EP2817428B1 - High strength bake-hardenable low density steel and method for producing said steel - Google Patents
High strength bake-hardenable low density steel and method for producing said steel Download PDFInfo
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- EP2817428B1 EP2817428B1 EP13704616.5A EP13704616A EP2817428B1 EP 2817428 B1 EP2817428 B1 EP 2817428B1 EP 13704616 A EP13704616 A EP 13704616A EP 2817428 B1 EP2817428 B1 EP 2817428B1
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- 229910000831 Steel Inorganic materials 0.000 title claims description 61
- 239000010959 steel Substances 0.000 title claims description 61
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 229910052719 titanium Inorganic materials 0.000 claims description 20
- 238000000137 annealing Methods 0.000 claims description 13
- 238000005246 galvanizing Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000005098 hot rolling Methods 0.000 claims description 10
- 238000005097 cold rolling Methods 0.000 claims description 9
- 238000005266 casting Methods 0.000 claims description 7
- 238000003303 reheating Methods 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 238000009749 continuous casting Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 2
- 239000010936 titanium Substances 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 14
- 239000010955 niobium Substances 0.000 description 11
- 239000006104 solid solution Substances 0.000 description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 238000005482 strain hardening Methods 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0263—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
- C21D8/0284—Application of a separating or insulating coating
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
-
- C—CHEMISTRY; METALLURGY
- 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
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
-
- 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
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
-
- 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
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
- C23C2/0224—Two or more thermal pretreatments
-
- 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
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/024—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by cleaning or etching
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/005—Ferrite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/4998—Combined manufacture including applying or shaping of fluent material
- Y10T29/49988—Metal casting
- Y10T29/49991—Combined with rolling
Definitions
- the invention relates to a high strength bake-hardenable low density steel and to a method for producing said steel.
- ferritic steel strip or sheet comprising, in weight percent
- the steel according to the invention has a tailored chemical composition to allow the steel to contain carbon in solid solution (C_solute) after the annealing and optional galvanising step.
- This carbon in solid solution allows the steel to be bake-hardenable e.g. in a paint-baking cycle.
- the car component is formed from the steel coming of the mill, and the component is painted and baked after it has been formed into its final shape.
- the steel according to the invention combines the good formability prior to forming a car component, i.e. before the paint-baking operation, with a higher strength after the paint-baking operation.
- solute carbon solute carbon
- the level of solute carbon may also not exceed a critical upper value because the steel is preferably free from natural ageing.
- Natural ageing is the spontaneous ageing of a supersaturated solid solution at room temperature and involves a spontaneous change in the physical properties of the steel, which occurs on being held at atmospheric temperatures after hot- or cold rolling or after a final heat treatment, e.g. during transport to or storage at a customers prior to processing the strip. This natural ageing involves changes of the mechanical properties which are considered undesirable as they lead to unpredictable variations in processability during the forming of the car components. Also, the surface quality may be adversely affected due to the formation of so-called Lüder-lines. Also, too high a carbon level in solid solution may result in a deterioration of the formability prior to bake-hardening.
- solute carbon For that reason a maximum value of 50 ppm of solute carbon is preferable. A more suitable maximum is 40 ppm of solute carbon (i.e. 0.004%).
- C_solute is at least 0.0010 (10 ppm) and/or at most 0.0030 (30 ppm). This achieves a stable process and reproducible properties.
- Nitrogen in particularly free nitrogen (i.e. nitrogen in solid solution), is not desirable but unavoidable in steel making. Titanium can be optionally added to bound nitrogen into TiN. The large amount of aluminium in the steel can also ensure that all nitrogen is bound. This means that the matrix is substantially free of nitrogen in solid solution.
- Boron is optionally added to the steel. Its presence is not mandatory, but it may help to suppress any tendency for secondary work embrittlement. If added, a minimum amount of 5 ppm boron is required.
- the manganese content is at least 0.1%.
- the aluminium content is at least 6 % and/or at most 9%, preferably at most 8%.
- the steel is preferably calcium treated.
- the chemical composition may therefore also contain calcium in an amount consistent with a calcium treatment.
- the amount of carbon in solid solution is controlled by the addition of microalloying elements (Ti, Nb, V, Zr) in combination with excellent control of the total carbon content in the steel.
- Ti or Nb should be strictly controlled. Too much titanium or niobium will combine with carbon to form carbides or, in the presence of sulphur, carbosulphides. As a consequence of this, no solute carbon is available and no bake-hardenability.
- the amount of carbon in solid solution according to this invention is calculated by subtracting from the total carbon content C_total the precipitates comprising carbon as follows:
- Ti is beneficial for binding nitrogen, but not strictly necessary. Up to 0.019% Ti can be added into the steel, mainly to bind nitrogen into TiN and secondarily to control the amount of solute carbon. The titanium content must 0.019% or lower, e.g. at most 0.018% or 0.015% or even at most 0.012%.
- titanium is added as an alloying element, a suitable minimum value for the titanium content is 0.005%. If added, then a suitable minimum value for Nb is 0.008%. If added, then for V and Zr suitable minimum values are 0.002 and 0.004 respectively.
- the composition of the ferritic steel according to the invention has a base composition where no titanium is added to the steel, and any titanium present is an unavoidable impurity.
- Titanium as an alloying element or as an inevitable impurity, will first form TiN. If there is excess nitrogen, then the remaining nitrogen will be bound to aluminium. If there is excess titanium, then the remaining titanium will form Ti 4 C 2 S 2 until all titanium is consumed.
- the factor Minimum[X,Y] calculates how much carbon is consumed by the formation of Ti 4 C 2 S 2 after all free nitrogen was bound to TiN. If the calculation results in a negative value for Y, then the factor is to be set to zero.
- solute carbon available for bake hardening.
- level of solute carbon below 50 ppm, and preferably below 40 ppm, the steel according to the invention is bake hardenable and nature-aging resistant.
- a method for producing a ferritic steel strip comprising the steps of:
- the coiling temperature is at least 600°C and/or the hot rolling finishing temperature is at least 900°C.
- This hot-rolled strip can be subsequently further processed in a process comprising the steps of:
- the hot-rolled strip is usually pickled and cleaned prior to the cold-rolling step.
- the peak metal temperature in the continuous annealing process is at least 750°C, preferably at least 800°C.
- the cold rolling reduction is at least 50%.
- the thickness of the hot-rolled strip is between 1 and 5 mm and/or the thickness of the cold-rolled strip is between 0.4 and 2 mm.
- the hot-rolled strip is annealed in a continuous annealing step and optionally galvanised in a hot-dip galvanising step.
- the annealing may also take place in a so called heat-to-coat cycle.
- a heat-to-coat cycle the hot-rolled steel is reheated to a temperature sufficient for performing the hot-dip galvanising, but not to a temperature as high as the conventional continuous annealing step.
- the carbon which may have precipitated during the slow cooling of the hot rolled coil after hot rolling is brought into solid solution again.
- After annealing and/or galvanising the steel has to be fast cooled to avoid precipitation of the carbon in solid solution.
- this galvanised steel sheet for producing a car component or other product by forming, followed by painting and baking, then the paint-baking also ensures the strength increase associated with the paint-baking cycle.
- the steels were produced by casting a slab and reheating the slab at a temperature of at most 1250°C. This temperature is the maximum temperature, because at higher reheating temperatures excessive grain growth may occur.
- the finishing temperature during hot rolling was 900°C, coiling temperature 650°C followed by pickling and cold rolling (67%) and continuous annealing at a peak metal temperature of 800°C and hot-dip-galvanising.
- Steel 3a also contained 16 ppm B.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Heat Treatment Of Sheet Steel (AREA)
- Metal Rolling (AREA)
Description
- The invention relates to a high strength bake-hardenable low density steel and to a method for producing said steel.
- In the continuing efforts to reduce the carbon emissions of vehicles the steel industry, together with the car manufacturers, continue to strive to steels which allow weight reduction without affecting the processability of the steels and the safety of the finished product. To meet future CO2-emission requirements, the fuel consumption of automobiles has to be reduced. One way towards this reduction is to lower the weight of the car body. A steel with a low density and high strength can contribute to this. At the same thickness, the use of a low density steel reduces the weight of car components. A problem with known high strength steels is that their high strength compromises the formability of the material during forming of the sheet into a car component.
- Ordinary high strength steels, for example dual phase steels, allow use of thinner sheets and therefore weight reduction. However, a thinner part will have a negative effect on other properties such as stiffness, crash - and dent resistance. These negative effects can only be solved by increasing the steel thickness, thus negating the effect of the downgauging, or by changing the geometry of the component which is also undesirable.
- It is an object of this invention to provide a low density steel with a high strength in the finished component combined with excellent formability prior to forming the car component.
- It is also an object of this invention to provide a high strength steel with excellent stiffness and dent resistance.
- One or more of these objects can be reached by providing a ferritic steel strip or sheet comprising, in weight percent,
- up to 0.01 % C_total;
- up to 0.5 % Si;
- 0.1 to 1.0 % Mn;
- from 5 to up to 10 % Al;
- up to 0.010% N;
- up to 0.01 % S;
- up to 0.1 % P;
- 0.005 to 0.019% Ti;
- 0.008 to 0.08% Nb;
- 0.002 to 0.1% V;
- 0.004 to 0.1% Zr;
- remainder iron and inevitable impurities;
- Minimum[X,Y]
- Maximum[Z,0]
- (12/93)*Nb
- (12/91)*Zr
- (12/51)*V;
- X = 2*12/(2*32)*S;
- Y = 2*12/(4*48)*(Ti-48/14*N);
- Z = 12/48*(Ti-48/14*N - 4*48/(2*32)*S);
- All percentages are in weight percent, unless otherwise indicated. For the sake of avoiding any misunderstanding, the formulae given above, when typed in in a commercial spreadsheet programme such as Microsoft Excel will result in the correct interpretation of the formulae. For instance 12/93*Nb is correctly interpreted as (12/93)*Nb as the skilled person will recognise the atomic masses of carbon (12) and Nb (93) in this formula. This is the same for the other numbers in the formulae (mutatis mutandis). So, superfluously:
- The steel according to the invention has a tailored chemical composition to allow the steel to contain carbon in solid solution (C_solute) after the annealing and optional galvanising step. This carbon in solid solution allows the steel to be bake-hardenable e.g. in a paint-baking cycle. The car component is formed from the steel coming of the mill, and the component is painted and baked after it has been formed into its final shape.
- In addition, the steel according to the invention combines the good formability prior to forming a car component, i.e. before the paint-baking operation, with a higher strength after the paint-baking operation.
- The inventors found that for the steel to be bake-hardenable in a paint baking cycle at least 5 ppm of solute carbon (C_solute) must be present in steel. At lower amounts of solute carbon the effect is negligible or not reproducible.
- The level of solute carbon may also not exceed a critical upper value because the steel is preferably free from natural ageing. Natural ageing is the spontaneous ageing of a supersaturated solid solution at room temperature and involves a spontaneous change in the physical properties of the steel, which occurs on being held at atmospheric temperatures after hot- or cold rolling or after a final heat treatment, e.g. during transport to or storage at a customers prior to processing the strip. This natural ageing involves changes of the mechanical properties which are considered undesirable as they lead to unpredictable variations in processability during the forming of the car components. Also, the surface quality may be adversely affected due to the formation of so-called Lüder-lines. Also, too high a carbon level in solid solution may result in a deterioration of the formability prior to bake-hardening.
- For that reason a maximum value of 50 ppm of solute carbon is preferable. A more suitable maximum is 40 ppm of solute carbon (i.e. 0.004%).
- In an embodiment of the invention C_solute is at least 0.0010 (10 ppm) and/or at most 0.0030 (30 ppm). This achieves a stable process and reproducible properties.
- Nitrogen, in particularly free nitrogen (i.e. nitrogen in solid solution), is not desirable but unavoidable in steel making. Titanium can be optionally added to bound nitrogen into TiN. The large amount of aluminium in the steel can also ensure that all nitrogen is bound. This means that the matrix is substantially free of nitrogen in solid solution.
- Boron is optionally added to the steel. Its presence is not mandatory, but it may help to suppress any tendency for secondary work embrittlement. If added, a minimum amount of 5 ppm boron is required.
- The manganese content is at least 0.1%. In another embodiment the aluminium content is at least 6 % and/or at most 9%, preferably at most 8%.
- The steel is preferably calcium treated. The chemical composition may therefore also contain calcium in an amount consistent with a calcium treatment.
- In the steels according to the invention the amount of carbon in solid solution is controlled by the addition of microalloying elements (Ti, Nb, V, Zr) in combination with excellent control of the total carbon content in the steel.
- The amount of Ti or Nb should be strictly controlled. Too much titanium or niobium will combine with carbon to form carbides or, in the presence of sulphur, carbosulphides. As a consequence of this, no solute carbon is available and no bake-hardenability.
- The amount of carbon in solid solution according to this invention is calculated by subtracting from the total carbon content C_total the precipitates comprising carbon as follows:
- C_solute = C_ total
- Minimum[X,Y]
- Maximum[Z,0]
- (12/93)*Nb
- (12/91)*Zr
- (12/51)*V;
- X= 2*12/(2*32)*S;
- Y = 2*12/(4*48)*(Ti-48/14*N);
- Z = 12/48*(Ti -48/14*N - 4*48/(2*32)*S);
Wherein - Minimum[X,Y] = lower value of X and Y and Minimum[X,Y] = zero if Y is negative;
- Maximum[Z,0] = higher value of zero and Z.
- For the interpretation of these formulae see herein above. The addition of Ti is beneficial for binding nitrogen, but not strictly necessary. Up to 0.019% Ti can be added into the steel, mainly to bind nitrogen into TiN and secondarily to control the amount of solute carbon. The titanium content must 0.019% or lower, e.g. at most 0.018% or 0.015% or even at most 0.012%.
- If titanium is added as an alloying element, a suitable minimum value for the titanium content is 0.005%. If added, then a suitable minimum value for Nb is 0.008%. If added, then for V and Zr suitable minimum values are 0.002 and 0.004 respectively.
- According to a preferable embodiment the composition of the ferritic steel according to the invention has a base composition where no titanium is added to the steel, and any titanium present is an unavoidable impurity.
- Titanium, as an alloying element or as an inevitable impurity, will first form TiN. If there is excess nitrogen, then the remaining nitrogen will be bound to aluminium. If there is excess titanium, then the remaining titanium will form Ti4C2S2 until all titanium is consumed. The factor Minimum[X,Y] calculates how much carbon is consumed by the formation of Ti4C2S2 after all free nitrogen was bound to TiN. If the calculation results in a negative value for Y, then the factor is to be set to zero.
- If there is no titanium at all, no TiN or Ti4C2S2 will be formed and then Minimum[X,Y] amounts to zero. The factor Maximum[Z,0] determines how much carbon is bound to titanium after accounting for the formation of TiN and Ti4C2S2.
- The other three factors account for the formation of NbC, ZrC and VC, and thereby together with the factors Minimum[X,Y] and Maximum[Z,0] determine the amount of solute carbon in the steel.
- By adding no or only small amounts of titanium and/or a specified amount of Nb, there will be sufficient solute carbon available for bake hardening. By controlling the level of solute carbon below 50 ppm, and preferably below 40 ppm, the steel according to the invention is bake hardenable and nature-aging resistant.
- According to a second aspect, a method for producing a ferritic steel strip is provided comprising the steps of:
- providing a steel slab or thick strip by:
- o continuous casting, or
- o by thin slab casting, or
- o by belt casting, or
- o by strip casting;
- optionally followed by reheating the steel slab or strip at a reheating temperature of at most 1250°C;
- hot rolling the slab or thick strip and finishing the hot-rolling process at a hot rolling finishing temperature of at least 850°C;
- coiling the hot-rolled strip at a coiling temperature of between 550 and 750°C.
- In preferable embodiment the coiling temperature is at least 600°C and/or the hot rolling finishing temperature is at least 900°C.
- This hot-rolled strip can be subsequently further processed in a process comprising the steps of:
- cold-rolling the hot-rolled strip at a cold-rolling reduction of from 40 to 90% to produce a cold-rolled strip;
- annealing the cold-rolled strip in a continuous annealing process with a peak metal temperature of between 700 and 900°C;
- optionally galvanising the annealed strip in a hot-dip galvanising or electro-galvanising or a heat-to-coat process.
- The hot-rolled strip is usually pickled and cleaned prior to the cold-rolling step. In an embodiment the peak metal temperature in the continuous annealing process is at least 750°C, preferably at least 800°C.
- In an embodiment the cold rolling reduction is at least 50%.
- In an embodiment the thickness of the hot-rolled strip is between 1 and 5 mm and/or the thickness of the cold-rolled strip is between 0.4 and 2 mm.
- In an embodiment of the invention the hot-rolled strip is annealed in a continuous annealing step and optionally galvanised in a hot-dip galvanising step. The annealing may also take place in a so called heat-to-coat cycle. In a heat-to-coat cycle the hot-rolled steel is reheated to a temperature sufficient for performing the hot-dip galvanising, but not to a temperature as high as the conventional continuous annealing step. During the reheating the carbon, which may have precipitated during the slow cooling of the hot rolled coil after hot rolling is brought into solid solution again. After annealing and/or galvanising the steel has to be fast cooled to avoid precipitation of the carbon in solid solution. When using this galvanised steel sheet for producing a car component or other product by forming, followed by painting and baking, then the paint-baking also ensures the strength increase associated with the paint-baking cycle.
- The invention is now further explained by means of the following, non-limiting examples.
- Steels were produced and processed into cold-rolled steel sheets having a thickness of 1 mm. The hot rolled strip had a thickness of 3.0 mm. The chemical composition of the steels is given in Table 1.
Table 1 - Chemical composition (I = invention, R = reference) Steel C Al Mn N Ti Nb S C_solute 1 0.0020 7.0 0.20 0.0035 0.000 0.000 0.004 0.0020 I 2 0.0020 7.0 0.20 0.0030 0.010 0.000 0.004 0.0020 I 3 0.0040 7.0 0.20 0.0030 0.000 0.020 0.004 0.0014 I 3a 0.0040 6.9 0.20 0.0025 0.005 0.010 0.001 0.0031 I 4 0.0030 8.0 0.20 0.0030 0.010 0.010 0.004 0.0017 I 5 0.0040 7.5 0.20 0.0040 0.000 0.020 0.004 0.0014 I 6 0.0050 6.5 0.25 0.0030 0.010 0.020 0.004 0.0024 I 7 0.0050 6.0 0.20 0.0030 0.010 0.040 0.005 0.0000 R 8 0.0050 6.8 0.20 0.0030 0.100 0.000 0.005 0.0000 R 9 0.0050 7.0 0.20 0.0030 0.010 0.050 0.005 0.0000 R - The steels were produced by casting a slab and reheating the slab at a temperature of at most 1250°C. This temperature is the maximum temperature, because at higher reheating temperatures excessive grain growth may occur. The finishing temperature during hot rolling was 900°C, coiling temperature 650°C followed by pickling and cold rolling (67%) and continuous annealing at a peak metal temperature of 800°C and hot-dip-galvanising. Steel 3a also contained 16 ppm B.
Table 2 - Mechanical properties before and after the paint-baking cycle As-produced After 2% + 170°C/20min steel YLD (MPa) UTS (MPa) A80 (%) YLD WH (MPa) BH (MPa) 1 340 460 32 420 35 45 2 345 465 31 425 35 45 3 351 470 30 426 36 39 4 420 530 17 498 34 44 5 408 518 18 483 35 40 6 349 468 29 424 35 40 7 295 420 34 330 35 0 8 359 475 29 394 35 0 9 362 480 29 398 36 0 3a 371 480 27 457 34 52 WH= workhardening due to 2% prestrain
BH = Bake-hardening due to 20min at 170°C - The results presented in Table 2 clearly demonstrate that the presence of solute carbon at levels of 14 to 24 or to 31 ppm results in an increase of about 40 MPa on top of the work-hardening and the base strength of the steel. The inventors found this effect to be present at solute carbon levels between 5 and 50 ppm.
Minimum[X,Y] = lower value of X and Y and Minimum[X,Y] = zero if Y is negative;
Maximum[Z,0] = higher value of zero and Z;
and wherein C_solute is at least 0.0005 (5 ppm).
Claims (14)
- Ferritic steel strip or sheet comprising, in weight percent, up to 0.01 % C_total;
up to 0.5 % Si;
0.1 to 1.0 % Mn;
from 5 to up to 10 % Al;
up to 0.010% N;
up to 0.01 % S;
up to 0.1% P;
at least one of- 0.005 to 0.019% Ti;- 0.008 to 0.08% Nb;- 0.002 to 0.1% V;- 0.004 to 0.1%Zr;at least one of- 0.005 to 0.019 % Ti;- 0.008 up to 0.08 % Nb;- 0.002 to 0.1 & V;- 0.004 to 0.1 % Zr;optionally between 5 and 50 nnm B.
optionally between 5 and 50 ppm B;
remainder iron and inevitable impurities;
wherein C_solute = C_total- Minimum[X,Y]- Maximum[Z,0]- (12/93)*Nb- (12/91)*Zr- (12/51)*V;wherein
Minimum[X,Y] = lower value of X and Y and Minimum[X,Y] = zero if Y is negative;
Maximum[Z,0] = higher value of zero and Z;
and wherein C_solute is at least 0.0005 (5 ppm). - Steel according to claim 1 wherein C_solute is at most 0.0050 (50 ppm).
- Steel according to any one of the preceding claims wherein Al is at least 6 % and/or at most 9%, preferably at most 8%.
- Steel according to any one of the preceding claims wherein C_total is at least 0.0010 % (10 ppm).
- Steel according to any one of the preceding claims wherein C_solute is at least 0.0010% (10 ppm) and/or at most 0.0040% (40 ppm), preferably at most 0.0030% (30 ppm).
- Steel according to any one of the preceding claims wherein N is at most 0.005% (50 ppm).
- Steel according to any one of the preceding claims wherein Si is at most 0.2%.
- Steel according to any one of the preceding claims wherein the specific density of the steel is between 6800 and 7300 kg/m3.
- Method for producing a ferritic steel strip according to any one of claims 1 to 8 comprising the steps of:• providing a steel slab or thick strip by:o continuous casting, oro by thin slab casting, oro by belt casting, oro by strip casting;• optionally followed by reheating the steel slab or strip at a reheating temperature of at most 1250°C;• hot rolling the slab or thick strip and finishing the hot-rolling process at a hot rolling finishing temperature of at least 850°C;• coiling the hot-rolled strip at a coiling temperature of between 550 and 750°C.
- Method according to claim 9 wherein the hot-rolled strip carbon is reheated in:• a continuous annealing step, optionally followed by hot-dip galvanising followed by fast cooling, or• a heat-to-coat step, followed by hot-dip galvanising and fast cooling.
- Method for producing the ferritic steel strip comprising the steps of• cold-rolling the ferritic steel strip of claim 9 at a cold-rolling reduction of from 40 to 90% to produce a cold-rolled strip;• annealing the cold-rolled strip in a continuous annealing process with a peak metal temperature of between 700 and 900°C;• optionally galvanising the annealed strip in a hot-dip galvanising or electro-galvanising or a heat-to-coat process.
- method according to claim 11 wherein the peak metal temperature in the continuous annealing process is at least 750°C, preferably at least 800°C.
- Method according to any one of claims 11 to 12 wherein the cold rolling reduction is at least 50%.
- Method according to any one of claims 10 to 13 wherein the thickness of the hot-rolled strip is between 1 and 5 mm and/or wherein the thickness of the cold-rolled strip is between 0.4 and 2 mm.
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PCT/EP2013/053257 WO2013124264A1 (en) | 2012-02-20 | 2013-02-19 | High strength bake-hardenable low density steel and method for producing said steel |
EP13704616.5A EP2817428B2 (en) | 2012-02-20 | 2013-02-19 | High strength bake-hardenable low density steel and method for producing said steel |
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US (1) | US20150027597A1 (en) |
EP (1) | EP2817428B2 (en) |
JP (1) | JP6342336B2 (en) |
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US10626485B2 (en) | 2015-02-17 | 2020-04-21 | Jfe Steel Corporation | Thin high-strength cold-rolled steel sheet and method of producing the same |
WO2023148087A1 (en) | 2022-02-03 | 2023-08-10 | Tata Steel Ijmuiden B.V. | Method of manufacturing a low-carbon steel strip having improved formability |
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- 2013-02-19 WO PCT/EP2013/053257 patent/WO2013124264A1/en active Application Filing
- 2013-02-19 KR KR1020147025378A patent/KR20140129150A/en active IP Right Grant
- 2013-02-19 EP EP13704616.5A patent/EP2817428B2/en active Active
- 2013-02-19 US US14/378,461 patent/US20150027597A1/en not_active Abandoned
- 2013-02-19 CN CN201380010086.XA patent/CN104126023B/en not_active Expired - Fee Related
- 2013-02-19 JP JP2014557076A patent/JP6342336B2/en not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
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EP2817428B2 (en) | 2019-06-19 |
CN104126023A (en) | 2014-10-29 |
KR20140129150A (en) | 2014-11-06 |
EP2817428A1 (en) | 2014-12-31 |
US20150027597A1 (en) | 2015-01-29 |
JP2015513608A (en) | 2015-05-14 |
WO2013124264A1 (en) | 2013-08-29 |
CN104126023B (en) | 2017-02-22 |
JP6342336B2 (en) | 2018-06-13 |
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