Patent Publication Number: US-2023160033-A1

Title: Galvannealed steel sheet coated with an iron and nickel layer topped by a zinc-based layer

Description:
This is a Divisional of U.S. Pat. Application 16/754,589, filed on Apr. 8, 2020, now published as U.S. 2020/0283868 A1, which is a National Phase of PCT/IB2018/058158, filed on Oct. 19, 2018 which claims the benefit of International Patent Application PCT/IB2017/001279, filed on Oct. 24, 2017. All of the above are hereby incorporated by reference herein. 
    
    
     The present invention relates to a galvannealed steel sheet. The invention is particularly well suited for the manufacture of automotive vehicles. 
     BACKGROUND 
     Zinc based coatings are generally used because they allow for a protection against corrosion, thanks to barrier protection and cathodic protection. The barrier effect is obtained by the application of a metallic coating on steel surface. Thus, the metallic coating prevents the contact between steel and corrosive atmosphere. The barrier effect is independent from the nature of the coating and the substrate. On the contrary, sacrificial cathodic protection is based on the fact that zinc is a metal less noble that steel. Thus, if corrosion occurs, zinc is consumed preferentially as compared to steel. Cathodic protection is essential in areas where steel is directly exposed to corrosive atmosphere, like cut edges where surrounding zinc will be consumed before steel. 
     However, when heating steps are performed on such zinc coated steel sheets, for example hot press hardening or welding, cracks are observed in steel which spread from the steel/coating interface. Indeed, occasionally, there is a reduction of metal mechanical properties due to the presence of cracks in the coated steel sheet after the above operation. These cracks appear with the following conditions: high temperature; contact with a liquid metal having a low melting point (such as zinc) in addition to the presence of tensile stress; heterogeneous diffusion of molten metal with substrate grain and grain boundaries. The designation for such phenomenon is known as liquid metal embrittlement (LME), also called liquid metal assisted cracking (LMAC). 
     Sometimes, zinc coated steel sheets are alloyed at high temperature in order to obtain a galvannealed steel sheet. This steel sheet is more resistance to LME than a zinc coated steel sheet because an alloy comprising Fe and Zn is formed which has higher melting point and forms less liquid during spot welding as compared to pure Zinc. 
     However, although galvannealed steel sheets are more resistance to LME, when heating steps are performed, some cracks can appear because the resistance to LME is not sufficient enough. 
     SUMMARY OF THE INVENTION 
     It is an object of the present invention to provide a galvannealed steel sheet which does not have LME issues. It aims to make available, in particular, an easy to implement method in order to obtain an assembly which does not have LME issues after the forming and/or the welding. 
     The present invention provides a method for the manufacture of a galvannealed steel sheet comprising the following steps:
     A. the provision of a pre-coated steel sheet coated with a first coating comprising iron and nickel, such steel sheet having the following chemical composition in weight percent: 
   0.10 &lt; C &lt; 0.40%,   1.5 &lt; Mn &lt; 3.0%,   0.7 &lt; Si &lt; 2.0%,   0.05 &lt; Al &lt; 1.0%   0.75 &lt; (Si+Al) &lt; 3.0%   
 and on a purely optional basis, one or more elements such as 
   Nb ≤ 0.5%,   B ≤ 0.005%,   Cr≤ 1.0%,   Mo ≤ 0.50%,   Ni ≤ 1.0%,   Ti ≤ 0.5%,   
 the remainder of the composition making up of iron and inevitable impurities resulting from the elaboration,   B. the thermal treatment of such pre-coated steel sheet at a temperature between 600 to 1000° C.,   C. the hot-dip coating of the steel sheet obtained in step B) with a second coating based on zinc and   D. an alloying treatment to form a galvannealed steel sheet.   

     The present invention also provides a method to obtain a galvannealed steel sheet with a first layer comprising iron and nickel directly topped by a second layer based on zinc, the first and second layers being alloyed through diffusion such that the second alloy layer comprising from 5 to 15 wt.% of iron, from 0 to 15 wt.% and preferably from 1 to 15 wt.% of nickel, the balance being zinc. 
     The present invention also provides a spot welded joint of at least two metal sheets, comprising the coated steel sheet according to the present invention, said joint containing less than 3 cracks having a size above 100 µm and wherein the longest crack has a length below 400 µm. 
     The present invention also provides a galvannealed steel sheet or a spot welded joint as above that can be used for the manufacture of parts for automotive vehicle. 
     Other characteristics and advantages of the invention will become apparent from the following detailed description of the invention. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWING 
         FIG.  1    shows schematically a non-limiting example of a spot welded joint with three steel sheets made according to the present invention. 
     
    
    
     DETAILED DESCRTIPTION 
     The designation “steel” or “steel sheet” means a steel sheet, a coil, a plate having a composition allowing the part to achieve a tensile strength up to 2500 MPa and more preferably up to 2000 MPa. For example, the tensile strength is above or equal to 500 MPa, preferably above or equal to 980 MPa, advantageously above or equal to 1180 MPa and even above or equal 1470 MPa. 
     The invention relates to a method for the manufacture of a galvannealed steel sheet comprising the following steps:
     A. the provision of a pre-coated steel sheet coated with a first coating comprising iron and nickel, such steel sheet having the following chemical composition in weight percent: 
   0.10 &lt; C &lt; 0.40%,   1.5 &lt; Mn &lt; 3.0%,   0.7 &lt; Si &lt; 2.0%,   0.05 &lt; Al &lt; 1.0%   0.75 &lt; (Si+Al) &lt; 3.0%   
and on a purely optional basis, one or more elements such as 
   Nb ≤ 0.5%,   B ≤ 0.005%,   Cr≤ 1.0%,   Mo ≤ 0.50%,   Ni ≤ 1.0%,   Ti ≤ 0.5%,   
 the remainder of the composition making up of iron and inevitable impurities resulting from the elaboration,   B. the thermal treatment of such pre-coated steel sheet at a temperature between 600 to 1000° C.,   C. the hot-dip coating of the steel sheet obtained in step B) with a second coating based on zinc and   D. an alloying treatment to form a galvannealed steel sheet.   

     Without willing to be bound by any theory, it seems that during the thermal treatment, on the one hand, Ni diffuses towards the steel sheet allowing a Fe—Ni alloy layer. On the other hand, some amount of Ni is still present at the interface between the steel and the coating interface which preventing liquid zinc penetration into steel during any heating steps being for example a welding. Moreover, the presence of iron in the first coating allows for the formation of the Fe—Zn alloy during step D). 
     The first coating comprising iron and nickel is deposited by any deposition method known by the man skilled in the art. It can be deposited by vacuum deposition or electro-plating method. Preferably, it is deposited by electro-plating method. 
     Preferably, in step A), the first coating comprises from 10% to 75%, more preferably between 25 to 65% and advantageously between 40 to 60% by weight of iron. 
     Preferably, in step A), the first coating comprises from 25.0 to 90%, preferably from 35 to 75% and advantageously from 40 to 60% by weight of nickel. 
     In a preferred embodiment, in step A), the first coating consists of iron and nickel. 
     Preferably, in step A), the first coating has a thickness equal or above 0.5 µm. More preferably, the first coating has a thickness between 0.8 and 5.0 µm and advantageously between 1.0 and 2.0 µm. 
     Preferably, in step B), the thermal treatment is a continuous annealing. For example, the continuous annealing comprises a heating, a soaking and a cooling step. It can further comprise a pre-heating step. 
     Advantageously, the thermal treatment is performed in an atmosphere comprising from 1 to 30% of H 2  at a dew point between -10 and -60° C. For example, the atmosphere comprises from 1 to 10% of H 2  at a dew point between -40° C. and -60° C. 
     Advantageously, in step C), the second layer comprises above 70%, more preferably above 80% of zinc and advantageously above 85% of zinc. The second layer can be deposited by any deposition method known by the man skilled in the art. It can be done by hot-dip coating, by vacuum deposition or by electro-galvanizing. 
     For example, the coating based on zinc comprises between 0.01 and0.18 wt.% Al, optionally 0.2-8.0% Mg, the remainder being Zn. 
     Preferably, the coating based on zinc is deposited by hot-dip galvanizing method. In this embodiment, the molten bath can also comprise unavoidable impurities and residuals elements from feeding ingots or from the passage of the steel sheet in the molten bath. For example, the optionally impurities are chosen from Sr, Sb, Pb, Ti, Ca, Mn, Sn, La, Ce, Cr, Zr or Bi, the content by weight of each additional element being inferior to 0.3% by weight. The residual elements from feeding ingots or from the passage of the steel sheet in the molten bath can be iron with a content up to 5.0%, preferably 3.0%, by weight. 
     In a preferred embodiment, the second layer consists of zinc. In this case, when the coating is deposited by hot-dip galvanizing, the percentage of Aluminum is comprised between 0.10 and 0.18 wt.% in the bath. 
     Preferably, in step D), the alloying treatment is performed by heating the coated steel sheet obtained in step C) at a temperature between 460 and 550° C. for 5 to 40 seconds. For example, step D is performed at 500° C. for 20 seconds. 
     With the method according to the present invention, a galvannealed steel sheet is obtained with a first layer comprising iron and nickel directly topped by a second layer based on zinc, the first and second layers being alloyed through diffusion such that the second alloy layer comprising from 5 to 15 wt.% of iron, from 0 to 15 wt.% and preferably from 1 to 15 wt.% of nickel, the balance being zinc. 
     Preferably, the steel sheet has a microstructure comprising from 1 to 50% of residual austenite, from 1 to 60% of martensite and optionally at least one element chosen from: bainite, ferrite, cementite and pearlite. In this case, the martensite can be tempered or untempered. 
     In a preferred embodiment, the steel sheet has a microstructure comprising from 5 to 25% of residual austenite. 
     Preferably, the steel sheet has a microstructure comprising from 1 to 60% and more preferably between 10 to 60% of tempered martensite. 
     Advantageously, the steel sheet has a microstructure comprising from 10 to 40% of bainite, such bainite comprising from 10 to 20% of lower bainite, from 0 to 15% of upper bainite and from 0 to 5% of carbide free bainite. 
     Preferably, the steel sheet has a microstructure comprising from 1 to 25% of ferrite. 
     Preferably, the steel sheet has a microstructure comprising from 1 to 15% untempered martensite. 
     After the manufacture of a steel sheet, in order to produce some parts of a vehicle, it is known to assembly by welding two metal sheets. Thus, a spot welded joint is formed during the welding of at least two metal sheets, said spot being the link between the at least two metal sheets. 
     To produce a spot welded joint according to the invention, the welding is performed with an effective intensity is between 3 kA and 15 kA and the force applied on the electrodes is between 150 and 850 daN with said electrode active face diameter being between 4 and 10 mm. 
     Thus, a spot welded joint of at least two metal sheets, comprising the coated steel sheet according to the present invention, is obtained, such said joint containing less than 3 cracks having a size above 100 µm and wherein the longest crack has a length below 400 µm. 
     Preferably, the second metal sheet is a steel sheet or an aluminum sheet. More preferably, the second metal sheet is a steel sheet according to the present invention. 
     In another embodiment, the spot welded joint comprises a third metal sheet being a steel sheet or an aluminum sheet. For example, the third metal sheet is a steel sheet according to the present invention.  FIG.  1    thus shows schematically a spot weld  40  for joining three metal sheets each with a steel substrate  10 ,  20 ,  30 , first coating  12 ,  22 ,  32  and second coating  14 ,  24 ,  34 , respectively. 
     The steel sheet or the spot welded joint according to the present invention can be used for the manufacture of parts for automotive vehicle. 
     The invention will now be explained in trials carried out for information only. They are not limiting. 
     Example 
     For all samples, steel sheets used have the following composition in weight percent: C=0.37 wt.%, Mn=1.9 wt.%, Si=1.9 wt.%, Cr=0.35 wt.%, Al=0.05 wt.% and Mo=0.1%. 
     Trial 1 to 4 were prepared by deposited a first coating comprising 55% and 75% of Ni, the balance being Fe. Then, a continuous annealing was performed in an atmosphere comprising 5% of H 2  and 95% of N 2  at a dew point of -45° C. The pre-coated steel sheet was heated at a temperature of 900° C. A zinc coating was deposited by hot-dip galvanizing, the zinc bath comprising 0.2% of Al. The bath temperature was of 460° C. Finally, an alloying treatment was performed at 500° C. for 20 seconds in order to obtain a galvannealed steel sheet. 
     For comparison purpose, Trial 5 was prepared by depositing a zinc coating by electro-galvanizing after the continuous annealing of the above steel sheet. 
     The resistance to LME of Trials 1 to 5 was evaluated. To this end, for each Trial, two coated steel sheets were welded together by resistance spot welding. The type of the electrode was ISO Type B with a diameter of 16 mm; the force of the electrode was of 5 kN and the flow rate of water of was 1.5 g/min. The welding cycle was cycle is reported in Table 1.  
     
       
         
          TABLE 1
           
               
               
               
               
               
             
               
                 Welding Schedule 
               
               
                 Weld time 
                 Pulses 
                 Pulse (cy) 
                 Cool time (cy) 
                 Hold time (cy) 
               
             
            
               
                 Cycle 
                 2 
                 12 
                 2 
                 10 
               
            
           
         
       
     
     The number of cracks above 100 µm was then evaluated using an optical as well as SEM (Scanning Electron Microscopy) as reported in Table 2.  
     
       
         
          TABLE 2
           
               
               
               
               
               
               
               
             
               
                 LME crack details after spot welding (2 layer stack-up condition) 
               
               
                 Trials 
                 1 St  coating 
                 Thickness (µm) 
                 2 nd  coating 
                 Thickness (µm) 
                 Number of cracks (&gt; 100 µm) per spot weld 
                 Maximum crack length (µm) 
               
             
            
               
                 Trial 1* 
                 Fe - (55%)Ni 
                 1 
                 Zn (GA) 
                 7 
                 0 
                 0 
               
               
                 Trial 2* 
                 Fe - (55%)Ni 
                 2 
                 Zn (GA) 
                 7 
                 0 
                 250 
               
               
                 Trial 3* 
                 Fe - (75%)Ni 
                 1 
                 Zn (GA) 
                 7 
                 0 
                 250 
               
               
                 Trial 4* 
                 Fe - (75%)Ni 
                 2 
                 Zn (GA) 
                 7 
                 0 
                 0 
               
               
                 Trial 5 
                 - 
                 - 
                 Zn (EG) 
                 7 
                 3 
                 760 
               
               
                 *: according to the present invention. 
               
            
           
         
       
     
     Trials according to the present invention show an excellent resistance to LME compared to Trial 5. Indeed, the number of cracks of Trials according to the present invention is very low, even nonexistent, compared to Trial 5. 
     For each Trial, three coated steel sheets were also welded together by resistance spot welding under three layer stack-up configuration. The number of cracks above 100 µm was then evaluated using an optical as well as SEM (Scanning Electron Microscopy) as reported in Table 3.  
     
       
         
          TABLE 3
           
               
               
               
             
               
                 LME crack details after spot welding (3 layer stack-up condition) 
               
               
                 Trials 
                 Number of cracks (&gt; 100 µm) per spot weld 
                 Maximum crack length (µm) 
               
             
            
               
                 Trial 1* 
                 1 
                 250 
               
               
                 Trial 2* 
                 2 
                 350 
               
               
                 Trial 3* 
                 1 
                 150 
               
               
                 Trial 4* 
                 1 
                 250 
               
               
                 Trial 5 
                 7 
                 850 
               
               
                 *: according to the present invention. 
               
            
           
         
       
     
     Trials according to the present invention show an excellent resistance to LME as compared to Trial 5. 
     Finally, Trials 1 to 4 were bent at a 90° angle followed. An adhesive tape was then applied and removed to verify the coating adhesion with the substrate steel. The coating adhesion of those Trials was excellent.