Addition agent for adding vanadium to iron base alloys
This application is a continuation-in-part of my earlier filed co-pending application Ser. No. 249,503 filed Mar. 31, 1981, now U.S. Pat. No. 4,396,425, issued on Aug. 2, 1983. 
    
    
     The present invention is related to the addition of vanadium to molten iron-base alloys, e.g., steel. More particularly, the present invention is directed to an addition agent comprising V 2  O 3  and a calcium-bearing reducing agent. 
     It is a common requirement in the manufacture of iron base alloys, e.g., steel, to make additions of vanadium to the molten alloy. 
     Previous commercial techniques have involved the use of ferrovanadium alloys and vanadium and carbon, and vanadium, carbon and nitrogen containing materials as disclosed in U.S. Pat. No. 3,040,814. 
     Such materials, while highly effective in many respects, require processing techniques that result in aluminium, carbon and nitrogen containing additions and consequently, cannot be satisfactorily employed in all applications, e.g., the manufacture of pipe steels and quality forging grades of steel. 
     Pelletized mixtures of V 2  O 5  plus aluminum; V 2  O 5  plus silicon plus calcium-silicon alloy; V 2  O 5  plus aluminium plus calcium-silicon, and &#34;red-cake&#34; plus 21%, 34% or 50% calcium-silicon alloy have been previously examined as a source of vanadium in steel by placing such materials on the surface of molten steel. The &#34;red-cake&#34; used was a hydrated sodium vanadate containing 85% V 2  O 5 , 9% Na 2  O and 2.5% H 2  O. The results were inconclusive, probably due to oxidation and surface slag interference. 
     It is therefore an object of the present invention to provide a vanadium addition for iron base alloys, especially a vanadium addition that does not require energy in preparation and which enables, if desired, the efficient addition of the vanadium metal constitutent without adding carbon or nitrogen. 
     Another object of the present invention is to provide such a vanadium addition which, due to its low density, is amenable to pneumatic injection into a molten iron base alloy with a carrier gas and which makes possible high recoveries and absolute control of processing conditions. 
    
    
     Other objects will be apparent from the following descriptions and claims taken in conjunction with the drawing wherein 
     FIG. 1 is a graph showing the effect of particle sizing on vanadium recovery and 
     FIG. 2 (a)-(c), show electron probe analysis of steel treated in accordance with the present invention. 
    
    
     The vanadium addition agent of the present invention is a blended, agglomerated mixture consisting essentially of V 2  O 3  (at least 95% by weight V 2  O 3 ) and a calcium-bearing reducing agent. The mixture contains about 55 to 65% by weight of V 2  O 3  and 35% to 45% by weight of calcium-bearing reducing agent. In a preferred embodiment of the present invention, the reducing agent is a calcium-silicon alloy, about 28-32% by weight Ca and 60-65% by weight Si, containing primarily the phases CaSi 2  and Si; the alloy may advantageously contain up to about 8% by weight iron, aluminum, barium, and other impurities incidental to the manufacturing process, i.e., the manufacture of calcium-silicon alloy by the electric furnace reduction of CaO and SiO 2  with carbon. (Typical analysis: Ca 28-32%, Si 60-65%, Fe 5.0%, Al 1.25%, Ba 1.0%, and small amounts of impurity elements.) 
     In the practice of the present invention a blended, agglomerated mixture of V 2  O 3  and calcium-silicon alloy is prepared in substantially the following proportions: 50% to 70%, preferably 55% to 65% by weight V 2  O 3  and 30% to 50%, preferably 35% to 45% by weight calcium-silicon alloy. The particle size of the calcium-silicon alloy is predominantly (more than 90%) 8 mesh and finer (8M×D) and the V 2  O 3  is sized predominantly (more than 90%) 100 mesh and finer (100M×D). 
     The mixture is thoroughly blended and thereafter agglomerated, e.g., by conventional compacting techniques so that the particles of the V 2  O 3  and reducing agent such as calcium-silicon alloy particles are closely associated in intimate contact. The closely associated agglomerated mixture is added to molten steel where the heat of the metal bath and the reducing power of the reducing agent are sufficient to activate the reduction of the V 2  O 3 . The metallic vanadium generated is immediately integrated into the molten metal. 
     It is important that the addition agent of the present invention be rapidly immersed in the molten metal to minimize any reaction with oxygen in the high temperature atmosphere above the molten metal which would oxidize the calcium-bearing reducing agent. Also, contact of the addition agent with any slag or slag-like materials on the surface of the molten metal should be avoided so that the reactivity of the addition is not diminished by coating or reaction with the slag. This may be accomplished by several methods. For example, by plunging the addition agent, encapsulated in a container, into the molten metal or by adding compacted mixture into the pouring stream during the transfer of the molten metal from the furnace to the ladle. In order to ensure rapid immersion of the addition agent into the molten metal, the ladle should be partially filled to a level of about one-quarter to one-third full before starting the addition, and the addition should be completed before the ladle is filled. The CaO and SiO 2  formed when the vanadium oxide is reduced enters the slag except when the steel is aluminum deoxidized. In that case, the CaO generated modifies the Al.sub. 2 O 3  inclusions resulting from the aluminum deoxidation practice. 
     Another method of adding the addition agent to the molten iron-base alloy is to inject the addition agent into the molten alloy with a carrier gas. The carrier gas may be argon or nitrogen, for example. In addition to minimizing reaction with oxygen and avoiding contact with slag or slag-like material, this method offers several advantages, for example, when compared to ferrovanadium addition, the V 2  O 3  -CaSi mixture is about two and one-half times less dense than ferrovanadium. This is shown by the data below. 
     
         ______________________________________                                    
Vanadium Addition                                                         
                 Apparent Density                                         
______________________________________                                    
Briquets, 60% V.sub.2 O.sub.3 +                                           
                 2.50 gm/cc                                               
40% CaSi                                                                  
60% FeV          6.35 gm/cc                                               
80% FeV          6.29 gm/cc                                               
______________________________________                                    
 
    
     Because the vanadium additive is less dense, the flow rate of the carrier gas-additive mixture can be significantly reduced, i.e., the weight of the heavier ferrovanadium is not a limiting factor. Therefore, greater control of the processing conditions is possible. In addition, the particle size of the additive mixture can be readily altered to suit the injection process by forming the mixture to a predetermined particle size during its preparation. This also provides for increased flexibility in the injection process. Typically, after its preparation as described above, the additive mixture should be reduced to a particle size in the range of from about 10 mesh up to about one-half inch. The concentration of the particles in the carrier gas may of course be varied over a wide range depending upon the particular particle size chosen. 
     V 2  O 3  (33% O) is the preferred vanadium oxide source of vanadium because of its low oxygen content. Less calcium-bearing reducing agent is required for the reduction reaction on this account and, also a smaller amount of CaO and SiO 2  is generated upon addition to molten metal. 
     In addition, the melting temperature of the V 2  O 3  (1970° C.) is high and thus, the V 2  O 3  plus calcium-silicon alloy reduction reaction temperature closely approximates the temperature of molten steel (&gt;1500° C.). Chemical and physical properties of V 2  O 3  and V 2  O 5  are tabulated in Table VI. 
     The following example further illustrates the present invention. 
     EXAMPLE 
     Procedure: 
     Armco iron was melted in a magnesia-lined induction furnace with argon flowing through a graphite cover. After the temperature was stabilized at 1600° C.±10° C., the heat was blocked with silicon. Next, except for the vanadium addition, the compositions of the heats were adjusted to the required grade. After stabilizing the temperature at 1600° C.±5° C. for one minute, a pintube sample was taken for analysis and then a vanadium addition was made by plunging a steel foil envelope containing the vanadium addition into the molten steel. The steel temperature was maintained at 1600° C.±5° C. with the power on the furnace for three minutes after addition of the V 2  O 3  plus reducing agent mixture. Next, the power was shut off and after one minute, pintube samples were taken and the steel cast into a 100-pound, 10.2 cm   2  (4 in) 2  ingot. Subsequently, specimens removed from mid-radius the ingot, one-third up from the bottom, were examined microscopically and analyzed chemically. Some were analyzed on the electron microprote. 
     Various mixtures of V 2  O 3  plus reducing agent were added as a source of vanadium in molten steel having different compositions. In Table I, the results are arranged in order of increasing vanadium recoveries for each of the steel compositions. The data in Table II compares the vanadium recoveries for various grades of steel when the vanadium additions were V 2  O 3  plus calcium-silicon alloy (8M×D) mixtures compacted under different conditions representing different pressures, and in Table III, when the particle size of the calcium-silicon alloy was the principal variable. In order to more completely characterize the preferred V 2  O 3  plus calcium-silicon alloy addition mixture, the particle size distribution of the commercial grade calcium-silicon alloy (8M×D) is presented in Table IV. It may be noted that 67% is less than 12 mesh and 45% less than 20 mesh. As shown in FIG. 1, finer particle size fractions of the calcium-silicon alloy are efficient in reducing the V 2  O 3 , however, the 8M×D fraction is not only a more economical but also a less hazardous product to produce than the finer fractions. 
     In some grades of steel, the addition of carbon or carbon and nitrogen is either acceptable or beneficial. Vanadium as well as carbon or carbon plus nitrogen can also be added to these steels by reducing the V 2  O 3  with CaC 2  or CaCN 2  as shown in Table V. 
     As noted above, Table I represents the experimental heats arranged in order of increasing vanadium recoveries for each steel composition. It may be noted that reducing agents such as aluminum and aluminum with various fluxes, will reduce V 2  O 3  in molten steel. However, for all of these mixtures, the vanadium recoveries in the steels were less than 80 percent. 
     As shown in Table I and FIG. 1, optimum vanadium recoveries were recorded when the vanadium source was a closely associated mixture of 60% V 2  O 3  (100M×D) plus 40% calcium-silicon alloy (8M×D). It may also be noted in Table I that the vanadium recoveries are independent of the steel compositions. This is particularly evident in Table II where the vanadium recovery from the 60% V 2  O 3  plus 40% calcium-silicon alloy, 8M×D, mixtures exceeded 80% in aluminum-killed steels (0.08-0.22% C), semi-killed steels (0.18-0.30%), and plain carbon steels (0.10-0.40% C). Moreover, Table II shows that the vanadium recovery gradually improved when the 60% V 2  O 3  plus 40% calcium-silicon alloy (8M×D) was briquetted by a commercial-type process using a binder instead of being packed by hand in the steel foil immersion envelopes. In other words, the close association of the V 2  O 3  plus calcium-silicon alloy mixture that characterizes commercial-type briquetting with a binder improves vanadium recoveries. For example, the heats with the addition methods emphasized by squarelike enclosures in Table II were made as duplicate heats except for the preparation of the addition mixture. In all but one pair of heats, the vanadium recoveries from the commercial-type briquets were superior to tightly packing the mixture in the steel foil envelopes. 
     The data in Table III show the effect of the particle size of the reducing agent, calcium-silicon alloy, in optimizing the vanadium recoveries. Again, the vanadium recoveries were independent of the steel compositions and maximized when the particle size of the calcium-silicon alloy was 8M×D or less as illustrated in the graph of FIG. 1. Although high vanadium recoveries &gt;90%, were measured when the particle size ranges of the calcium-silicon alloy were 150M×D and 100M×D, the potential hazards and costs related to the production of these size ranges limit their commercial applications. For this reason, 8M×D calcium-silicon alloy has optimum properties for the present invention. The particle size distribution of commercial grade 8M×D is shown in Table IV. 
     When small increases in the carbon or carbon-plus-nitrogen contents of the steel are either acceptable or advantageous for the steel maker, CaC 2  and/or CaCN 2  can be employed as the reducing agent instead of the calcium-silicon alloy. It has been found that commercial grade CaC 2  and CaCN 2  are also effective in reducing V 2  O 3  and adding not only vanadium but also carbon or carbon and nitrogen to the molten steel. The results listed in Table V show the vanadium recoveries and increases in carbon and nitrogen contents of the molten steel after the addition of V 2  O 3  plus CaC 2  and V 2  O 3  plus CaCN 2  mixtures. 
     Specimens removed from the ingots were analyzed chemically and also examined optically. Frequently, the inclusions in the polished sections were analyzed on the electron microprobe. During this examination, it was determined that the CaO generated by the reduction reaction modifies the alumina inclusions characteristic of aluminum-deoxidized steels; for example, see the electron probe illustrations of FIG. 2 where the contained calcium and aluminum co-occur in the inclusions. Thus, the addition of the V 2  O 3  plus calcium-bearing reducing agent to molten steel in accordance with present invention is not only a source of vanadium but also the calcium oxide generated modifies the detrimental effects of alumina inclusions in aluminum-deoxidized steels. The degree of modification depends on the relative amounts of the CaO and Al 2  O 3  in the molten steel. 
     In view of the foregoing it can be seen that a closely associated agglomerated mixture of V 2  O 3  and calcium-bearing reducing agent is an effective, energy efficient source of vanadium when immersed in molten steel. 
     The mesh sizes referred herein are United States Screen series. 
     
                                           TABLE I                                 
__________________________________________________________________________
Vanadium Additives for Steel                                              
                                           % V                            
            Source.sup.(1)                                                
                  Reducing Agent.sup.(2)                                  
                                  V        Recovered                      
        Heat                                                              
            %            %  Particle                                      
                                  Addition                                
                                       % V Furnace -                      
Type Steel                                                                
        No. V.sub.2 O.sub.3                                               
                  Identity                                                
                         Wt.                                              
                            Size  Method.sup.(3)                          
                                       Added                              
                                           &#34;3-Min.&#34;                       
                                                 % C                      
__________________________________________________________________________
Low Carbon:                                                               
0.036-0.5% Al                                                             
        J635                                                              
            65    Al     32 Powder                                        
                                  P    0.25                               
                                            4                             
0.10-0.12% C      +3%   40% Cryolite                                      
0.16-0.31% Si     Flux  +60% CaF.sub.2 (oil)                              
1.50-1.60% Mn                                                             
        J636                                                              
            67    CaF.sub.2 (Flux)                                        
                          3                                               
                  Al     30 Powder                                        
                                  P    0.25                               
                                           10                             
        J639                                                              
            65    Al     35 7-100 M                                       
                                  P    0.25                               
                                           36                             
                            (Granules)                                    
        J637                                                              
            65    Al     35 Shot  P    0.25                               
                                           52                             
        J647                                                              
            60    &#34;Hypercal&#34;                                              
                         40 1/8&#34;  P    0.25                               
                                           64                             
        J645                                                              
            60    CaSi   40 1/4&#34;  P    0.25                               
                                           72                             
        J676                                                              
            60    CaSi   40 1/2&#34;  P    0.25                               
                                           76                             
        J644                                                              
            60    CaSi   40 1/8&#34;  P    0.25                               
                                           80                             
        J641                                                              
            60    CaSi   40 1/8&#34;  P    0.25                               
                                           80                             
        J619                                                              
            65    CaSi   35 8 M × D                                 
                                  P    0.13                               
                                           80                             
        J615                                                              
            50    CaSi   50 8 M × D                                 
                                  P    0.13                               
                                           85                             
        J614                                                              
            55    CaSi   45 8 M × D                                 
                                  P    0.13                               
                                           87                             
        J620                                                              
            60    CaSi   40 8 M × D                                 
                                  P    0.13                               
                                           88                             
        J798                                                              
            60    CaSi   40 150 M × D                               
                                  B    0.25                               
                                           92                             
        J800                                                              
            60    CaSi   40 8 M × D                                 
                                  BC   0.25                               
                                           92                             
        J799                                                              
            60    CaSi   40 100 M × D                               
                                  B    0.25                               
                                           96                             
Carbon Steels:                                                            
        J654                                                              
            60    CaSi   40 1/8&#34;  P    0.20                               
                                           75                             
0.03-0.07% Al                                                             
        J672                                                              
            65    CaC.sub.2                                               
                         35 1/4&#34; × 1/12&#34;                            
                                  P    0.20                               
                                           76                             
0.23-0.29% C                                                              
        J671                                                              
            55    CaC.sub.2                                               
                         45 1/4&#34; × 1/12&#34;                            
                                  P    0.20                               
                                           77                             
0.27-0.33% Si                                                             
        J669                                                              
            65    CaSi   35 8 M × D                                 
                                  P    0.20                               
                                           79                             
1.35-1.60% Mn                                                             
        J670                                                              
            70    CaSi   30 8 M × D                                 
                                  P    0.20                               
                                           81                             
        J657                                                              
            60    Ca.sub.2                                                
                         40 1/12&#34; × 1/4&#34;                            
                                  P    0.20                               
                                           83                             
        J656                                                              
            60    CaSi   40 8 M × D                                 
                                  P    0.20                               
                                           87                             
        J655                                                              
            60    CaSi   40 8 M × D                                 
                                  P    0.20                               
                                           90                             
Carbon Steels:                                                            
         J678*                                                            
            60    CaCN.sub.2                                              
                         40 &lt;325 M                                        
                                  P    0.20                               
                                           50                             
0.04-0.07% Al                                                             
         J677*                                                            
            65    CaCN.sub.2                                              
                         35 &lt;325 M                                        
                                  P    0.20                               
                                           55                             
0.15-0.20% C                                                              
         J679*                                                            
            55    CaCN.sub.2                                              
                         45 &lt;325 M                                        
                                  P    0.20                               
                                           60                             
0.22-0.28% Si                                                             
         J680*                                                            
            50    CaCN.sub.2                                              
                         50 &lt;325 M                                        
                                  P    0.20                               
                                           60                             
1.40-1.50% Mn                                                             
        J674                                                              
            65    CaSi   35 8 M × D                                 
                                  B    0.20                               
                                           80                             
        J675                                                              
            60    CaC.sub.2                                               
                         40 16 M × D                                
                                  P    0.20                               
                                           85                             
        J676                                                              
            65    CaC.sub.2                                               
                         35 16 M × D                                
                                  P    0.20                               
                                           85                             
        J673                                                              
            60    CaSi   40 8 M × D                                 
                                  B    0.20                               
                                           85                             
Carbon Steels:                                                            
        J634                                                              
            60    CaSi   40 8 M × D                                 
                                  P    0.25                               
                                            68** 0.08                     
0.03-0.07% Al                                                             
        J699                                                              
            60    CaSi   40 8 M × D                                 
                                  Loose                                   
                                       0.20                               
                                           81    0.17                     
0.27-0.33% Si                                                             
        J673                                                              
            60    CaSi   40 8 M × D                                 
                                  B    0.20                               
                                           85    0.13                     
1.35-1.60% Mn                                                             
        J714                                                              
            60    CaSi   40 8 M × D                                 
                                  P    0.20                               
                                           86    0.16                     
        J734                                                              
            60    CaSi   40 8 M × D                                 
                                  BC   0.19                               
                                           89    0.08                     
        J747                                                              
            60    CaSi   40 8 M × D                                 
                                  BC   0.21                               
                                           90    0.10                     
Semi-Killed:                                                              
        J709                                                              
            60    CaSi   40 8 M × D                                 
                                  P     0.149                             
                                           75    0.30                     
0.07-0.12% Si                                                             
        J708                                                              
            60    CaSi   40 8 M × D                                 
                                  P    0.15                               
                                           75    0.21                     
0.62-0.71% Mn                                                             
        J707                                                              
            60    CaSi   40 8 M × D                                 
                                  P    0.16                               
                                           79    0.16                     
        J702                                                              
            60    CaSi   40 8 M × D                                 
                                  BC   0.15                               
                                           89    0.38                     
        J735                                                              
            60    CaSi   40 70 M × D                                
                                  BC   0.20                               
                                           90    0.08                     
        J700                                                              
            60    CaSi   40 8 M × D                                 
                                  BC   0.16                               
                                           93    0.10                     
        J701                                                              
            60    CaSi   40 8 M × D                                 
                                  BC   0.16                               
                                           93    0.25                     
Plain Carbon:                                                             
        J710                                                              
            60    CaSi   40 8 M × D                                 
                                  P    0.15                               
                                           75    0.10                     
0.19-0.29% Si                                                             
        J711                                                              
            60    CaSi   40 8 M × D                                 
                                  P    0.17                               
                                           85    0.20                     
0.54-0.85% Mn                                                             
        J713                                                              
            60    CaSi   40 8 M × D                                 
                                  BC   0.17                               
                                           86    0.38                     
        J706                                                              
            60    CaSi   40 8 M × D                                 
                                  BC   0.15                               
                                           88    0.40                     
        J705                                                              
            60    CaSi   40 8 M × D                                 
                                  BC   0.15                               
                                           88    0.31                     
        J703                                                              
            60    CaSi   40 8 M × D                                 
                                  BC   0.15                               
                                           90    0.11                     
        J712                                                              
            60    CaSi   40 8 M × D                                 
                                  P    0.18                               
                                           92    0.29                     
        J704                                                              
            60    CaSi   40 8 M × D                                 
                                  BC   0.16                               
                                           92    0.18                     
__________________________________________________________________________
 .sup.(1) Vanadium Source: V.sub.2 O.sub.3  &gt;99% pure, 100 M × D    
 (commercial product, UCC).                                               
 .sup.(2) Reducing Agents:                                                
 CaSi Alloy  29.5% Ca, 62.5% Si, 4.5% Fe, trace amounts of Mn, Ba, Al, C, 
 etc. (commercial product UCC).                                           
 CaN.sub.2  &gt;99% pure, 325 M × D (chemical reagent).                
 CaC.sub.2  Foundry grade, 66.5% CaC.sub.2 (commercial product UCC)  (1/4&#34;
 × 1/12 &#34; particle size).                                           
 Al Powder  Alcoa Grade No. 121978.                                       
 &#34;Hypercal&#34; 10.5% Ca, 39% Si, 10.3% Ba, 20% Al, 18% Fe.                   
 ##STR1##                                                                 
 *About 10 pounds of metal thrown from the furnace when the V.sub.2 O.sub.
 + CaCN.sub.2 was plunged.                                                
 **Presumed erratic result                                                
 
    
     
                                           TABLE II                                
__________________________________________________________________________
Effect of Packing Density and Steel Compositions on Vanadium Recoveries   
Vanadium Source: 60% V.sub.2 O.sub.3 + 40% CaSi (8 M × D)           
              Composition of Furnace                                      
% Y      Addition                                                         
              &#34;3 Minute&#34; Pintube (Steel)                                  
                                  % V                                     
Heat No.                                                                  
     Added                                                                
         Method*                                                          
              % C % Si                                                    
                      % Al                                                
                          % Mn                                            
                              % V Recovery                                
__________________________________________________________________________
 **J634J620J673J714                                                       
      0.250.130.200.20                                                    
          PPBP                                                            
               0.0770.0850.1300.16                                        
                   0.240.300.230.275                                      
                       0.0570.0590.0740.061                               
                           1.491.511.511.514                              
                               0.160.1140.170.172                         
                                   68888586                               
                                         ##STR2##                         
                                           Al-KilledincreasingC content   
  J699J655J656                                                            
      0.200.200.20                                                        
          No PPP                                                          
               0.170.210.22                                               
                   0.2840.290.32                                          
                       0.0630.0550.05                                     
                           1.6091.641.69                                  
                               0.1610.1800.17                             
                                   819087                                 
                                         ##STR3##                         
  JZ734J747                                                               
      0.1860.2052                                                         
          BCBC                                                            
                0.080.10                                                  
                   0.160.39                                               
                       ##STR4##                                           
                           0.500.82                                       
                               0.1650.19                                  
                                   8993                                   
                                         ##STR5##                         
                                           Semi-KilledincreasingC         
                                          content                         
  J700J707                                                                
      0.1720.20                                                           
          ##STR6##                                                        
               0.180.16                                                   
                   0.0690.107                                             
                       ##STR7##                                           
                           0.6570.704                                     
                               0.160.158                                  
                                   ##STR8##                               
                                         ##STR9##                         
  J701J708                                                                
      0.1720.20                                                           
          ##STR10##                                                       
               0.250.21                                                   
                   0.0690.106                                             
                       ##STR11##                                          
                           0.640.704                                      
                               0.160.15                                   
                                   ##STR12##                              
                                         ##STR13##                        
  J702J709                                                                
      0.1720.20                                                           
          ##STR14##                                                       
               0.380.30                                                   
                   0.0670.121                                             
                       No AlAdded                                         
                           0.7080.626                                     
                               0.1530.149                                 
                                   ##STR15##                              
                                         ##STR16##                        
  J703J710                                                                
      0.1720.20                                                           
          ##STR17##                                                       
               0.110.10                                                   
                   0.210.245                                              
                       ##STR18##                                          
                           0.5430.573                                     
                               0.1540.15                                  
                                   ##STR19##                              
                                         ##STR20##                        
                                           Plain Cincreasing              
  J704J711                                                                
      0.1720.20                                                           
          ##STR21##                                                       
               0.180.20                                                   
                   0.1950.287                                             
                       ##STR22##                                          
                           0.5430.616                                     
                               0.1590.17                                  
                                   ##STR23##                              
                                         ##STR24##                        
  J705J712                                                                
      0.1720.20                                                           
          ##STR25##                                                       
               0.310.29                                                   
                   0.2330.253                                             
                       ##STR26##                                          
                           0.8730.861                                     
                               0.1520.183                                 
                                   ##STR27##                              
                                         ##STR28##                        
                                          Plain CincreasingC content      
  J706J713                                                                
      0.1720.20                                                           
          ##STR29##                                                       
               0.400.38                                                   
                   0.2240.252                                             
                       ##STR30##                                          
                           0.8310.845                                     
                               0.1520.172                                 
                                   ##STR31##                              
                                         ##STR32##                        
__________________________________________________________________________
 *The vanadium additions were made by plunging steel foil envelopes       
 containing the 60% V.sub.2 O.sub.3 + 40% calciumsilicon mixtures into    
 molten steel (1660° C. ± 5° C.). The mixtures were place
 in envelopes as [1] tightly packed mix (P); [2 ] not packed (no P); [3]  
 briquets made in a hand press, no binder (B); or [4] commercialtype      
 briquets made on a briquetting machine with a binder (BC).               
 **presumed erratic result                                                
 
    
     
                                           TABLE III                               
__________________________________________________________________________
Influence of Calcium-Silicon Alloy Particle Size on the                   
Recovery of Vanadium from Vanadium Oxide in Steel                         
                       V Source                                           
                              CaSI                                        
                       Heat                                               
                          %     Particle                                  
                                       Addition                           
                                            % V % V                       
                       No.                                                
                          V.sub.2 O.sub.3                                 
                              % Size   Method*                            
                                            Added                         
                                                Recovered                 
__________________________________________________________________________
Low Carbon:                                                               
        0.036-0.05% Al, 0.10-0.12% C,                                     
                       J798                                               
                          60  40                                          
                                150 M × 0                           
                                       B    0.25                          
                                                92                        
        0.16-0.31% Si, 1.50-1.60% Mn                                      
                       J799                                               
                          60  40                                          
                                100 M × 0                           
                                       B    0.25                          
                                                96                        
                       J800                                               
                          60  40                                          
                                8 M × D                             
                                       C    0.25                          
                                                92                        
                       J645                                               
                          60  40                                          
                                1/4&#34;   P    0.25                          
                                                72                        
                       J646                                               
                          60  40                                          
                                1/2&#34;   P    0.25                          
                                                76                        
                       J644                                               
                          60  40                                          
                                1/8&#34;   P    0.25                          
                                                80                        
                       J641                                               
                          60  40                                          
                                1/8&#34;   P    0.25                          
                                                80                        
                       J640                                               
                          60  40                                          
                                8 M × D                             
                                       P    0.13                          
                                                88                        
Carbon Steels:                                                            
        0.04-0.07% Al, 0.23-0.29% C,                                      
                       J654                                               
                          60  40                                          
                                1/8&#34;   P    0.20                          
                                                75                        
        0.27-0.33% Si, 1.35-1.60% Mn                                      
                       J656                                               
                          60  40                                          
                                8 M × D                             
                                       P    0.20                          
                                                87                        
                       J655                                               
                          60  40                                          
                                8 M × D                             
                                            0.20                          
                                                90                        
Semi-Killed:                                                              
        0.19-0.40% Si, J735                                               
                          60  40                                          
                                70 M × D                            
                                       BC    0.195                        
                                                90                        
        0.60-0.80% Mn, 0.08-0.10% C                                       
                       J747                                               
                          60  40                                          
                                70 M × D                            
                                       BC    0.205                        
                                                93                        
__________________________________________________________________________
 ##STR33##                                                                
 
    
     
                       TABLE IV                                                    
______________________________________                                    
Particle Size Distribution of                                             
Calcium-Silicon Alloy (8 Mesh × Down)                               
______________________________________                                    
            6 Mesh - Maximum                                              
             4% on  8 M                                                   
            33% on  12 M                                                  
            55% on  20 M                                                  
            68% on  32 M                                                  
            78% on  48 M                                                  
            85% on  65 M                                                  
            89% on 100 M                                                  
            93% on 150 M                                                  
            95% on 200 M                                                  
______________________________________                                    
 Products of Union Carbide Corporation, Metals Division                   
 
    
     
                                           TABLE V                                 
__________________________________________________________________________
Vanadium Additives for Steel Containing Carbons or Carbon Plus Nitrogen   
                Reducing Agent.sup.(2)                                    
                             V        % V       N                         
        Heat                                                              
            %          Particle                                           
                             Addition                                     
                                  % V Recovered                           
                                            % C (ppm)                     
Carbon Steel:                                                             
        No. V.sub.2 O.sub.3.sup.(1)                                       
                Identity                                                  
                     % Size  Method.sup.(3)                               
                                  Added                                   
                                      Furnace                             
                                            Inc..sup.(4)                  
                                                Inc..sup.(4)              
__________________________________________________________________________
0.03-0.7% Al                                                              
        J672                                                              
            65  CaC.sub.2                                                 
                     35                                                   
                       1/4&#34; × 1/2&#34;                                  
                             P    0.20                                    
                                      76    0.02                          
0.23-0.29% C                                                              
        J671                                                              
            55  CaC.sub.2                                                 
                     45                                                   
                       1/4&#34; × 1/2&#34;                                  
                             P    0.20                                    
                                      77    0.03                          
0.27-0.33% Si                                                             
        J657                                                              
            60  CaC.sub.2                                                 
                     40                                                   
                       1/2&#34; × 1/4&#34;                                  
                             P    0.20                                    
                                      83    0.03                          
1.35-1.60% Mn                                                             
0.04-0.07% Al                                                             
         J678*                                                            
            60  CaCn.sub.2                                                
                     40                                                   
                       &lt;200 M                                             
                             P    0.20                                    
                                      50    0.02                          
                                                120                       
0.15-0.20% C                                                              
         J677*                                                            
            65  CaCn.sub.2                                                
                     35                                                   
                       &lt;200 M                                             
                             P    0.20                                    
                                      55    0.01                          
                                                102                       
0.22-0.28% Si                                                             
         J679*                                                            
            55  CaCn.sub.2                                                
                     45                                                   
                       &lt;200 M                                             
                             P    0.20                                    
                                      60    0.03                          
                                                194                       
1.40-1.50% Mn                                                             
         J680*                                                            
            50  CaCN.sub.2                                                
                     50                                                   
                       &lt;200 M                                             
                             P    0.20                                    
                                      60    0.03                          
                                                225                       
        J675                                                              
            60  CaC.sub.2                                                 
                     40                                                   
                       16 M × D                                     
                             P    0.20                                    
                                      85    0.04                          
        J676                                                              
            65  CaC.sub.2                                                 
                     35                                                   
                       16 M × D                                     
                             P    0.20                                    
                                      85    0.04                          
__________________________________________________________________________
 .sup.(1) V.sub.2 O.sub.3 : 99% pure, 100 M × D (commercial product,
 UCC).                                                                    
 .sup.(2) CaC.sub.2 : 80% CaC.sub.2, 14% CaO, 2.9% SiO.sub.2, 1.6% Al.sub.
 O.sub.3 (commercial product, UCC). CaCn.sub.2 : 50% Ca, 15% C, 35% N     
 (chemically pure).                                                       
 .sup.(3) Mixture tightly packed in steel foil envelope and plunged into  
 molten steel  1600° C. ± 5° C.                          
 .sup.(4) Increase in % C and ppm N in molten steel due to addition of    
 vanadium plus CaC.sub.2 or CaCN.sub.2 mixture (&#34;3minute&#34; pintube samples)
 *About 10 pounds of metal thrown out of furnace due to violence of the   
 reaction.                                                                
 
    
     
                       TABLE VI                                                    
______________________________________                                    
Comparison of Properties of V.sub.2 O.sub.5                               
                                     Ref-                                 
Property V.sub.2 O.sub.3                                                  
                       V.sub.2 O.sub.5                                    
                                     erence                               
______________________________________                                    
Density  4.87          3.36          1                                    
Melting Point                                                             
         1970° C.                                                  
                       690° C.                                     
                                     1                                    
Color    Black         Yellow        1                                    
Character of                                                              
         Basic         Amphoteric    2                                    
Oxide                                                                     
Composition                                                               
         68% V + 32% O 56% V + 44% O (Calc.)                              
Free Energy                                                               
         -184,500 cal/mole                                                
                       -202,000 cal/mole                                  
                                     3                                    
of Formation                                                              
(1900° K.)                                                         
Crystal  a.sub.o = 5.45 ± 3 A                                          
                       a.sub.o = 4.359 ± 5 A                           
                                     4                                    
Structure                                                                 
          α = 54°49&#39; ± 8&#39;                                 
                       b.sub.0 = 11.510 ± 8 A                          
         Rhombohedral  c.sub.o = 3.563 ± 3 A                           
                       Orthohrombic                                       
______________________________________