Martenstitic stainless steel with improved machinability
The present invention relates to a stainless steel of the martensitic type with improved machinability. 
     Iron alloys containing at least 10.5% of chromium are referred to as stainless steels. 
     Other elements form part of the composition of the steel in order to modify the structure and the properties of the alloys. The four main structures are: 
     martensitic steels 
     ferritic steels 
     austenitic steels 
     austenoferritic steels. 
     Martensite steels generally include 12 to 18% of chromium and carbon contents which can range up to approximately 1%. Many alloy elements such as Ni, Mo, Si, Ti, V, Nb, etc. make possible a wide range of properties and result in applications which are as varied as: mechanical construction, tooling, cutlery, oxides when heated, etc. 
     Their originality is that of combining good corrosion resistance due essentially to the chromium with high mechanical characteristics which are accounted for by the martensitic structure. 
     There is a vast range of martensitic stainless steels with very varied compositions and use properties. Among the most common grades there may be mentioned: 
     the nickel-free carbon-chromium grades. The characteristics sought after are hardness, corrosion resistance and polishability; 
     grades containing 16% of chromium plus nickel. The presence of chromium gives them a good corrosion resistance, the nickel (2 to 4%) enables a martensitic structure to be obtained after quenching; 
     grades with structural hardening. These have an excellent corrosion resistance with high mechanical characteristics; 
     improved 12% chromium grades (addition of elements such as vanadium, molybdenum, tungsten, silicon, niobium, titanium, etc.). The aim is to optimize one or more use properties of the material such as strength when hot, creep, resilience, corrosion resistance, etc. 
     In all these grades the structure of the final product and its mechanical characteristics depend broadly on the thermal treatments. The three common treatments are quenching, tempering and softening annealing. 
     The aim of quenching is to give the steel a martensitic structure and a very high hardness. 
     Tempering makes it possible to increase ductility, which is very low after quenching, and softening annealing makes it possible to obtain a metal that can be subjected to sophisticated processing operations such as certain methods of machining or forming. 
     All the treatments are defined as a function of the composition of the grade (adjustment of the tempering temperature, of its length, of the type of cooling, etc.). 
     Martensitic stainless steels are difficult to machine. This state of things is explained by a number of reasons. 
     In fact, their high hardness causes a mechanical fatigue of the tools, which are subjected to very high cutting stresses and may be taken beyond their break point. 
     Furthermore, the high frictional forces, added to a mediocre heat conductivity, will give rise to high temperatures at the tool/material interface, resulting in a thermal fatigue and deterioration due to diffusion. 
     Furthermore, the chip splitting regions are quite often reduced. 
     Finally, the presence of hard oxides such as alumina or chromite is a factor which worsens wear on cutting tools. 
     The sources of the wear on tools are therefore different in the case of martensitic steels (high hardness, considerable friction) than in the case of austenitic steels (cold workability, poor heat conductivity, poor chip splitting). 
     Many routes are employed to improve machinability, but all have disadvantages. 
     The addition of sulphur, which will form manganese sulphides, which are sometimes chromium-substituted, worsens the corrosion resistance, hot and cold deformability, weldability and the mechanical characteristics in a transverse direction. 
     The addition of selenium acts as a complement to the sulphur; it tends to globulize the sulphides and as a result improves the mechanical characteristics in a transverse direction. In addiction to the cost, this element is highly toxic. 
     The addition of tellurium allows, also, to globulize the sulphides, and thus tends to reduce the steel anisotropy particularly the anisotropy of the steel mechanical properties. It also improves, in itself, the machinability but has the disadvantage of reducing the hot-workability. For this reason, its use is restricted. 
     The addition of lead, which is insoluble in steel, appears in the form of spherical modules, but this element has the disadvantage of being toxic and of worsening forgeability. 
     A resulphurized austenitic steel with improved machinability, containing in its weight composition a proportion of calcium and of oxygen which improves machinability, is known from FR-A-2,648,477. 
     Now, it is well known that austenitic stainless steels are difficult to machine, to a large extent because of their low heat conductivity, resulting in poor flow of the heat produced at the point of a cutting tool and rapid deterioration of the tool, and because of their high work-hardenability, giving rise locally to regions of high hardness. 
     When the steel is being machined, as a result of the high cutting temperatures, these inclusions act as a lubricant at the interface of the steel to be machined and the cutting tool, thus resulting in a reduced wear of the cutting tools and a better surface appearance of the machined articles. 
     In addition, in the machining field, austenitic steels do not require any extensive thermal treatment that is liable to modify the physicochemical state of the steel and of the inclusions. 
     Martensitic steels, for their part, are quenchable and one of their characteristics is high hardness. As a result, the problem of the difficulty of machining is not completely solved. 
     The objective of the invention is to reduce the difficulties encountered in the machining of martensitic steels, while retaining their deformability or hot and cold forgeability properties, their mechanical characteristics and their individual behaviour in heat treatments. 
     The subject of the invention is a martensitic steel with high machinability, which is characterized by the following weight composition: 
     carbon lower than 1.2% 
     silicon lower than or equal to 2% 
     manganese lower than or equal to 2% 
     chromium: 10.5≦Cr≦19% 
     sulphur lower than or equal to 0.55% 
     calcium higher than 32×10% 
     oxygen higher than 70×10 -4  % 
     the ratio of the calcium and oxygen content Ca/O being 0.2≦Ca/O≦0.6, the said steel being subjected to at least one quenching heat treatment to give it a martensitic structure. 
     According to other characteristics of the invention: 
     the steel includes sulphur in a proportion lower than or equal to 0.035%, 
     the steel includes sulphur in a proportion 0.15%≦S≦O0.45%, the said steel being resulphurized, 
     the steel additionally includes nickel in a proportion lower than or equal to 6%, 
     the steel additionally includes molybdenum in a proportion lower than or equal to 3%, 
     the steel additionally includes in its weight composition elements chosen from tungsten, cobalt, niobium, titanium, tantalum, zirconium, vanadium and molybdenum in the following proportions by weight: 
     tungsten lower than or equal to 4% 
     cobalt lower than or equal to 4.5% 
     niobium lower than or equal to 1% 
     titanium lower than or equal to 1% 
     tantalum lower than or equal to 1% 
     zirconium lower than or equal to 1% 
     vanadium lower than or equal to 1% 
     molybdenum lower than or equal to 3% 
     the steel includes nickel in a proportion 2%≦Ni≦6% and copper in a proportion 1%≦Cu≦5% 
     the steel contains lime silicoaluminate inclusions of the anorthite and/or pseudowollastonite and/or gehlenite type. 
    
    
     The tests described below and the appended figures will make the invention easier to understand. 
     FIG. 1 shows SiO 2  --CaO--Al 2  O 3  on a ternary diagram giving the compositions of the oxides introduced into the steel according to the invention, 
     FIG. 2 shows curves representing the change in the wear of a tool for different examples which are given. 
    
    
     Martensitic steels have compositions and above all a structure which are completely different when compared with, for example, austenitic steels. The behaviours of martensitic steels during machining are related to specific problems. 
     A modification of the composition of martensitic steels does not make it possible to ensure that their properties will be maintained, let alone improved. 
     Martensitic steels can be quenched and their characterisics include high hardness. 
     These steels are metallurgically very different from austenitic steels. On the one hand, they can be subjected to quenching and the crystal structure obtained in these steels when cold is not comparable to the austenitic structure. 
     On the other hand, the production of martensitic steels differs in many ways from that of austenitic steels. 
     In particular, the heat treatments of the former are numerous and give the metal its use characteristics. The quenching (rapid cooling from a high temperature below a temperature Ms of onset of martensitic transformation, which depends on the steel&#39;s composition) enables a martensitic structure to be obtained by starting from an austenitic structure when hot. It is generally followed by a tempering (maintaining at an intermediate temperature depending on the steel) which makes it possible to increase the ductility, which is very low after quenching. 
     Some grades of martensitic steels undergo softening treatments. The latter are employed when the metal must undergo sophisticated conversion operations such as certain machining or forming methods. The metal structure is then no longer a martensitic structure but a ferritic structure with chromium carbides at the grain boundaries. 
     However, it recovers its martensitic structure and its mechanical characteristics after appropriate thermal treatments. 
     Finally, the chemical composition of martensitic steels is very different from that of austenitic steels and this is partly explained, furthermore, by the need to have a sufficiently high temperature Ms of onset of martensitic transformation. They contain only little nickel (less than 6%), and low chromium contents for stainless steels (from 11 to 19% of chromium). 
     According to the invention the martensitic steel is characterized by its weight composition which is the following: 
     carbon lower than 1.2% 
     silicon lower than or equal to 2% 
     manganese lower than or equal to 2% 
     chromium: 10.5≦Cr≦19% 
     sulphur lower than or equal to 0.4% 
     calcium higher than 32×10 -4  % 
     oxygen higher than 70×10 -4  % 
     the ratio of the calcium and oxygen content Ca/O being 0.2≦Ca/O≦0.6, the said steel being subjected to at least one quenching to give it a martensitic structure. 
     Unexpectedly, when introducing malleable oxides to a martensitic composition, it has been found that the oxides chosen, that is to say lime silicoaluminates of the anorthite and/or pseudowollastonite and/or gehlenite type which are shown in the ternary diagram of FIG. 1, maintain the main properties of the martensitic steel after the thermal treatments which the said steel undergoes, without deterioration in the mechanical properties and while markedly improving the machinability properties. 
     Now, the inclusions of malleable oxides do not have a favourable effect on machinability merely because the matrix lends itself thereto. 
     The Applicant Company was surprised to find that in a structure matrix as different as the structure of martensitic steels these oxides also have a beneficial effect on machinability. 
     Furthermore, it was not obvious that, as a result of the differences in production, the Applicant Company would succeed in obtaining the same type of inclusions in steel. 
     In particular, the Applicant Company was surprised to find that the nature of the inclusions was not changed in any way by the thermal treatments. 
     No modification, or at least no significant modification, in the analytical composition of the inclusions is produced, inter alia, by diffusion in the solid state, this being during the thermal treatments to which the martensitic steels are subjected. 
     The problems of the machining of martensitic steels are furthermore very different from the problems presented by austenitic steels. 
     In contrast to the latter, they cannot be workhardened and their heat conductivity is not as bad. 
     On the other hand, the main problem with the machining of martensitic steels is the hardness. 
     There was no reason whatever to expect that identical inclusions could have a beneficial effect when the reasons for the problems in machining were so different. 
     It has been found that when martensitic steels are machined, the malleable oxides are sufficiently heated at the machining temperatures of these steels to form a lubricating film which is continuously regenerated by the oxide inclusions present in the metal. This lubricating film makes it possible to reduce the friction of the material on the tool. The effect of the large load due to the high hardness of the material is thus found to be reduced. 
     Two classes of martensitic steels have been tested, one including sulphur in a proportion of between 0.15 and 0.45% in its weight composition, the other including sulphur in a proportion lower than 0.035% in its weight composition. 
     It has been observed that the presence of the malleable oxides in the steel does not alter the resistance to corrosion, either pitting or cavity corrosion, both in the case of the low-sulphur composition and in the resulphurized composition. 
     In general, the gain brought about in machinability is not, in any event, achieved at the expense of characteristics such as forgeability or hot or cold deformability. 
     It has also been observed that the oxides introduced retain their properties whatever heat treatment performed. 
     According to the invention the introduction of the malleable oxides is done without taking into account the carbon content to which nitrogen has been added, a decrease in which tends--as has been proved--to lower the mechanical characteristics. 
     The invention also relates to a martensitic steel to which there has been added, in its weight composition, from 2 to 6% of nickel and from 1 to 5% of copper or else less than 3% of molybdenum. 
     In steels containing more than 16% of chromium, nickel is necessary in order to obtain a martensitic structure after the quenching. 
     In so-called structural hardening grade, nickel besides its function referred to above (decrease in the quantity of delta ferrite) will form with copper the &#34;Ni 3  Cu&#34; phase which will harden the metal. In this case the hardening is not obtained merely by means of the carbon which, moreover, is relatively low. 
     In combination with the metal, the copper makes it possible to obtain a structural hardening and therefore to increase the mechanical characteristics. 
     Molybdenum improves corrosion resistance and has a beneficial effect on hardness after tempering and it also improves impact strength. 
     The martensitic steel according to the invention may also contain stabilizing elements chosen from tungsten, cobalt, niobium, titanium, tantalum and zirconium in the following proportions by weight: 
     tungsten lower than or equal to 4% 
     cobalt lower than or equal to 4.5% 
     niobium lower than or equal to 1% 
     titanium lower than or equal to 1% 
     tantalum lower than or equal to 1% 
     zirconium lower than or equal to 1%. 
     In an example of application a martensitic steel A according to the invention, the composition of which is the following: 
     
         ______________________________________                                    
       C    Si     Mn     Cr   Mo   S    P    N                           
______________________________________                                    
STEEL A  0.205  0.462  0.52 12.34                                         
                                 0.041                                    
                                      0.024                               
                                           0.022                          
                                                0.046                     
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     Ca=30×10 -4  % 
     O=129×10 -4  % 
     The ratio of the calcium and oxygen content Ca/O being equal to 0.22. 
     In this example steel A contains, by way of residue, less than 0.5% of nickel and less than 0.2% of copper. 
     This steel was compared with two reference steels whose compositions are the following: 
     
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C      Si  Mn Ni  Cr Mo  Cu S   P  N                                      
__________________________________________________________________________
Ref. 1                                                                    
    0.184                                                                 
       0.359                                                              
           0.530                                                          
              0.180                                                       
                  12.63                                                   
                     0.135                                                
                         0.084                                            
                            0.022                                         
                                0.018                                     
                                   0.056                                  
Ref. 2                                                                    
    0.194                                                                 
       0.364                                                              
           0.731                                                          
              0.313                                                       
                  12.77                                                   
                     0.093                                                
                         0.088                                            
                            0.002                                         
                                0.017                                     
                                   0.049                                  
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     The three steels were subjected to tests for turning machinability. 
     The turning is performed with solid carbide tips, a test denoted by Vb 30/0.3, which consists in determining the speed at which the flank wear is 0.3 mm after 30 min. of machining and also, with coated carbide tips, a test denoted by Vb 15/0.15 which consists in determining the speed at which the flank wear is 0.15 mm after 15 min. of machining. 
     It is found in Table 1 below that the mechanical properties are not altered in any way by the introduction of malleable oxide inclusions for two thermal softening treatments, that is to say comprising a quenching with oil at 950° C., a hold for four hours at 820° C., a slow cooling to 650° C. and then a cooling with air and &#34;treated&#34;, that is to say having undergone a quenching at 950° C., a tempering at 640° C. and a cooling in air. 
     
                                           TABLE 1                                 
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        THERMAL  Rm Rp 0.2      HARDNESS                                  
GRADE   TREATMENT                                                         
                 MPa                                                      
                    MPa  A %                                              
                            Z % HRB/HRC                                   
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INV                                                                       
   A    SOFTENED 535                                                      
                    282  29 82                                            
REF                                                                       
   2    SOFTENED 544                                                      
                    296  29.2                                             
                            64.1                                          
                                82.3 HBR                                  
REF                                                                       
   1    SOFTENED 544                                                      
                    280  28.6                                             
                            60.6                                          
                                80.6 HRB                                  
INV                                                                       
   A    TREATED  858                                                      
                    737  14 51                                            
REF                                                                       
   2    TREATED  967                                                      
                    837  12 52.6                                          
                                29.1 HRC                                  
REF                                                                       
   1    TREATED  899                                                      
                    754  15.5                                             
                            55.8                                          
                                27.3 HRC                                  
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     The tests have shown that the so-called &#34;treated&#34; steels are machined better than the softened steels. 
     In another example of application, a martensitic steel according to the invention and whose weight composition is only the following: 
     
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C        Si Mn Cr Mo 9   P  N  Ca    O     Ca/O                           
__________________________________________________________________________
STEEL B                                                                   
      0.196                                                               
         0.444                                                            
            0.555                                                         
               12.10                                                      
                  0.073                                                   
                     0.0263                                               
                         0.019                                            
                            0.053                                         
                               41 × 10.sup.-4                       
                                     99 × 10.sup.-4                 
                                           0.41                           
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     In this example, steel B contains, by way of residue, less than 0.5% of nickel and less than 0.2% of copper. 
     This steel is compared with a reference standard steel containing no malleable oxides in its composition and the composition of which is the following: 
     
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C      Si Mn Ni Cr Mo Cu S  P  N  Ca                                      
                                    O     Ca/O                            
__________________________________________________________________________
REF 3                                                                     
    0.214                                                                 
       0.344                                                              
          0.564                                                           
             0.354                                                        
                12.32                                                     
                   0.097                                                  
                      0.106                                               
                         0.261                                            
                            0.017                                         
                               0.054                                      
                                    45 × 10.sup.-4                  
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     In Table 2 below it is noted that the mechanical characteristics compared between the reference steel 3 and the steel B according to the invention show no significant differences both in the case of a softened and a treated state. 
     
                                           TABLE 2                                 
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       REF. 3          STEEL B                                            
       SOFTENED                                                           
               TREATED SOFTENED                                           
                               TREATED                                    
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Rm(MPa)                                                                   
       559     803     566     787                                        
Rp 0.2(MPa)                                                               
       418     636     408     600                                        
A %     29       18.7   29      19                                        
Z %      67.5    60.5   67      63                                        
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     Table 3 below shows characteristic values for the machining tests and shows that the treated steels according to the invention give a machinability gain of to 30%. 
     
                       TABLE 3                                                     
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METALLURGICAL STATE                                                       
TREATED              SOFTENED                                             
test:                                                                     
 Vb 30/0.3    Vb 15/0.15 Vb 30/0.3 Vb 15/0.15                             
(m/min)       (m/min)    (m/min)   (m/min)                                
______________________________________                                    
Steel ref. 1                                                              
        195       250        --      --                                   
Steel ref. 2                                                              
        150       205        --      --                                   
Steel ref. 3                                                              
        230       250        200     220                                  
Steel A 250       --         --      --                                   
Steel B 250       290        --      --                                   
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     In a third example of application, two martensitic steels C and D according to the invention, the compositions of which are the following: 
     
         __________________________________________________________________________
C       Si Mn Ni Cr Mo Cu P  N  Nb S × 10.sup.-4                    
                                         Ca × 10.sup.-4             
                                               O × 10.sup.-4        
__________________________________________________________________________
Steel C                                                                   
     0.018                                                                
        0.443                                                             
           0.825                                                          
              4.517                                                       
                 15.2                                                     
                    0.005                                                 
                       3.189                                              
                          0.01                                            
                             0.018                                        
                                0.202                                     
                                   110   65    132                        
Steel D                                                                   
     0.012                                                                
        0.448                                                             
           0.818                                                          
              3.739                                                       
                 15.37                                                    
                    0.005                                                 
                       3.236                                              
                          0.01                                            
                             0.021                                        
                                0.192                                     
                                   233   70    157                        
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     Steels C and D were compared with reference steels containing no malleable oxides and the weight compositions of which are the following: 
     
         __________________________________________________________________________
C      Si Mn Ni Cr Mo Cu P  N  Nb S × 10.sup.-4                     
                                        Ca × 10.sup.-4              
                                              O × 10.sup.-4         
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Ref. 4                                                                    
    0.011                                                                 
       0.45                                                               
          0.815                                                           
             4.548                                                        
                15.26                                                     
                   0.006                                                  
                      3.245                                               
                         0.011                                            
                            0.017                                         
                               0.182                                      
                                  270   &lt;5    138                         
Ref. 5                                                                    
    0.013                                                                 
       0.405                                                              
          0.878                                                           
             4.509                                                        
                15.26                                                     
                   0.006                                                  
                      3.228                                               
                         0.011                                            
                            0.016                                         
                               0.202                                      
                                  110   &lt;5     48                         
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     These reference steels contain copper and nickel in their composition and form part of the grades with structural hardening. 
     Three metallurgical states corresponding to different thermal treatments are commonly encountered: 
     the quenched state: oil quenching at 1050° C. then tempering at 250° C. Rm≈1000 MPa, 
     the aged state in which the metal has its maximum hardness: 1050° C. quenching then tempering at about 450° C. Rm≈1400 MPa 
     softened state: 1050° C. quenching, tempering at 760° C. for 4 hours, second tempering at about 620° C. Rm 900 MPa 
     The special feature of grades of this type is that it does not undergo dimensional changes as a result of the heat treatments. It can therefore be machined and then aged. 
     Steel D according to the invention was treated by machining in the quenched state. This is to say that it underwent a quenching at 1050° C. in oil. As shown in the curves of FIG. 2, it became apparent that the presence of malleable oxides did improve the machinability, which can be ascertained on the curves by the decrease in the tool wear. This wear changes, in fact, from 0.15 mm after 15 min. of machining at a speed of 190 m/min., an advance of 0.15 mm/turn, a pass depth of 1.5 mm for reference steel 4, to a wear of 0.125 mm for steel D. 
     Steel D according to the invention made it possible to obtain in the softened state a cutting speed of 240 m/min. whereas reference steel 5 made possible a cutting speed of 210 m/min. The recorded gain is 20%. 
     These various examples of application clearly demonstrate that the martensitic steels containing malleable oxides in their composition have an improved machinability, while the oxides do not degrade the other characteristics of the said steels.