 1% by weight of unavoidable impurities and the rest of aluminum.
- the edition is set to 70 g / m 2 per side.
- the strip After passing through the melt pool, the strip passes through a coater in a direct line.
- the coating is carried out with an aqueous potassium sulfate solution with a concentration of 50 g / l, the rollers applying 0.2 g / m 2 of potassium sulfate per surface.
- a heterogeneously distributed layer with an average layer of 90 nm remains on the surface.
- the tape is then wound up without further drying.
- the steel strip is then rolled in such a way that there are sudden changes in thickness at short intervals, for example from 1.7 mm to 1.25 mm etc.
- the coating acts as a release agent and there is a reduced cleaning effort, while remaining the surface of the tape preserved in their quality and quantity. This is followed by blank cutting and hot forming at 925 ° C and a holding time of 5 minutes.
- a steel strip with the composition given in Table 2 is electrolytically coated with zinc.
- the zinc coating has a circulation of 7 pm on each side.
- the rinsing unit is used to spray octa-decylphosphonic acid ester dissolved in ethanol at a concentration of 1 mM / l onto the belt.
- the liquid film is then squeezed off by means of rollers. A coating of 0.1 g / m 2 per side of the solution of the ester remains on the surface. There is then no drying step. A layer with an average layer of 10 nm per side remains on the surface.
- the tape is then wound up. In a later processing step, the rolling takes place in different stages. Initial thickness is 3mm and the steps are as follows: 2.75mm, 2.2mm, 1.5mm and 1.35mm.
- the octadecylphosphonic acid ester acts as a release agent between the surface of the anti-corrosion coating and the roller surface. With higher degrees of rolling there are increased forces, which in some cases allow the corrosion-protecting coating to be mechanically welded to the roller. In the presence of the octadecylphosphonic acid ester, this would partially remove the anti-corrosion coating.
- a steel strip with the composition according to Table 3 is coated on both sides with a protective coating of 8.5% by weight Si, 2.5% by weight Fe, 1% by weight of unavoidable impurities and the rest of aluminum.
- the overlay is set to 75 g / m 2 per side.
- Table 3 Composition of the steel strip from Example 3
- the strip After passing through the melt pool, the strip passes through a coater in a direct line. This is followed by coating with an aqueous potassium sulfate solution (as in Example 1) by applying the rollers at 0.4 g / m 2 on each side. A heterogeneously distributed layer with an average layer of 170 nm per side remains on the surface.
- the tape is then wound up without a further drying unit.
- the steel strip is then rolled in such a way that there are jumps in thickness at short intervals, for example from 1.7 mm to 1.25 mm. In this process, the coating acts as a release agent and there is less cleaning effort, while the surface and quality of the strip are retained. With layer thicknesses above, increased soiling can occur due to abrasion. This is followed by blank cutting and hot forming at 925 ° C and a holding time of 5 minutes.
- Coated steel strips can be obtained by the method according to the invention, which show advantages in a subsequent hot forming step.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electrochemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Coating With Molten Metal (AREA)
Abstract
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102018209737.2A DE102018209737A1 (de) | 2018-06-18 | 2018-06-18 | Trennschicht für die Warmumformung |
PCT/EP2019/065424 WO2019243146A1 (fr) | 2018-06-18 | 2019-06-13 | Couche de séparation pour formage à chaud |
Publications (1)
Publication Number | Publication Date |
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EP3807435A1 true EP3807435A1 (fr) | 2021-04-21 |
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ID=67105985
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP19733973.2A Pending EP3807435A1 (fr) | 2018-06-18 | 2019-06-13 | Couche de séparation pour formage à chaud |
Country Status (4)
Country | Link |
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EP (1) | EP3807435A1 (fr) |
CN (1) | CN112334590A (fr) |
DE (1) | DE102018209737A1 (fr) |
WO (1) | WO2019243146A1 (fr) |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5555756A (en) * | 1995-01-24 | 1996-09-17 | Inland Steel Company | Method of lubricating steel strip for cold rolling, particularly temper rolling |
DE19508164C2 (de) * | 1995-03-08 | 2000-06-29 | Wieland Werke Ag | Korrosionsbeständiges Rohr und Verfahren zu dessen Herstellung |
FR2783256B1 (fr) * | 1998-09-15 | 2000-10-27 | Lorraine Laminage | Traitement anodique de toles d'acier zingue dans des solutions aqueuses contenant des sulfates |
DE10256639A1 (de) * | 2002-12-03 | 2004-06-24 | Thyssenkrupp Stahl Ag | Schmierstoffbeschichtetes Metallblech mit verbesserten Umformeigenschaften |
WO2010063618A1 (fr) * | 2008-12-04 | 2010-06-10 | Basf Se | Procédé de fabrication d'objets moulés à partir d'une tôle d'acier galvanisée sur une face ou sur les deux faces |
DE102011001140A1 (de) * | 2011-03-08 | 2012-09-13 | Thyssenkrupp Steel Europe Ag | Stahlflachprodukt, Verfahren zum Herstellen eines Stahlflachprodukts und Verfahren zum Herstellen eines Bauteils |
DE102011077654B4 (de) * | 2011-06-16 | 2020-12-03 | BSH Hausgeräte GmbH | Verfahren zur Herstellung eines Blechteils durch Umformen |
KR20140035034A (ko) * | 2012-09-13 | 2014-03-21 | 주식회사 포스코 | 열간 프레스 성형품 제조방법 및 이를 이용한 열간 프레스 성형품 |
PL2993248T3 (pl) | 2014-09-05 | 2020-11-30 | Thyssenkrupp Steel Europe Ag | Płaski wyrób stalowy z powłoką al, sposób jego wytwarzania, oraz sposób wytwarzania elementu konstrukcyjnego kształtowanego na gorąco |
EP2995674B1 (fr) * | 2014-09-11 | 2020-07-15 | thyssenkrupp AG | Utilisation d'un sulfate et procede pour la production d'un élément en acier par formage dans une machine de formage |
TWI613324B (zh) * | 2015-03-31 | 2018-02-01 | Nippon Steel & Sumitomo Metal Corp | 鋅系鍍敷鋼板 |
-
2018
- 2018-06-18 DE DE102018209737.2A patent/DE102018209737A1/de active Pending
-
2019
- 2019-06-13 CN CN201980041220.XA patent/CN112334590A/zh active Pending
- 2019-06-13 WO PCT/EP2019/065424 patent/WO2019243146A1/fr unknown
- 2019-06-13 EP EP19733973.2A patent/EP3807435A1/fr active Pending
Also Published As
Publication number | Publication date |
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CN112334590A (zh) | 2021-02-05 |
DE102018209737A1 (de) | 2019-12-19 |
WO2019243146A1 (fr) | 2019-12-26 |
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