Classifications

• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
  • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
  • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
  • C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
  • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
  • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
  • C21D8/0226—Hot rolling
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
  • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
  • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
  • C21D8/0236—Cold rolling
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
  • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
  • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
  • C21D8/0273—Final recrystallisation annealing
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
  • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
  • C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
• • C—CHEMISTRY; METALLURGY
  • 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
  • C22C38/06—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
  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
• • 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
  • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
  • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
  • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
  • C23G1/08—Iron or steel
• • 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
  • C21D2211/002—Bainite
• • 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
• • 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
  • C21D2211/008—Martensite

Definitions

• the present invention relates to a high strength cold rolled and galvannealed steel sheet and to a method to obtain such steel sheet.
• These steels are usually coated with a metallic coating improving properties such corrosion resistance.
• the metallic coatings can be deposited by hot-dip galvanizing after the annealing of the steel sheets. To obtain an improved spot weldability, the hot dip coating can be followed by an alloying treatment to obtain a galvannealed steel sheet, so that the iron of the steel sheet diffuses towards the zinc coating in order to obtain a zinc-iron alloy on the steel sheet.
• the publication WO2019188190 relates to a high strength galvanized or galvannealed steel sheet, having a tensile strength higher than 1470MPa.
• the carbon content of the steel sheet is comprised between 0.200%wt and 0.280%wt, which may reduce the weldability of the steel sheet.
• the formation of ferrite and bainite, whose total amount of the sum of the two with pearlite is less than 2%, is avoided to ensure good level of tensile strength.
• the soaking step after cold rolling has to be performed at a temperature above Ac3.
• the publication WO2016199922 relates to a high strength galvannealed steel sheet with a tensile strength higher than 1470MPa.
• the high amount of carbon between 0.25% and 0.70% allow to obtain this high level of tensile strength. But the weldability of the steel sheet may be reduced.
• the steel sheet After the alloying step, the steel sheet must be cooled in a controlled manner, in order to obtain at the end of the cooling, more than 10% of retained austenite.
• the galvannealed steel sheet is subjected to a step of tempering to obtain tempered martensite, to promote bainite transformation and to cause carbon to concentrate into retained austenite, in order to obtain the desired final microstructure : between 10% and 60% of retained austenite, less than 5% of high temperature tempered martensite, less than 5% of low temperature tempered martensite, less than 10% of fresh martensite, less than 15% of ferrite, less than 10% of pearlite, the balance being bainite.
• US 2016/319385 A1 discloses a high-strength galvanized steel sheet excellent in terms of spot weldability, anti-crash property, and bending formability which can preferably be used as an automotive steel sheet.
• the purpose of the invention therefore is to solve the above-mentioned problem and to provide a galvannealed steel sheet having a tensile strength above or equal to1450MPa and easily processable on conventional process route.
• the yield strength YS is above or equal to 1050MPa.
• the object of the present invention is achieved by providing a steel sheet according to claim 1.
• the steel sheet can also comprise characteristics of anyone of claims 2 to 5.
• Another object is achieved by providing the method according to claim 6.
• the method can also comprise characteristics of anyone of claims 7 to 8.
• Ac3 designates the temperature above which microstructure is fully austenitic
• Ac1 designates the temperature above which austenite begins to form.
• composition of the steel according to the invention will now be described, the content being expressed in weight percent.
• the carbon content is comprised from 0.15% to 0.25% to ensure a satisfactory strength. If the carbon content is too high, the weldability of the steel sheet is insufficient. A carbon content level below 0.15% does not make it possible to achieve a sufficient tensile strength.
• the manganese content is comprised from 2.4% to 3.5% to ensure satisfactory strength and to limit bainitic transformation. Above 3.5% of addition, the risk of central segregation increases to the detriment of the ductility. An amount of at least 2.4% of manganese is mandatory in order to provide the strength and hardenability of the steel sheet as well as to stabilize austenite. Preferably, the manganese content is comprised from 2.5% to 3.2%.
• the silicon content is comprised from 0.30% to 0.90%.
• Silicon is an element participating in the hardening in solid solution. A silicon addition of at least 0.30% makes it possible to obtain sufficient hardening of the ferrite and bainite. Above 0.90%, silicon oxides form at the surface, which impairs the coatability of the steel. Moreover, silicon can impair the weldability.
• the silicon content is comprised from 0.30% to 0.70%. In an other preferred embodiment, the silicon content is comprised from 0.30% to 0.50%.
• the chromium content is comprised from 0.30% to 0.70%.
• Chromium is an element participating in the hardening in solid solution.
• a chromium content level below 0.30% does not make it possible to achieve a sufficient tensile strength.
• the chromium content has to be below or equal to 0.70% to obtain a satisfactory elongation at break and limit costs.
• the molybdenum content is comprised between 0.05% and 0.35%.
• a molybdenum addition of at least 0.05% improves the hardenability of the steel and limits bainitic transformation before and during the hot dip coating. Above 0.35%, the addition of molybdenum is costly and ineffective in view of the properties which are required.
• the molybdenum content is comprised between 0.05% and 0.20%.
• the aluminium content is comprised between 0.001% and 0.09% as it is a very effective element for deoxidizing the steel in the liquid phase during elaboration.
• the aluminium content is lower than 0.09% to avoid oxidation problems and ferrite formation during cooling after intercritical soaking.
• the aluminium amount is between 0.001% and 0.06%.
• Titanium is added in an amount between 0.01% and 0.06% to provide precipitation strengthening and to protect boron against the formation of BN.
• the boron content is comprised between 0.0010% and 0.0040%.
• molybdenum boron improves the hardenability of the steel.
• the boron content is lower than 0.0040% to avoid a risk of breaking the slab during continuous casting.
• Niobium is added between 0.01% and 0.05% to refine the austenite grains during hot-rolling and to provide precipitation strengthening.
• the remainder of the composition of the steel is iron and impurities resulting from the smelting.
• P, S and N at least are considered as residual elements which are unavoidable impurities.
• Their content is less than 0.010 % for S, less than 0.020 % for P and less than 0.008 % for N.
• the cold rolled steel sheet is heated to a soaking temperature T soak and maintained at said temperature for a holding time t soak , both chosen in order to obtain, at the end of this intercritical soaking, a steel sheet with a microstructure consisting of between 85% and 95% of austenite and between 5% and 15% of ferrite.
• a part of austenite is transformed in bainite after the cooling after the intercritical soaking, during the hot dip coating.
• the cold rolled and galvannealed steel sheet has a final microstructure consisting of, in surface fraction, between 80% and 90% of martensite, the balance being ferrite and bainite.
• This martensite comprises auto tempered martensite and fresh martensite.
• the sum of ferrite and bainite is between 10% and 20% in order to ensure that the galvannealing step is successful.
• the ferrite is above or equal to 5%. In an other preferred embodiment of the invention, the bainite is above or equal to 5%.
• the cold rolled and galvannealed steel sheet according to the invention has a tensile strength TS above or equal to 1450 MPa.
• the yield strength YS is above or equal to 1050 MPa.
• TS and YS are measured according to ISO standard ISO 6892-1.
• the steel sheet according to the invention can be produced by any appropriate manufacturing method and the man skilled in the art can define one. It is however preferred to use the method according to the invention comprising the following steps: A semi-product able to be further hot-rolled, is provided with the steel composition described above. The semi product is heated to a temperature comprised from 1150°C to 1300°C, so to make it possible to ease hot rolling, with a final hot rolling temperature FRT comprises from 850°C to 950°C.
• the hot-rolled steel is then cooled and coiled at a temperature Tcoil comprised from 250°C to 650°C.
• the sheet After the coiling, the sheet is pickled to remove oxidation.
• the steel sheet is annealed to an annealing temperature T A comprised from 500°C and 650°C and maintaining at said temperature T A for a holding time t A in order to improve the cold-rollability.
• the sheet After the annealing, the sheet can be pickled to remove oxidation.
• the steel sheet is then cold rolled with a reduction rate between 20% and 80%, to obtain a cold rolled steel sheet, having a thickness that can be, for example, between 0.7 mm and 3 mm, or even better in the range of 0.8 mm to 2 mm.
• the cold-rolling reduction ratio is comprised between 20% and 80%. Below 20%, the recrystallization during subsequent heat-treatment is not favored, which may impair the ductility of the cold-rolled and galvannealed steel sheet. Above 80%, the force required to deform during cold-rolling would be too high.
• the cold rolled steel sheet is then reheated to a soaking temperature T soak comprised from Ac1 and Ac3 and maintained at said temperature T soak for a holding time t soak comprised from 30s and 200s so to obtain, at the end of this intercritical soaking, a microstructure comprising between 85% and 95% of austenite and between 5% and 15% of ferrite.
• the cold rolled steel sheet is then cooled to a temperature comprised from 440°C to 480°C in order for the sheet to reach a temperature close to the coating bath, before to be coated by continuous dipping in a zinc bath at a temperature T Zn comprised from 450° C to 480° C.
• the hot dip coated steel sheet is then reheated to a galvannealed temperature T GA comprised from 510°C to 550°C, and maintained at said temperature T GA for a holding time t GA comprised from 10s to 30s.
• the steel sheet is then cooled to room temperature to obtain a cold rolled and galvannealed steel sheet.
• the annealing step of the hot rolled steel sheet is performed by batch in an inert atmosphere, at a heat-treating temperature T A comprised from 500°C to 650°C and maintaining at said T A temperature for a holding time t A comprised from 1800s to 36000s.
• the annealing step of the hot rolled steel sheet is performed by continuous annealing, at a heat-treating temperature T A comprised from 550°C to 650°C. and maintaining at said T A temperature for a holding time t A comprised from 30s to 100s.
• the cold rolled steel sheets are reheated to a soaking temperature T soak and maintained at said temperature during t soak , and coated by hot dip coating in a zinc bath at temperature T Zn of 460°C, followed by galvannealing, with a galvannealed temperature T GA comprised from 510°C to 550°C and maintained at said temperature during t GA of 20s.
• the steel sheets are quenched after the soaking to transform 100% of austenite in martensite, austenite being instable at room temperature. Martensite amount thus corresponds to the austenite amount at the end of the soaking. Martensite and ferrite amounts are then quantified through image analysis.
• the surface fractions are determined through the following method: a specimen is cut from the cold-rolled and galvannealed steel sheet, polished and etched with a reagent (Nital), to reveal the microstructure.
• the determination of the surface fraction of each constituent are performed with image analysis through optical microscope: Martensite has a darker contrast than ferrite and bainite. Bainite is quantified by measuring the difference of martensite fractions of the sample quenched after soaking and of the sample cooled after galvannealing.
• the bainite is identified thanks to the carbides inside this bainite.
• Table 5 Properties of the cold rolled and galvannealed steel sheets Trials TS (MPa) YS (MPa) Success of GA 1 1522 1095 Yes 2 1634 1055 Yes 3 1519 1163 No 4 1611 1096 No 5 1363 954 Yes Underline values: Insufficient TS or YS, or fail of the galvannealing step.
• the success of the galvannealing step is checked by measuring the amount of iron in the coating.
• the steel is galvannealed if the iron content in the coating is between 7% and 12%.
• the examples show that the steel sheet according to the invention, namely examples 1 and 2 are the only one to show all the targeted mechanical properties with success of the galvannealing, thanks to their specific composition and microstructures.
• the mechanical properties are ensured thanks to the martensite between 80% and 90%.
• the galvannealing step is ensured thanks to the presence of ferrite and bainite in a total comprised between 10% and 20%.

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• Coating With Molten Metal (AREA)

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