Patent Publication Number: US-3969111-A

Title: Alloy compositions

Description:
This invention relates to alloy compositions and particularly to nickel-base cast alloys having high retention of ductility and high thermal stability on aging coupled with low thermal expansion and good oxidation resistance. 
     The present invention is directed to cast thermally stable high temperature nickel-base alloys and castings made therefrom and more particularly to an essentially non-ferrous, solid solution type, nickel-base alloy of the Ni-Cr-Mo class which possesses high thermal stability, high thermal strength, oxidation resistance up to about 1400°F., low thermal expansion and high retention of ductility on aging. 
     Great emphasis has been placed in recent years, in the field of solid solution strengthened nickel-base alloys, on attempts to provide improved structural material for use in equipment exposed to various high temperature conditions on the order of about 1600°F. and above. The field of jet engine manufacture is but one of the fields where there is and has been a continuing push to higher operating temperature levels in order to attain higher performance characteritics. In this prior art work, the primary emphasis has been in the field of wrought alloys. 
     Generally the area of cast alloys for use at somewhat lower temperatures (i.e., 1400°F.) has been essentially ignored or the higher temperature alloys have been used. This, of course, places a premium price material in a use where it is not really needed. Moreover, in addition to the problems outlined above in the wrought alloy field, the cast alloy field has also been faced with the problem of avoiding loss of ductility on aging particularly in those alloys subject to temperatures in the 1000°-1600°F range. 
     Thus, although many approaches have been tried in an effort to improve nickel-base alloys with regard to service life at temperatures in the range above 1600°F. there have been no alloys, to our knowledge, designed for use in the 1000°-1600°F. range and having a combination of superior oxidation and corrosion resistance, sustainable hot strength, thermal stability and retention of ductility on aging. 
     We have discovered a cast alloy and casting made therefrom which do, for the first time, attain all of these objectives. We have found that these objectives can be obtained by simultaneously controlling the composition of the alloy within certain limits while controlling the electron vacancy (N v ) number within narrow limits. Predicting the aged thermal stability of high temperature alloys using the N v  electron vacancy approach is discussed in the Journal of Metals October 1962 by C. T. Sims. 
     We have discovered that, for castings which are characterized by good oxidation resistance, sustainable high hot strength, thermal stability and retention of ductility on aging, the following broad composition may be employed: 
     
                Mo        13.7% to 15.5%                                           
       Cr        14.7% to 16.5%                                           
       C         0.02% max.                                               
       B         Up to 0.02%                                              
       Mn        0.3% to 1.0%                                             
       Si        0.2% to 0.75%                                            
       Co        2.0% max.                                                
       Fe        3.0% max.                                                
       W         1.0% max.                                                
       P         0.02% max.                                               
       S         0.015% max.                                              
       Al        0.1% to 0.5%                                             
       Ni        Balance                                                  
 
    
     said alloy having an Nv number between 2.23 and 2.31. All compositions herein are in weight percent unless otherwise stated. 
     The specific composition which we prefer is: 
     
         Mo            14.0%                                                       
Cr            15.5%                                                       
C             LAP (lowest amt. possible)                                  
B             0.01%                                                       
Mn            0.5%                                                        
Si            0.4%                                                        
Co            LAP                                                         
Fe            LAP                                                         
W             LAP                                                         
P             LAP                                                         
S             LAP                                                         
Al            0.25%                                                       
Ni            Balance                                                     
 
    
     said alloy having an Nv number as close to 2.28 as possible but within the range 2.23 and 2.31. 
    
    
     The unique properties of this casting alloy and of castings produced therefrom can best be recognized by the following examples. 
     EXAMPLE I 
     Pin molds were poured under vacuum using a 20-pound remelt charge from a master heat. The chemical analyses of the castings are reported in Table I. Each mold produced 10, 1/2-inch diameter pins approximately 4 inches long from which tensile test bars were machined for testing. Samples from each casting were submitted for (1) metallographic examination, (2) tensile testing at room temperature (RT) and 1400°F., and (3) stress rupture testing at 1400°F. under a load of 25,000 psi. In addition, two samples from each casting were tensile tested at room temperature after aging for 1000 hours at 1600°F. Appropriate specimens were also machined from the bottom casting date and submitted for oxidation testing as follows: 
     Static Oxidation: Exposed to dry flowing air (7 cfh) at 1600°F. for 500 hours. 
     Dynamic Oxidation: Exposed to high velocity combustion gases (No. 2 fuel oil) at 1600°F. for 300 hours. Specimens were cycled out of the hot zone every 30 minutes. 
     
                       TABLE I                                                     
______________________________________                                    
CHEMICAL ANALYSIS OF                                                      
ALLOY OF EXAMPLE I                                                        
Element         Weight Percent                                            
______________________________________                                    
Ni              69.07                                                     
Cr              15.55                                                     
Mo              14.14                                                     
Al              .17                                                       
B               .014                                                      
Co              .01                                                       
Cu              .01                                                       
Fe              .10                                                       
Mg              .01                                                       
Mn              .43                                                       
P               .005                                                      
S               .01                                                       
Si              .33                                                       
Ti              .01                                                       
W               .10                                                       
C               .003                                                      
Nv = 2.28                                                                 
______________________________________                                    
 
    
     The metallographic appearance of the cast pins revealed no undesirable structures. 
     Table II summarizes the mechanical properties of the alloy of Example I. 
     
                       TABLE II                                                    
______________________________________                                    
SUMMARY OF MECHANICAL PROPERTIES                                          
DATA REPORTED IS AN AVERAGE OF TWO TESTS                                  
Property                                                                  
______________________________________                                    
RT Yield             36 ksi                                               
RT Ultimate          82 ksi                                               
RT %E                62%                                                  
RT %RA               51%                                                  
RT* Yield            35 ksi                                               
RT* Ultimate         76 ksi                                               
RT* %E               42%                                                  
RT* %RA              33%                                                  
1400°F Yield  20 ksi                                               
1400°F Ultimate                                                    
                     40 ksi                                               
1400°F %E     33%                                                  
1400°F %RA    37%                                                  
1400°F/25 ksi                                                      
stress rupture                                                            
life                 34 hours                                             
______________________________________                                    
 *After aging at 1600° F for 1000 hours.                           
 
    
     Table III summarizes the environmental resistance of the castings. 
     
                       TABLE III                                                   
______________________________________                                    
OXIDATION RESISTANCE OF                                                   
NICKEL BASE ALLOY CASTINGS                                                
(DATA REPRESENT AVERAGE OF TWO TESTS)                                     
         Test                                                             
Type     Temp.     Time                                                   
Test     °F.                                                       
                   Hrs.      Value                                        
______________________________________                                    
Static   1600      500       M.sub.L.sup. (1)                             
                                      .08                                 
Dynamic  1600      300       M.sub.L.sup.(2)                              
                                      2.15                                
______________________________________                                    
 NOTES:                                                                   
 .sup.(1) M.sub.L is the metal loss in mils per side as determined by     
 weight change after descaling.                                           
 .sup.(2) M.sub.L is the metal loss in mils per surface (determined by    
 change in diameter of the specimen).                                     
 
    
     EXAMPLE II 
     The alloy of this invention was compared for elongation against two well-known commercially available, high performance nickel base cast alloys, Hastelloy* alloy B and Hastelloy* alloy C. The compositions of the alloys are set out in Table IV. 
    
     
                       TABLE IV                                                    
______________________________________                                    
COMPOSITION OF CAST NICKEL BASE ALLOYS,                                   
wt/%                                                                      
Hastealloy     Hastelloy   Alloy of                                       
Alloy B        Alloy C     Invention                                      
______________________________________                                    
Ni     Bal.        Bal.        Bal.                                       
Mo     28.0        17.0        14.5                                       
Cr      0.8        16.5        15                                         
Al     --          --          0.23                                       
B      --          --          0.017                                      
C      0.1         0.1         Less than 0.002                            
Co     2.0         2.0         0.08                                       
Cu     --          --          Less than 0.01                             
Fe     5.0         6.0         0.09                                       
Mg     --          --          Less than 0.01                             
Mn     0.5         0.5         0.56                                       
Si     0.5         0.5         0.34                                       
V      0.2         0.2         --                                         
P      0.015       0.015       Less than 0.005                            
S      0.015       0.015       Less than 0.006                            
W      --          4           --                                         
______________________________________                                    
 
    
     Cast pins of the alloy invention specified in Example II were made by vacuum melting and pouring techniques. These pins were subjected to isothermal aging for various lengths of time and then machined into tensile test bars. 
     The mechanical properties are compared in Table V. 
     
                       TABLE V                                                     
______________________________________                                    
ELONGATION, %                                                             
               Hastelloy Hastelloy Alloy of                               
       Tensile at                                                         
               Alloy B   Alloy C   Invention                              
______________________________________                                    
As Cast   R.T.     6         11      62                                   
Aged 1475°F                                                        
         R.T.      5         0       26                                   
for 100 hrs.                                                              
         1500°F                                                    
                   10        22      37                                   
Aged 1475°F                                                        
         R.T.      3         2       21                                   
for 1000 hrs.                                                             
         1500°F                                                    
                   4         6       17                                   
Aged 1600°F                                                        
         R.T.      --        2       30                                   
for 16 hrs.                                                               
______________________________________                                    
 
    
     The foregoing data show the unusually high values of elongation in the as cast condition and after aging which characterize the alloy of this invention. 
     In the foregoing specification we have set out certain preferred embodiments of this invention, however, it will be understood that this invention may be otherwise embodied within the scope of the following claims.