Abstract:
A nickel-molybdenum-chromium alloy, capable of withstanding both strong oxidizing and strong reducing acid solutions, contains 20.0 to 23.5 wt. % molybdenum and 13.0 to 16.5 wt. % chromium with the balance being nickel plus impurities and residuals of elements used for control of oxygen and sulfur.

Description:
CROSS REFERENCE TO RELATED APPLICATION 
       [0001]    This application claims the benefit of provisional application Ser. No. 60/836,609, filed Aug. 9, 2006. 
     
     FIELD OF INVENTION 
       [0002]    The invention relates to corrosion-resistant, nickel-based alloys. 
       BACKGROUND OF THE INVENTION 
       [0003]    In the nineteen twenties, it was discovered by Becket (U.S. Pat. No. 1,710,445) that the addition of 15 to 40 wt. % molybdenum to nickel resulted in alloys highly resistant to non-oxidizing acids, notably hydrochloric and sulfuric, two of the most important industrial chemicals. Since the least expensive source of molybdenum was ferro-molybdenum, a significant quantity of iron was included in these alloys. At about the same time, it was also discovered by Franks (U.S. Pat. No. 1,836,317) that nickel alloys containing significant quantities of molybdenum, chromium, and iron, could cope with an even wider range of corrosive chemicals. We now know that this is because chromium encourages the formation of protective (passive) films in so-called oxidizing acids (such as nitric), which induce cathodic reactions of high potential. These inventions led to the introduction of the cast HASTELLOY A, B, and C alloys, and subsequently to the wrought B, C, and C-276 alloys. The need to minimize the carbon and silicon contents of such alloys, to improve their thermal stability (Scheil, U.S. Pat. No. 3,203,792) was factored into the composition of HASTELLOY C-276 alloy. 
         [0004]    With regard to the quantities of molybdenum and chromium that can be added to nickel, these are dependent upon thermal stability. Nickel itself possesses a face-centered cubic structure, at all temperatures below its melting point. Such a structure provides excellent ductility and resistance to stress corrosion cracking. Thus, it is desirable that alloys of nickel designed to resist corrosion also possess this structure, or phase. However, if the combined additions exceed their limit of solubility in nickel, second phases of a less-desirable nature are possible. Metastable or supersaturated nickel alloys are possible if high temperature annealing (to dissolve unwanted second phases), followed by rapid quenching (to lock in the high temperature structure) are employed. The Ni—Mo alloys and most of the Ni—Cr—Mo alloys fall into this category. The main concern with such alloys is their propensity to form second phase precipitates, particularly at microstructural imperfections such a grain boundaries, when reheated to temperatures in excess of about 500° C., where diffusion becomes appreciable. Such elevated temperature excursions are common during welding. The term thermal stability relates to the propensity for second phase precipitation at elevated temperatures. 
         [0005]    In the nineteen fifties, Ni—Mo and Ni—Cr—Mo alloys with low iron contents, covered by G.B. Patent 869,753 (Junker and Scherzer) were introduced, with narrower compositional ranges and stricter controls on carbon and silicon, to ensure corrosion resistance yet minimize thermal instability. The molybdenum range of the nickel-molybdenum (Ni—Mo) alloys was 19 to 32 wt. %, and the molybdenum and chromium ranges of the nickel-chromium-molybdenum (Ni—Cr—Mo) alloys were 10 to 19 wt. % and 10 to 18 wt. %, respectively. These led to the introduction of wrought HASTELLOY B-2 and C-4 alloys in the nineteen seventies. 
         [0006]    Since then, it has been discovered that HASTELLOY B-2 alloy is prone to rapid, deleterious phase transformations during welding. To remedy this, HASTELLOY B-3 alloy, the phase transformations of which are much slower, was introduced in the nineteen nineties after discoveries by Klarstrom (U.S. Pat. No. 6,503,345). With regard to recent developments in the field of Ni—Cr—Mo alloys, these include HASTELLOY C-22 alloy (Asphahani, U.S. Pat. No. 4,533,414), HASTELLOY C-2000 alloy (Crook, U.S. Pat. No. 6,280,540), NICROFER 5923 hMo (Heubner, Köhler, Rockel, and Wallis, U.S. Pat. No. 4,906,437), and INCONEL 686 alloy (Crum, Poole, and Hibner, U.S. Pat. No. 5,019,184). These newer alloys require molybdenum within the approximate range 13 to 18 wt. %, and chromium within the approximate range 19 to 24.5 wt. %. 
         [0007]    With a view to enhancing the corrosion performance of the Ni—Cr—Mo alloys, additions of tantalum (of the so-called reactive element series) have been used. Notably, U.S. Pat. No. 5,529,642 describes an alloy containing from 1.1 to 8 wt. % tantalum. This has been commercialized as MAT-21 alloy. 
         [0008]    Although the Ni—Mo alloys possess outstanding resistance to non-oxidizing acids (i.e. those which induce the evolution of hydrogen at cathodic sites), they are intolerant of additions, residuals, or impurities which result in cathodic reactions of higher potential. One of these so-called “oxidizing species” is oxygen, which is hard to avoid. While the Ni—Cr—Mo alloys can tolerate such species, they do not possess sufficient resistance to the non-oxidizing acids for many applications. Thus there is a need for materials which possess the attributes of both the Ni—Mo and Ni—Cr—Mo alloys. 
         [0009]    Materials with compositions between those of the Ni—Mo and Ni—Cr—Mo alloys do exist. For example, a Ni—Mo—Cr alloy containing approximately 25 wt. % molybdenum and 8 wt. % chromium (242 alloy, U.S. Pat. No. 4,818,486) was developed for use at high temperatures in gas turbines, but has been used to resist aqueous environments involving hydrofluoric acid. Also, B-10 alloy, a nickel-based material containing about 24 wt. % molybdenum, 8 wt. % chromium, and 6 wt. % iron was promoted as being tolerant of oxidizing species in strong non-oxidizing acids. As will be shown, however, the properties of these two Ni—Mo—Cr alloys are generally similar to those of the Ni—Mo alloys, and do not provide the desired versatility. 
       SUMMARY OF THE INVENTION 
       [0010]    The principal object of this invention is to provide wrought alloys which exhibit characteristics of both the Ni—Mo and Ni—Cr—Mo alloys, possess good thermal stability, and are thus extremely versatile. These highly desirable properties have been unexpectedly attained using a nickel base, molybdenum between 20.0 and 23.5 wt. %, and chromium between 13.0 and 16.5 wt. %. To enable the removal of oxygen and sulfur during the melting process, such alloys typically contain small quantities of aluminum and manganese (up to about 0.5 and 1 wt. %, respectively, in the Ni—Cr—Mo alloys), and possibly traces of magnesium and rare earth elements (up to about 0.05 wt. %). 
         [0011]    Iron is the most likely impurity in such alloys, due to contamination from other nickel alloys melted in the same furnaces, and maxima of 2.0 wt. % or 3.0 wt. % are typical of those Ni—Cr—Mo alloys that do not require an iron addition. Thus a maximum of 2.0 wt. % iron is proposed for the alloys of this invention. Other metallic impurities are possible, including, tungsten (up to 0.75 wt. %), cobalt (up to 1.0 wt. %), copper (up to 0.5 wt. %), titanium (up to 0.2 wt. %), niobium (up to 0.5 wt. %), tantalum (up to 0.2 wt. %), and vanadium (up to 0.2 wt. %). 
         [0012]    By use of special melting techniques, in particular argon-oxygen decarburization, it is possible to achieve very low carbon and silicon contents in such alloys, to enhance their thermal stability. However, it is not possible to exclude these elements completely. 
         [0013]    With regard to carbon content, the preferred experimental alloy of the study which led to this discovery contained 0.013 wt. % carbon (because it was not possible to apply the argon-oxygen decarburization process during melting of the experimental alloys). Thus it is evident that at least 0.013 wt. % carbon can be tolerated in the alloys of this invention. This is therefore the proposed maximum for carbon in the alloys of this invention. 
         [0014]    With regard to silicon, a maximum of 0.08 wt. % is typical of the wrought Ni—Cr—Mo alloys; thus a maximum of 0.08 wt. % is proposed for the alloys of this invention. 
     
     
       BRIEF DESCRIPTION OF THE DRAWING 
         [0015]      FIG. 1  is a chart showing the corrosion characteristics of certain prior art alloys and the alloys of this invention. 
       
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 
       [0016]    It is believed that the extreme versatility of the alloys of this invention is best illustrated by  FIG. 1 , a plot of corrosion rates in a strong, oxidizing acid solution versus corrosion rates in a strong, non-oxidizing (reducing) acid solution. B-3, B-10, 242, C-22, C-276, and C-2000 are commercially available, wrought, Ni—Mo, Ni—Mo—Cr, and Ni—Cr—Mo alloys, the compositions of which are given in Table 1. The HYBRID alloy is the preferred composition of this invention. Of these materials, only the HYBRID alloy provides sufficient resistance to both the strong, oxidizing and strong, non-oxidizing acid environments to be useful. Other commercially available, wrought Ni—Cr—Mo alloys (C-4, MAT-21, 59, and 686 alloys) behaved like the C-type alloys shown in  FIG. 1 , but were off-scale (see the test results in Table 4). 
         [0000]    
       
         
               
             
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Nominal Compositions of Alloys in FIG. 1, Weight % 
               
             
          
           
               
                   
                 Alloy 
               
             
          
           
               
                   
                 Ni 
                 Mo 
                 Cr 
                 Fe 
                 W 
                 Cu 
                 Mn 
                 Al 
                 Si 
                 C 
                 Other 
               
               
                   
                   
               
             
          
           
               
                 HYBRID 
                 BAL. 
                 22 
                 15 
                 — 
                 — 
                 — 
                 0.3 
                 0.3 
                 — 
                 — 
                 — 
               
               
                 B-3 
                 65** 
                 28.5 
                 1.5 
                 1.5 
                 3* 
                 0.2* 
                 3* 
                 0.5* 
                 0.1* 
                 0.01* 
                 — 
               
               
                 B-10 
                 62 
                 24 
                 8 
                 6 
                 — 
                 0.5* 
                 1* 
                 — 
                 0.1* 
                 0.01* 
                 — 
               
               
                 242 
                 65 
                 25 
                 8 
                 2* 
                 — 
                 0.5* 
                 0.8* 
                 0.5* 
                 0.8* 
                 0.03* 
                 Co 1* 
               
               
                 C-22 
                 56 
                 13 
                 22 
                 3 
                 3 
                 0.5* 
                 0.5* 
                 — 
                 0.08* 
                 0.01* 
                 V 0.35* 
               
               
                 C-276 
                 57 
                 16 
                 16 
                 5 
                 4 
                 0.5* 
                 1* 
                 — 
                 0.08* 
                 0.01* 
                 V 0.35* 
               
               
                 C-2000 
                 59 
                 16 
                 23 
                 3* 
                 — 
                 1.6 
                 0.5* 
                 0.5* 
                 0.08* 
                 0.01* 
                 — 
               
               
                   
               
               
                 *Maximum, 
               
               
                 **Minimum 
               
             
          
         
       
     
       DETAILED DESCRIPTION OF THE INVENTION 
       [0017]    The discovery of these extremely versatile alloys involved the testing of small, experimental heats of material (each about 22.7 kg in weight). These were produced by vacuum induction melting, electroslag remelting, ingot homogenizing (50 h at 1232° C.), hot forging, and hot rolling into 3.2 mm thick sheets at 1149 to 1177° C. For each experimental alloy, an appropriate solution annealing treatment (in most cases at 1149° C.) was determined by furnace trials. As may be deduced from Tables 2 and 3 (nominal compositions and chemical analyses of experimental alloys), deliberate additions of manganese and aluminum were used to help minimize the sulfur and oxygen contents of all the alloys. Except in the case of the HYBRID alloy, the experimental materials also contained traces of rare earth elements, for enhanced sulfur and oxygen control. 
         [0018]    The upper compositional boundaries were determined without corrosion testing, since it was not possible to generate a single phase microstructure in alloy EN1406. Thus, 23.67 wt. % molybdenum and 16.85 wt. % chromium are regarded as outside the compositional range of this invention. 
         [0000]    
       
         
               
             
               
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Nominal Compositions of Experimental Alloys, Weight % 
               
             
          
           
               
                   
                 ALLOY 
               
             
          
           
               
                   
                 Ni 
                 Mo 
                 Cr 
                 Mn 
                 Al 
               
               
                   
                   
               
             
          
           
               
                   
                 HYBRID 
                 BAL. 
                 22 
                 15 
                 0.3 
                 0.3 
               
               
                   
                 EN1006 
                 BAL. 
                 20 
                 15 
                 0.3 
                 0.3 
               
               
                   
                 EN1106 
                 BAL. 
                 23 
                 15 
                 0.3 
                 0.3 
               
               
                   
                 EN1206 
                 BAL. 
                 22 
                 14 
                 0.3 
                 0.3 
               
               
                   
                 EN1306 
                 BAL. 
                 22 
                 16 
                 0.3 
                 0.3 
               
               
                   
                 EN1406 
                 BAL. 
                 24 
                 17 
                 0.3 
                 0.3 
               
               
                   
                 EN5900* 
                 BAL. 
                 23 
                 13 
                 0.4 
                 0.2 
               
               
                   
                   
               
               
                   
                 *Nominal composition also included 1 wt. % iron 
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
             
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                 Chemical Analyses of Experimental Alloys (Prior to 
               
               
                 Electroslag Remelting), Weight % 
               
             
          
           
               
                   
                 ALLOY 
               
             
          
           
               
                   
                 Ni 
                 Mo 
                 Cr 
                 Mn 
                 Al 
                 C 
                 Si 
                 Fe 
                 Ce 
                 La 
               
               
                   
                   
               
             
          
           
               
                 HYBRID* 
                 63.34 
                 21.64 
                 14.93 
                 0.27 
                 0.25 
                 0.013 
                 0.02 
                 0.07 
                 — 
                 — 
               
               
                 EN1006 
                 64.82 
                 19.82 
                 14.56 
                 0.22 
                 0.26 
                 0.008 
                 0.04 
                 0.22 
                 0.012 
                 0.011 
               
               
                 EN1106* 
                 61.21 
                 23.06 
                 14.86 
                 0.27 
                 0.27 
                 0.005 
                 0.05 
                 0.06 
                 0.023 
                 0.019 
               
               
                 EN1206* 
                 63.73 
                 21.63 
                 13.77 
                 0.27 
                 0.31 
                 0.005 
                 0.04 
                 0.05 
                 0.017 
                 0.012 
               
               
                 EN1306* 
                 62.01 
                 21.46 
                 15.60 
                 0.26 
                 0.27 
                 0.004 
                 0.05 
                 0.06 
                 0.013 
                 0.010 
               
               
                 EN1406 
                 58.58 
                 23.67 
                 16.85 
                 0.26 
                 0.26 
                 0.004 
                 0.04 
                 0.15 
                 0.012 
                 0.008 
               
               
                 EN5900 
                 62.29 
                 22.60 
                 12.67 
                 0.35 
                 0.23 
                 0.010 
                 0.03 
                 1.19 
                 0.022 
                 — 
               
               
                   
               
               
                 *Alloys of this invention 
               
             
          
         
       
     
         [0019]    The corrosion rates for the other experimental alloys (i.e. those which responded well to solution annealing and water quenching, yielding a single phase microstructure) and commercial materials in the strong, oxidizing and strong, reducing acid media previously mentioned are given in Table 4. The steep decline in resistance to the strong, oxidizing solution (oxygenated 2.5% HCl at 121° C.) associated with reducing the chromium content from 14.86 to 12.67 wt. % in alloys containing about 23 wt. % molybdenum (EN1106 versus EN5900) indicates that the chromium content should be at least 13.0 wt. %. Also, the steep decline in resistance to the strong, reducing solution (nitrogenated 2.5% HCl at 121° C.) associated with reducing the molybdenum content from 21.64 to 19.82 wt. % in alloys containing about 15 wt. % chromium (the HYBRID alloy versus EN1006) indicates that the molybdenum content should be at least 20.0 wt. %. 
         [0000]    
       
         
               
             
               
               
               
               
             
               
               
               
               
             
           
               
                 TABLE 4 
               
             
             
               
                   
               
               
                 Corrosion Rates (mm/y) for Experimental Alloys and Prior Art Alloys 
               
               
                 in Strong Oxidizing and Strong Reducing Acid Solutions 
               
             
          
           
               
                   
                   
                 OXYGENATED 
                 NITROGENATED 
               
               
                   
                 ALLOY 
                 2.5% HCl at 121° C. 
                 2.5% HCl at 121° C. 
               
               
                   
                   
               
             
          
           
               
                   
                 HYBRID* 
                 0.37 
                 0.27 
               
               
                   
                 EN1006 
                 0.41 
                 0.93 
               
               
                   
                 EN1106* 
                 0.40 
                 0.23 
               
               
                   
                 EN1206* 
                 0.54 
                 0.46 
               
               
                   
                 EN1306* 
                 0.31 
                 0.53 
               
               
                   
                 EN5900 
                 1.22 
                 0.13 
               
               
                   
                 B-3 
                 4.58 
                 &lt;0.01 
               
               
                   
                 B-10 
                 4.45 
                 0.09 
               
               
                   
                 242 
                 4.31 
                 0.04 
               
               
                   
                 C-4 
                 16.52 
                 8.75 
               
               
                   
                 C-22 
                 0.02 
                 4.13 
               
               
                   
                 C-276 
                 4.17 
                 2.52 
               
               
                   
                 C-2000 
                 0.02 
                 3.99 
               
               
                   
                  59 
                 0.08 
                 5.65 
               
               
                   
                 686 
                 8.93 
                 8.23 
               
               
                   
                 MAT-21 
                 1.27 
                 5.98 
               
               
                   
                   
               
               
                   
                 *Alloys of this invention 
               
             
          
         
       
     
         [0020]    To provide additional evidence of the unique behavior and versatility of the HYBRID alloy, it was compared with B-3 alloy (as the representative of the Ni—Mo system) and C-276 alloy (as the representative of the Ni—Cr—Mo system) in several other oxidizing and reducing environments. The results of these comparative tests are given in Table 5. In hydrochloric acid (HCl), hydrofluoric acid (HF), and sulfuric acid (H 2 SO 4 ), which are reducing, the HYBRID alloy provides resistance approaching that of the Ni—Mo alloys. In nitric acid (HNO 3 ) and a mixture of ferric chloride (FeCl 3 ) plus hydrochloric acid, which is oxidizing, the HYBRID alloy approaches the performance of the Ni—Cr—Mo alloys, whereas the Ni—Mo alloys exhibit extremely high corrosion rates in such environments. 
         [0000]    
       
         
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 5 
               
             
             
               
                   
               
               
                 Corrosion Rates (mm/y) of the HYBRID Alloy, B-3 Alloy, and 
               
               
                 C-276 alloy in other Environments 
               
             
          
           
               
                   
                 CONC., 
                 TEMP., 
                 HYBRID 
                 B-3 
                 C-276 
               
               
                 CHEMICAL 
                 wt. % 
                 ° C. 
                 ALLOY 
                 ALLOY 
                 ALLOY 
               
               
                   
               
             
          
           
               
                 HCl 
                  5 
                 93 
                 0.40 
                 0.30 
                 2.14 
               
               
                 HCl 
                 10 
                 79 
                 0.43 
                 0.29 
                 1.18 
               
               
                 HCl 
                 20 
                 66 
                 0.30 
                 0.21 
                 0.55 
               
               
                 HF 
                 20 
                 66 
                 0.58 
                 0.66 
                 0.84 
               
               
                 H 2 SO 4   
                 30 
                 93 
                 0.08 
                 0.09 
                 0.42 
               
               
                 H 2 SO 4   
                 50 
                 93 
                 0.06 
                 0.04 
                 0.62 
               
               
                 H 2 SO 4   
                 70 
                 93 
                 0.04 
                 0.01 
                 0.50 
               
               
                 HNO 3   
                 10 
                 93 
                 0.10 
                 1,440.57 
                 0.07 
               
               
                 FeCl 3  + HCl 
                 6 + 1 
                 120 
                 0.26 
                 47.69 
                 0.12 
               
               
                   
               
             
          
         
       
     
         [0021]    Even though the samples tested were all wrought sheets, the alloys should exhibit comparable properties in other wrought forms (such as plates, bars, tubes, pipes, forgings, and wires) and in cast and powder metallurgy forms. Consequently, the present invention encompasses all forms of the alloy composition. 
         [0022]    Although I have disclosed certain present preferred embodiments of the alloys, it should be distinctly understood that the present invention is not limited thereto but may be variously embodied within the scope of the following claims.