Patent Publication Number: US-2023141248-A1

Title: High strength cold rolled and galvannealed steel sheet and manufacturing process thereof

Description:
The present invention relates to a high strength cold rolled and galvannealed steel sheet and to a method to obtain such steel sheet. 
     BACKGROUND 
     Decreasing the weight of vehicles to reduce CO2 emissions is a major challenge in the automotive industry. This weight saving must be coupled with safety requirements. To meet these requirements, an increased demand of very high strength steels with tensile strength higher than 1450 MPa have led to steelmaking industry to continuously develop new grades. 
     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 1470 MPa. To obtain such a level of tensile strength, 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. Moreover, 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. To do so, 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 1470 MPa. 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. 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. After this cooling step, 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. These controlled cooling and tempering steps complicate the manufacturing process. 
     SUMMARY OF THE INVENTION 
     It is an object of the present invention to solve the above-mentioned problem and to provide a galvannealed steel sheet having a tensile strength above or equal to 1450 MPa and easily processable on conventional process route. 
     In a preferred embodiment of the invention, the yield strength YS is above or equal to 1050 MPa. 
     The present invention provides a cold rolled and galvannealed steel sheet having a chemical composition comprising, in weight %:
         C: 0.15-0.25%   Mn: 2.4-3.5%   Si: 0.30-0.90%   Cr: 0.30-0.70%   Mo: 0.05-0.35%   Al: 0.001-0.09%   Ti: 0.01-0.06%   B: 0.0010-0.0040%   Nb 0.01-0.05%   P≤0.020%   S≤0.010%   N≤0.008%
 
the remainder of the composition being iron and unavoidable impurities resulting from the smelting, said steel sheet having a microstructure consisting of, in surface fraction:
   from 80% to 90% of martensite,   the balance being ferrite and bainite.       

     The present invention also provides a process for manufacturing a cold rolled and galvannealed steel sheet comprising the following and successive steps:
         casting a steel to obtain a semi-product, said semi product having a composition as described above,   reheating the slab to a temperature T reheat  comprised from 1150° C. to 1300° C.,   hot rolling the reheated slab with a final rolling temperature comprised from 850° C. to 950° C., so to obtain a hot rolled steel sheet, then   cooling said steel sheet to a coiling temperature T coil  comprised from 250° C. to 650° C., then   coiling the steel sheet at said temperature T coil  so to obtain a coiled steel sheet, then   pickling the steel sheet   annealing the steel sheet to an annealing temperature T A  comprised from 500° C. to 650° C. and maintaining the steel sheet at said temperature T A  for a holding time t A      optionally pickling the steel sheet   cold rolling the hot-rolled steel sheet with a reduction rate between 20% and 80%, to obtain a cold rolled steel sheet,   heating the cold rolled steel sheet to a soaking temperature T soak  comprised from Ac1 to Ac3 and maintaining the steel sheet at said temperature T soak  for a holding time t soak  comprised from 30 s to 200 s, in order to obtain between 85% and 95% of austenite and between 5% and 15% of ferrite,   cooling the steel sheet to a temperature comprised from 440° C. to 480° C.,   coating the steel sheet by continuous dipping in a zinc bath at a temperature T Zn  comprised from 450° C. to 480° C.,   reheating the steel sheet to a galvannealed temperature T GA  comprised from 510° C. and 550° C., and maintaining the steel sheet at said temperature T GA  for a holding time t GA  comprised from 10 s and 30 s   cooling the reheated steel sheet to room temperature to obtain a cold rolled and galvannealed steel sheet.       

    
    
     DETAILED DESCRIPTION 
     The invention will now be described in detail and illustrated by examples without introducing limitations. 
     Hereinafter, Ac3 designates the temperature above which microstructure is fully austenitic, Ac1 designates the temperature above which austenite begins to form. 
     The 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%. 
     According to the invention, 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. In a preferred embodiment, 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%. 
     According to the invention, 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. 
     According to the invention, 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. Preferably, the molybdenum content is comprised between 0.05% and 0.20%. 
     According to the invention, 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. Preferably 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. 
     According to the invention, the boron content is comprised between 0.0010% and 0.0040%. As 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. In this respect, 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 microstructure of the cold rolled and galvannealed steel sheet according to the invention will now be described. 
     After cold rolling, 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. 
     During the cooling step at room temperature after the galvannealing step, austenite transforms in martensite. 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. 
     These 80% to 90% of martensite ensures a good level of tensile strength. 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. 
     In a preferred embodiment of the invention, 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. In a preferred embodiment of the invention, 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. 
     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. 
     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 preferably 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 30 s and 200 s 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 10 s to 30 s. 
     The steel sheet is then cooled to room temperature to obtain a cold rolled and galvannealed steel sheet. 
     In a preferred embodiment of the invention, 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 1800 s to 36000 s. 
     In an other preferred embodiment of the invention, 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 30 s to 100 s. 
     The invention will be now illustrated by the following examples, which are by no way limitative 
     EXAMPLES 
     2 grades, which compositions are gathered in table 1, were cast in semi-products and processed into steel sheets following the process parameters gathered in table 2. 
     Table 1-Compositions 
     The tested compositions are gathered in the following table wherein the element contents are expressed in weight percent. 
     
       
         
           
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
             
               
                   
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 Ac1 
                 Ac3 
               
               
                 Steel 
                 C 
                 Mn 
                 Si 
                 Cr 
                 Mo 
                 Al 
                 Ti 
                 B 
                 Nb 
                 P 
                 S 
                 N 
                 (° C.) 
                 (° C.) 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 A 
                 0.18 
                 2.8 
                 0.49 
                 0.41 
                 0.10 
                 0.04 
                 0.03 
                 0.0022 
                 0.02 
                 0.01 
                 0.002 
                 0.004 
                 735 
                 805 
               
               
                 
                   B 
                 
                 0.15 
                 2.6 
                 0.45 
                 0.48 
                 
                   0.03 
                 
                 0.01 
                 0.03 
                 0.0020 
                 0.013 
                 0.01 
                 0.002 
                 0.004 
                 715 
                 820 
               
               
                   
               
               
                 Steel A is according to the invention. Steel B out of the invention 
               
               
                 Underlined values: not corresponding to the invention 
               
            
           
         
       
     
     For a given steel, Ac1 and Ac3 are measured through dilatometry tests and metallography analysis. 
     Table 2-Process Parameters 
     Steel semi-products, as cast, were reheated to 1200° C., hot rolled with finish rolling temperature FRT of 910° C., coiled at a temperature T coil  of 550° C. Some steel sheets are first annealed to a temperature T A  of 600° C., and maintained at said T A  temperature for a holding time to before to be pickled. Steel sheets are then cold rolled at a reduction rate of 45%. 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 a 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 20 s. The following specific conditions were applied: 
     
       
         
           
               
               
               
               
            
               
                   
                   
               
               
                   
                 Annealing 
                 Soaking 
                 Galvannealing 
               
            
           
           
               
               
               
               
               
               
            
               
                 Trials 
                 Steel 
                 T A (° C.) 
                 T soak (° C.) 
                 t soak  (s) 
                 T GA  (° C.) 
               
               
                   
               
               
                 1 
                 A 
                 600 
                 790 
                 180 
                 540 
               
               
                 2 
                 A 
                 600 
                 790 
                 138 
                 520 
               
               
                 
                   3 
                 
                 A 
                 600 
                 
                   843 
                 
                 138 
                 520 
               
               
                 
                   4 
                 
                 A 
                 600 
                 
                   810 
                 
                 138 
                 520 
               
               
                 
                   5 
                 
                 
                   B 
                 
                 
                   — 
                 
                 790 
                 180 
                 520 
               
               
                   
               
               
                 Underlined values: not corresponding to the invention 
               
            
           
         
       
     
     The cold rolled steel sheets were analyzed after soaking and the corresponding microstructure elements were gathered in table 3. 
     
       
         
           
               
             
               
                 TABLE 3 
               
             
            
               
                   
               
               
                 Microstructure of the cold rolled steel sheets after soaking 
               
            
           
           
               
               
               
            
               
                 Trials 
                 Austenite (%) 
                 Ferrite (%) 
               
               
                   
               
               
                 1 
                 94 
                 6 
               
               
                 2 
                 94 
                 6 
               
               
                 
                   3 
                 
                   100   
                 
                   0 
                 
               
               
                 
                   4 
                 
                   100   
                 
                   0 
                 
               
               
                 
                   5 
                 
                 90 
                 10  
               
               
                   
               
               
                 Underlined values: not corresponding to the invention 
               
            
           
         
       
     
     In order to quantify this microstructure at the end of the soaking, 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 cold rolled and galvannealed steel sheets were then analyzed and the corresponding microstructure elements and properties were respectively gathered in table 4 and 5. 
     
       
         
           
               
             
               
                 TABLE 4 
               
             
            
               
                   
               
               
                 Microstructure of the cold rolled and galvannealed steel sheets 
               
            
           
           
               
               
               
               
               
            
               
                   
                   
                 Ferrite + 
                   
                   
               
               
                 Trials 
                 Martensite (%) 
                 Bainite (%) 
                 Ferrite (%) 
                 Bainite (%) 
               
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 1 
                 85 
                 15 
                 5 
                 10 
               
               
                 2 
                 89 
                 11 
                 5 
                 6 
               
               
                 
                   3 
                 
                 
                   98 
                 
                   2   
                 0 
                 2 
               
               
                 
                   4 
                 
                 
                   92 
                 
                   8   
                 0 
                 8 
               
               
                 
                   5 
                 
                 
                   75 
                 
                 
                   25 
                 
                 15 
                 10 
               
               
                   
               
               
                 Underlined values: not corresponding to the invention 
               
            
           
         
       
     
     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 sheets according to the invention, namely examples 1 and 2, are the only ones 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%. 
     In trials 3 and 4 steel A is heated above a temperature T soak  ensuring between 85% and 95% of austenite and between 5% and 15% of ferrite at the end of the soaking, thus forming too many austenite and not enough ferrite. This leads to the formation of less than 10% of the sum of ferrite and bainite at the end of the hot dip coating, which hinder the galvannealing step. 
     In Trial 5, the absence of molybdenum, which is a hardening element delaying the bainitic transformation, leads to the formation of 25% of the sum of ferrite and bainite at the end of the hot dip coating. Then, martensite formed during the last cooling step is less than 80% which leads to a low value of mechanical properties.