Abstract:
An austenitic alloy has high strength and corrosion resistance and includes from 27 to 32 weight percent nickel and 24 to 28 weight percent chromium. Up to 2.75 weight percent silicon, 3 weight percent copper and molybdenum and 2 weight percent manganese are included for contributing to the characteristics to the alloy rendering the alloy particularly useful for fabricating oil well tubular products. Only very low components of nitrogen, carbon, phosphorus and sulfur are included.

Description:
FIELD AND BACKGROUND OF THE INVENTION 
     The present invention relates, in general, to high strength corrosion resistant alloys, and, in particular, to a new and useful austenitic alloy containing critical amounts of nickel, chromium, silicon, copper, molybdenum and manganese, with iron and incidental impurities. 
     The need for a high strength and corrosion resistant alloy that will retain its integrity in the hostile environment of deep oil sour wells, has become apparent with the decrease of easily obtained sweet oil reserves. Since sour wells can contain significant amounts of hydrogen sulfide, carbon dioxide, and chloride solutions at high temperatures and pressures, alloys with better resistance to failure under stress and corrosive conditions would be desirable. 
     To minimize corrosion, various high alloy stainless steels and nickel alloys are now being used for other applications. Some disadvantages with most of these alloys have been, however, the relatively high cost because of the increased alloying content, relatively complicated manufacturing, and the fact that these alloys are still subject to stress corrosion cracking. Many metalurgical factors influence the mechanical and corrosion behavior of these alloys. These factors include microstructure, composition, and strength. All of these factors are interrelated and must be closely controlled or optimized with respect to sour well applications. 
     U.S. Pat. Nos. 4,400,209; 4,400,210; 4,400,211; 4,400,349; and 4,421,571, all to Kudo et al, disclose high strength alloys which are particularly useful for deep well casing, tubing and drill pipes, and which utilize compositions including nickel, chromium, manganese and molybdenum. These patents also rely on tungsten additions that satisfies a specific relationship with the presence of chromium and molybdenum to make up a significant proportion of the alloy as a whole. 
     U.S. Pat. No. 4,489,040 to Asphahani et al, also discloses a corrosion resistant alloy including nickel and chromium plus tungsten. 
     Titanium is also utilized as an additive for corrosion resistant nickel-chromium alloys as disclosed in U.S. Pat. Nos. 4,409,025 and 4,419,129 to Sugitani et al, and U.S. Pat. No. 4,385,933 to Ehrlich et al. 
     Niobium is an additive for corrosion resistant alloys as disclosed by U.S. Pat. No. 4,505,232 to Usami et al, U.S. Pat. No. 4,487,744 to DeBold et al, and U.S. Pat. No. 4,444,589 to Sugitani et al. 
     An oxidation resistant austenitic steel advocating relatively low chromium and nickel contents is disclosed by U.S. Pat. No. 4,530,720 to Moroishi et al. 
     Lanthanum can be an additive for austenitic stainless steel as disclosed by U.S. Pat. No. 4,421,557 to Rossomme et al. 
     As evidenced by several of the foregoing reference which include relatively high chromium contents, the presence of nitrogen is desireable. Nitrogen additions is used in some alloys to replace chromium for maintaining a stable austenitic structure. Chromium normally exists in the ferritic form. 
     SUMMARY OF THE INVENTION 
     It is a principle object of the present invention to provide a fully austenitic alloy having a combination of chemical elements whose synergistic effect gives it a highly desireable combination of mechanical and corrosion resistant properties. Since the alloy of the present invention is intended primarily for use in oil tubular products, cost is an important consideration. Accordingly, another object of the present invention is to provide an alloy that achieves a good combination of high strength, ductility, corrosion resistance under stress and metallurgical stability, while being cost effective. 
     The invention provides an alloy that is easily fabricated either hot or cold. The high strength alloy has excellent resistance to stress corrosion cracking under test conditions equivalent to or more severe than conditions than the alloy would experience in use. The alloy also has improved pitting and galling resistance. For cost effectiveness, the most expensive elements, especially nickel, are reduced to relatively low levels, without however sacrificing the desirable characteristics of the alloy. 
     According to the invention thus, an austenitic alloy having high strength and corrosion resistance under stress, in particular for oil well tubular products, consists essentially of, in weight percent; 27-32 Ni; 24-28 Cr; 1.25-3.0 Cu; 1.0-3.0 Mo; 1.5-2.75 Si; 1.0-2.0 Mn; with no more than 0.015 N, 0.10 each of B, V and C, 0.30 A1, 0.03 P and 0.02 S; the balance being Fe and incidental impurities. 
     The alloy is substantially free of tungsten, titanium, niobium and lanthanum and uses substantially less nitrogen than is conventional in the prior art. 
     Comparative screening tests were conducted on 46 different alloys in discovering the foregoing critical combination of components. Among the alloys tested was a commercial alloy identified as Alloy 825 which contains 38 to 46 weight percent nickel, rendering the alloy of the present invention about 17% cheaper to manufacture. The alloy of the present invention performed substantially as well as, and in some instances, better than alloy 825. 
     Other alloys tested were inadequate in other various ways. If the content of manganese, for example was too low or too high, forging of the alloy became very difficult. This was particularly true when the alloys were made by electroslag remelting (ESR). 
    
    
     DESCRIPTION OF THE PREFERRED EMBODIMENT 
     The alloy of the present invention which was derived by computer design and was one of many alloys tested, reached the objectives cited above for a high strength corrosion resistant alloy. 
     Table 1 shows the composition, in weight percent, of a laboratory sample of the invention as well as preferred and allowable ranges for each of the components of the alloy. 
     
                       TABLE 1______________________________________COMPOSITION IN WEIGHT PERCENT              Preferred  Laboratory Sample              Range    Allowable Range______________________________________C        0.01          .01-.03  .10 Max.Mn       1.42          1.25-1.75                           1.0-2.0Si       2.20          1.75-2.25                            1.5-2.75P        0.009         .02 Max. .03 Max.S        0.004         .009 Max.                           .02 Max.Cr       25.3          25.5-26.5                           24-28Ni       30.3          29.5-30.5                           27-32Mo       1.53          1.4-1.6  1.0-3.0Cu       1.88          1.75-2.25                           1.25-3.0Al       0.17          .05 Max. .30 Max.B (less than)    0.001         --       .10 Max.V        0.014         --       .10 Max.N        0.0053        .006 Max.                           .015 Max.O ppm    53            --       --______________________________________ 
    
     Since the alloy of the present invention is austenitic, and even though carbon and nitrogen are powerful austenite stabilizers, neither carbon nor nitrogen is essential in the composition. Nickel insures the austenitic balance of the alloy and its desired properties, particularly hot workability and corrosion resistance. Higher nickel adds to the cost of the alloy without correspondingly contributing to its usefulness. The added cost is thereby unwarranted. Advantageously, no more than 30.5 weight percent nickel is needed. This is contrasted to Alloy 825 which contains 38 to 40 percent weight nickel. Chromium at about 25.3 weight percent is the primary additive for rendering the alloy corrosion resistant. Higher chromium content risks the precipitation of ferrite and sigma-phase. 
     Phosphorus and sulfur are purposely kept low to avoid the undesireable effects these components have upon corrosion resistance or forgeability. Silicon is provided to enhance resistance to stress corrosion cracking. Copper is believed to contribute to corrosion resistance as well, particularly in acid environments. Like nickel, copper works to stabilize the austenitic balance. Molybdenum is incorporated so as to improve general corrosion and pitting resistance. Manganese, at the levels provided, improves workability at high temperatures and is useful in obtaining a proper structure in the alloy. 
     The following tests were conducted to verify the advantageous properties of the alloy. 
     A 20 lb. ingot was cast from the alloy described in Table 1. The alloy was prepared by vacuum induction melting. After soaking at 2200° F. for 1 hour, the ingot was forged between 1800°-2050° F. into 0.920&#34; diameter bars. The bars were cold swagged down to 43 and 72 percent reductions. The room temperature tensile properties were then measured in the cold worked condition. 
     The results of these measurements are set forth in Table 2. 
     
                       TABLE 2______________________________________               Elonga-  Reduction                                Cold0.2% Y.S.    UTS        tion     of Area Reductionksi  (MPa)   ksi    (MPa) (%)    (%)     (%)______________________________________124.0(854)   133.6   (921)                     21.2   74.6    43140.6(969)   149.3  (1029)                     18.1   71.2    72______________________________________ 
    
     The alloy of the present invention is characterized by a unique combination of resistance to corrosive media. Samples cut from the swagged bars were machined into 0.200&#34; diameter smooth tensile specimens and stress corrosion tested. Test results are given in Table 3. 
     
                       TABLE 3______________________________________    Mate-    rial.sup.(3)           Yield       Test     Time ToTest     Condi- Strength    Stress   FailureEnvironment    tion   ksi    (MPa).sup.(1)                         ksi  (MPa) (hours).sup.(2)______________________________________MgCl.sub.2 Test:Boiling 42%    43%    124.6  (854)  111.7                              (776) 1000 NFMgCl.sub.2    CW(310° F.)Boiling 42%    72%    140.6  (969)  112.5                              (775) 1000 NFMgCl.sub.2    CW(310° F.)Autoclave Test:25% NaCl -    43%10% H.sub.2 S    CW     124.0  (854)  111.7                              (770) 720 NF90% CO.sub.2,1000 psig@ 500° F.______________________________________ .sup.(1) Longitudinal Tests Y.S. is Stress For 0.2% Offset .sup.(2) NF -- No Failure in Hours Shown .sup.(3) CW -- Cold Worked by Swagging. 
    
     Aside from having excellent stress corrosion resistance, this alloy has improved resistance to pitting in chloride environments (5% FeCl 3  -10% NaCl (75° F.) solutions) and significantly improved galling resistance compared to similar tests performed on Alloy 825. 
     The alloy of the present invention is primarily intended for use in high strength tubulars and the like when cold worked. The inventive alloy is significantly better in hot workability, cold formability, resistance to stress corrosion cracking, especially in MgCl 2  solutions, and shows improved pitting and galling resistance compared with other more expensive high alloys, such as Alloy 825. The alloy of the present invention while developed primarily for tubing can also be used in other shapes. 
     Some of the alloys which were prepared for comparison have compositions shown in Table 4. 
     Table 5 shows a summary of a galling test that was conducted on some of the alloys as well as some commercially available alloys. The invention is included for comparison. Table 6 shows tensile properties of some of the alloys, including four tests conducted with the inventive alloy. 
     
                                           TABLE 4__________________________________________________________________________Alloy No. C    Mn   P   S  Si  Cr Wi Mo  Cu Al  Ti B    H   V  O__________________________________________________________________________                                                      ppm1     .012 1.54 .011               .003                  .31 24.69                         30.39                            2.02                                1.82                                   &lt;.05                                       .10                                          &lt;.005                                               .040                                                   .035                                                      --2     .010 1.60 .012               .003                  .34 25.69                         30.33                            2.00                                1.77                                   &lt;.05                                       .11                                          &lt;.005                                               .033                                                   .036                                                      --3     .010 1.76 .008               .003                  .68 26.17                         29.85                            1.08                                1.72                                   &lt;.05                                       .10                                          &lt;.005                                               .049                                                   .036                                                      --4     .010 1.73 .012               .003                  .78 27.85                         30.50                            1.09                                1.81                                   &lt;.05                                       .12                                          &lt;.005                                               .039                                                   .039                                                      --5     .010 1.18 .010               .003                  1.29                      26.60                         31.66                            .36 1.84                                   .027                                       .022                                           .0018                                               .090                                                   -- --6     .029 1.27 .010               .003                  1.72                      26.88                         31.95                            .36 1.75                                   .034                                       .027                                           .0014                                               .090                                                   -- 4307     .014 1.38 .010               .002                  1.99                      28.73                         29.65                            &lt;.05                                1.87                                   .025                                       .021                                          &lt;.001                                               .12 -- --8     .017 1.30 .010               .002                  2.11                      29.34                         31.23                            &lt;.05                                1.89                                   .045                                       .027                                          &lt;.001                                               .11 -- 1209     .010 7.96 .011               .008                  1.30                      29.86                         17.68                            1.93                                1.82                                   &lt;.005                                       -- .005 .58 -- 7310    .010 6.87 .014               .007                  .67 23.39                         16.39                            1.74                                2.31                                   &lt;.006                                       -- .005 .51 -- 40011    .021 5.25 .020               .006                  1.90                      28.26                         20.39                            1.86                                1.73                                   &lt;.01                                       -- .004 .60 -- 7412    .010  .43 .014               .003                  .33 18.38                         45.70                            3.16                                2.07                                   .73 2.50                                          .005 .022                                                   -- 34013    .012  .62 .013               .002                  .42 16.65                         48.00                            5.61                                1.83                                   1.0 2.55                                          .008  .0092                                                   -- 5714    .012  .60 .010               .002                  .38 19.31                         48.00                            3.75                                1.83                                   .81 2.95                                          .008 .010                                                   -- 8915    .013  .40 .011               .003                  .32 17.06                         47.80                            5.61                                1.85                                   .82 2.68                                          .004  .0089                                                   -- 6116    .010 3.69 .005               .004                  .59 13.44                         40.96                            5.94                                4.76                                   1.0 2.65                                          .007 .010                                                   -- 6717    &lt;.01  .55 .013               .003                  .33 25.07                         35.87                            1.15                                1.84                                   .52 1.01                                          .003 .027                                                   -- 80 .010  .77 .012               .001                  .35 27.94                         34.28                            1.00                                1.77                                   .47 1.09                                          .003 .021                                                   -- 6318    .013  .54 .012               .002                  .18 28.68                         36.20                            &lt;.05                                1.85                                   .53 1.05                                          .003 .032                                                   -- 9119    .012  .50 .013               .003                  .22 23.85                         41.00                            1.11                                1.94                                   .75 1.28                                          .001  .024                                                   -- 12020    .021  .47 .012               .002                  .13 27.37                         40.68                            .054                                1.92                                   .67 1.28                                          .002  .027                                                   --  9021    .013 2.59 .011               .002                  .78 24.11                         34.97                            1.83                                1.85                                   .48 091                                          .005  .025                                                   -- --22    .020 1.63 .014               .007                  2.01                      28.44                         29.73                            .56 2.67                                   &lt;.05                                       &lt;.01                                          .004 .66 .037                                                      39023    .019 1.48 .026               .004                  2.49                      28.14                         29.68                            .97 2.76                                   &lt;.01                                       &lt;.01                                          .003 .52 .048                                                      22024    .024 1.51 .019               .005                  2.07                      29.76                         31.34                            1.47                                2.79                                   &lt;.005                                       &lt;.01                                           .0042                                               .27 .042                                                      17025    .047 1.40 .017               .005                  3.01                      30.32                         31.30                            .66 2.89                                   &lt;.05                                       &lt;.05                                          .005 .53 .052                                                      23026    .022 1.47 .028               .003                  3.15                      27.71                         29.39                            .96 2.73                                   &lt;.01                                       &lt;.01                                          .004 .49 .050                                                      17027    .022 1.57 .019               .006                  2.85                      30.17                         31.41                            1.48                                2.82                                   &lt;.005                                       &lt;.01                                           .0034                                               .22 .042                                                      18028    .017 1.04 .017               .005                  3.60                      29.96                         31.40                            .71 2.86                                   &lt;.05                                       &lt;.05                                          .004 .53 .050                                                      28029    .018 1.43 .024               .006                  3.68                      28.16                         30.44                            1.01                                2.82                                   &lt;.01                                       &lt;.01                                          .001 .42 .048                                                      22030    .020 1.55 .020               .007                  3.32                      30.02                         32.12                            1.53                                2.96                                   &lt;.005                                       &lt;.01                                           .0025                                               .25 .043                                                      17031    .023 2.99 .020               .006                  2.95                      30.89                         32.91                            1.06                                2.86                                   &lt;.005                                       &lt;.01                                           .0024                                               .37 .047                                                      17032    .021 4.61 .018               .004                  3.30                      37.96                         30.52                            1.11                                2.94                                   &lt;.005                                       &lt;.01                                          .003 .38 .045                                                      23033 (Alloy 7) .013 1.49 .012               .005                  2.00                      29.37                         29.50                            &lt;.05                                1.75                                   &lt;.05                                       &lt;.05                                          .002 .17 .046                                                      20034 (825) .020  .57 .019               .003                  .23 22.62                         41.45                            2.71                                2.26                                   .066                                       1.23                                          .003  .006                                                   .045                                                       80INVEN- &lt;.01 1.42 .009               .004                  2.20                      25.27                         30.31                            1.53                                1.88                                   .17 -- &lt;.001                                                .0053                                                   .014                                                       53TION__________________________________________________________________________ 
    
     
                                           TABLE 5__________________________________________________________________________Summary of Galling Test Results.sup.1             Threshold  Threshold  Threshold   Yield     Lower                  Maximum                        Lower                             Maximum                                   Lower                                        MaximumAlloy   Strength        Hardness             Galling                  Burnishing                        Galling                             Burnishing                                   Galling                                        BurnishingNumber  ksi(*)        (HR.sub.A)             Load (lbs) Stress (ksi)                                   (% of Y.S.)__________________________________________________________________________1       124.3(T)        63.6 2740 3790  20.6 28.5  16.6 22.92       123.4(T)        63.9 1230 1430   9.2 10.7   7.5  8.73       119.2(T)        63.6 1280 1410   9.6 10.6   8.1  8.94       121.7(T)        63.3 1020 1100   7.7  8.3   6.3  6.85       130.0(T)        64.7 1150 2300  10.1 17.3   7.8 13.36       131.9(T)        65.2 3790 5770  28.5 43.4  21.6 32.97       130.9(T)        65.9 3990 6770  30.0 50.9  22.9 38.98       135.2(T)        65.9 2190 4980  16.5 37.4  12.2 27.711      129.7(T)        68.0 3480 7950  26.2 59.8  20.2 46.111      134.3(L)        68.0 3480 7970  26.2 60.0  19.5 44.612      116.7(T)        68.4 2480 7960  18.7 60.0  16.0 51.312      117.1(L)        68.4 2490 7970  18.7 60.0  16.0 51.215      143.1(T)        70.8 2610 3980  19.6 29.9  13.7 20.915      123.5(L)        70.8 2610 3990  19.6 30.0  15.9 24.317      129.1(T)        66.8 2250 2990  16.9 22.5  13.1 17.4INVENTION   125.0(L)        63.8 2160 4790  16.3 36.0  13.0 28.8Sanicro 28   101.3(T)        65.7 2380 4280  17.9 32.2  17.7 31.8Sanicro 28   127.1(L)        65.7 2380 4280  17.9 32.2  14.1 25.3Alloy 825   115.6(T)        65.5 1200 1590   9.0 12.0   7.6 10.1Alloy 825   135.8(L)        65.5 1200 1590   9.0 12.0   6.5  8.6__________________________________________________________________________ .sup.1 Tests were performed at Hydril Mechanical Products Division, Houston, Texas. Each alloy was run against each other to determine the threshold values. *T  Transverse L  Longitudinal 
    
     
                                           TABLE 6__________________________________________________________________________Tensile Properties and Hardness Data0.2% Yield      Ult. Ten.                      Amount ofAlloyStrength      Strength             Elongation                     Red. of Area                               Hardness                                     Cold Reduction                                             Test   WorkingNo.  (10.sup.3 psi)      (10.sup.3 psi)             (% in 2 inches)                     (%)       (R.sub.A)                                     (%)     Direction                                                    Process__________________________________________________________________________24   177.8 186.8   7.4    42.8      67.3  43.7    Longitudinal                                                    Swagged24   132.8 148.3  24.9    64.2      65.4  27.6    Longitudinal                                                    Swagged24   153.1 156.2  20.6    62.8      66.4  32.7    Longitudinal                                                    Swagged31   177.5 184.1   5.5    27.0      68.2  41.1    Longitudinal                                                    Swagged31   146.1 157.4  16.9    40.9      66.7  24.5    Longitudinal                                                    Swagged33   172.2 176.3   5.0    24.8      67.5  43.7    Longitudinal                                                    Swagged33   158.8 165.2  12.6    59.1      65.5  33.7    Longitudinal                                                    Swagged33   153.2 160.8  14.4    63.7      67.5  40.0    Longitudinal                                                    Swagged33   172.6 176.4  10.8    41.0                    Longitudinal                                                    Swagged33   103.0 129.5  38.4    68.8                    Longitudinal                                                    Swagged32   133.5 144.5  20.0    66.0            32.0    Longitudinal                                                    Swagged34   157.9 164.6  13.8    62.6      65.7  67.2    Longitudinal                                                    Swagged34   150.9 153.4  15.0    63.3                    Longitudinal                                                    Swagged34   137.4 140.2  19.6    69.9                    Longitudinal                                                    SwaggedINVEN-TION140.6 149.3  18.1    71.2      65.2  74.3    Longitudinal                                                    Swagged124.1 133.6  21.2    74.6            40.0    Longitudinal                                                    Swagged125.0 132.5  18.1    65.8      63.8  47.2    Longitudinal                                                    Cold Rolled                                                    Plate133.0 152.0  12.5    47.4      64.8  61.0    Transverse                                                    Cold Rolled                                                    Plate__________________________________________________________________________