Nickel-chromium alloy having good processability, creep resistance and corrosion resistance

Abstract

The invention relates to a nickel-chromium alloy comprising (in wt.-%) 29 to 37% chromium, 0.001 to 1.8% aluminum, 0.10 to 7.0% iron, 0.001 to 0.50% silicon, 0.005 to 2.0% manganese, 0.00 to 1.00% titanium and/or 0.00 to 1.10% niobium, 0.0002 to 0.05% each of magnesium and/or calcium, 0.005 to 12% carbon, 0.001 to 0.050% nitrogen, 0.001 to 0.030% phosphorus, 0.0001 to 0.020% oxygen, not more than 0.010% sulfur, not more than 2.0% molybdenum, not more than 2.0% tungsten, the remainder nickel and the usual process-related impurities, wherein the following relations must be satisfied: Cr+Al30 (2a) and Fp39.9 (3a) with Fp=Cr+0.272*Fe+2.36*Al+2.22*Si+2.48*Ti+0.374*Mo+0.538*W11.8*C (4a), wherein Cr, Fe, Al, Si, Ti, Mo, W and C is the concentration of the respective elements in % by mass.

Claims

1. Nickel-chromium alloy with (in % by wt) 31 to 37% chromium, 0.001 to 1.8% aluminum, 0.10 to 7.0% iron, 0.001 to 0.50% silicon, 0.005 to 2.0% manganese, 0.00 to 1.00% titanium and 0.10 to 1.10% niobium, respectively 0.0002 to 0.05% magnesium and/or calcium, 0.005 to 0.12% carbon, 0.001 to 0.050% nitrogen, 0.001 to 0.030% phosphorus, 0.0001-0.020% oxygen, max. 0.010% sulfur, max. less than 0.5% molybdenum, max. less than 0.5% tungsten, the rest nickel and the usual process-related impurities, wherein the following relationships must be satisfied:
Cr+Al>30(2a)
and Fp36.6 with(3a)
Fp=Cr+0.272*Fe+2.36*AI+2.22*Si+2.48*Ti+1.26*Nb+0.374*Mo+0.538*W11.8*C(4a) where Cr, Fe, Al, Si, Ti, Nb, C, W and Mo are the concentrations of the elements in question in % by mass, and wherein the following formula is satisfied:
Fa60(5a)
with Fa=Cr+6.15*Nb+20.4*Ti+201*C(6a) where Cr, Ti, Nb and C are the concentrations of the elements in question in % by mass.

2. Alloy according to claim 1, with a chromium content >32-37%.

3. Alloy according to claim 1, with an aluminum content of 0.001 to 1.4%.

4. Alloy according to claim 1, with an iron content of 0.1 to 4.0%.

5. Alloy according to claim 1, with a silicon content of 0.001 to 0.2%.

6. Alloy according to claim 1, with a manganese content of 0.005 to 0.50%.

7. Alloy according to claim 1, with a titanium content of 0.001 to 0.60%.

8. Alloy according to claim 1, with a niobium content of 0.10 to 1.0%.

9. Alloy according to claim 1, with a carbon content of 0.01 to 0.12%.

10. Alloy according to claim 1, further containing yttrium with a content of 0.01 to 0.20%.

11. Alloy according to claim 1, further containing lanthanum with a content of 0.001 to 0.20%.

12. Alloy according to claim 1, further containing cerium with a content of 0.001 to 0.20%.

13. Alloy according to claim 12, with a content of cerium mixed metal of 0.001 to 0.20%.

14. Alloy according to claim 1, further containing zirconium with a content of 0.01 to 0.20%.

15. Alloy according to claim 14, in which the zirconium is substituted completely or partly by 0.001 to 0.20% hafnium.

16. Alloy according to claim 1, further containing boron with a content of 0.0001 to 0.008%.

17. Alloy according to claim 1, further containing 0.00 to 5.0% cobalt.

18. Alloy according to claim 1, further containing at most 0.5% copper if necessary, wherein Formula 4a is supplemented by a term with Cu:
Fp=Cr+0.272*Fe+2.36*AI+2.22*Si+2.48*Ti+1.26*Nb+0.477*Cu+0.374*Mo+0.538*W11.8*C(4b) and Cr, Fe, Al, Si, Ti, Nb, Cu, W and Mo are the concentrations of the elements in question in % by mass.

19. Alloy according to claim 1, further containing at most 0.5% vanadium.

20. Alloy according to claim 1, wherein the impurities are adjusted in contents of max. 0.002% Pb, max. 0.002% Zn, max. 0.002% Sn.

21. Alloy according to claim 1, wherein the following formula is satisfied:
Fk40(7a)
with Fk=Cr+19*Ti+34.3*Nb+10.2*Al+12.5*Si+98*C(8a) for an alloy without B, where Cr, Ti, Nb, Al, Si and C are the concentrations of the elements in question in % by mass,
or with Fk=Cr+19*Ti+34.3*Nb+10.2*Al+12.5*Si+98*C+2245*B(8b) for an alloy with B, where Cr, Ti, Nb, Al, Si, C and B are the concentrations of the elements in question in % by mass.

Description

EXAMPLES

Manufacture

(1) Tables 3a and 3b show the analyses of the batches smelted on the laboratory scale together with some industrially smelted batches, cited for comparison, according to the prior art, of Alloy 602CA (N06025), Alloy 690 (N06690), Alloy 601 (N06601). The batches according to the prior art are marked with a T, those according to the invention with an E. The batches corresponding to the laboratory scale are marked with an L, those smelted industrially with a G.

(2) The ingots of the alloys smelted in vacuum on the laboratory scale in Table 3a and b were annealed for 8 h between 900 C. and 1270 C. and hot-rolled to a final thickness of 13 mm or 6 mm by means of hot rolls and further intermediate annealings for 0.1 to 1 h between 900 C. and 1270 C. The sheets produced in this way were solution-annealed for 1 h between 900 C. and 1270 C. The specimens needed for the measurements were taken from these sheets.

(3) For the industrially smelted alloys, a sample from the industrial production was taken from a commercially produced sheet of suitable thickness. The specimens needed for the measurements were taken from this sample.

(4) All alloy variants typically had a grain size between 65 and 310 m.

(5) For the exemplary batches in Table 3a and 3b, the following properties were compared. Metal dusting resistance Phase stability Formability on the basis of the tension test at room temperature Heat resistance/creep resistance by means of hot tension tests Corrosion resistance by means of an oxidation test

(6) Batches 2294 to 2314 and 250053 to 250150 were smelted on the laboratory scale. The batches according to the invention marked with E satisfy the Formula (2a) with Cr+AI>30 and are therefore more resistant to metal dusting than is Alloy 690. Batches 2298, 2299, 2303, 2304, 2305, 2308, 2314, 250063, 260065, 250066, 250067, 250068, 250079, 250139, 250140 and 250141 satisfy formula (2b) AI+Cr31. They are therefore particularly resistant to metal dusting.

(7) For the selected alloys according to the prior art in Table 2 and for all laboratory batches (Tables 3a and 3b), the phase diagrams were calculated and the formation temperature T.sub.s BCC was entered in Tables 2 and 3a. For the compositions in Tables 2 as well as 3a and 3b, the value for Fp according to Formula 4a was also calculated. Fp is larger the higher the formation temperature T.sub.s BCC. All examples of Alloy 693 (N06693) with a formation temperature T.sub.s BCC higher than that of Alloy 10 have an Fp>39.9. The requirement Fp39.9 (Formula 3a) is therefore a good criterion for obtaining an adequate phase stability in an alloy. All laboratory batches (marking L) in Table 3a and 3b satisfy the criterion Fp39.9.

(8) The yield strength R.sub.p0.2, the tensile strength R.sub.m and the elongation A.sub.5 for room temperature RT and for 600 C. are entered in Table 4, as is the tensile strength R.sub.m for 800 C. The values for Fa and Fk are also entered.

(9) Exemplary batches 156817 and 160483 of the alloy according to the prior art, Alloy 602 CA in Table 4, have a comparatively small elongation A5 at room temperature of 36 or 42%, which fall short of the requirements for good formability. Fa is >60 and therefore above the range that characterizes good formability. All alloys according to the invention exhibit an elongation >50%. Thus they satisfy the requirements. Fa is <60 for all alloys according to the invention. They therefore lie in the range of good formability. The elongation is particularly high when Fa is comparatively small.

(10) Exemplary batch 156658 of the alloy according to the prior art, Alloy 601 in Table 4, is an example of the range that the yield strength and tensile strength should reach at 600 C. and 800 C. This is described by the Formulas 7a to 7d. The value for Fk is >40. The alloys 2298, 2299, 2303, 2304, 2305, 2308, 2314, 250060, 250063, 260065, 250066, 250067, 250068, 250079, 250139, 250140, 250141, 250143, 250150 meet the requirement that at least 3 of the 4 Formulas 7a to 7d be satisfied. For these alloys, Fk is also larger than 40. The laboratory batches 2295, 2303, 250053, 250054 and 250057 are examples wherein fewer than 3 of the 4 Formulas 7a to 7d are satisfied. Then Fk is also <45.

(11) Table 5 shows the specific changes in mass after an oxidation test at 1100 C. in air after 11 cycles of 96 h, i.e. a total of 1056 h. The gross change in mass, the net change in mass and the specific change in mass of the spalled oxides after 1056 h are indicated in Table 5. The alloys according to the prior art, Alloy 601 and Alloy 690, exhibited a much higher gross change in weight than Alloy 602 CA. This is due to the fact that, although Alloy 601 and Alloy 690 form a chromium oxide layer that grows faster than an aluminum oxide layer, Alloy 602 CA has an at least partly closed aluminum oxide layer under the chromium oxide layer. This reduces the growth of the oxide layer markedly and thus also the specific increase in mass. The alloys according to the invention should have a corrosion resistance in air similar to that of Alloy 690 or Alloy 601. This means that the gross change in mass should be smaller than 60 g/m.sup.2. This is the case for all laboratory batches in Table 5, and therefore also for the batches according to the invention.

(12) The claimed limits for the alloy E according to the invention can therefore be substantiated in detail as follows:

(13) Too low Cr contents mean that the Cr concentration sinks very rapidly below the critical limit during use of the alloy in a corrosive atmosphere, and so a closed chromium oxide can no longer be formed. Therefore 29% Cr is the lower limit for chromium. Too high Cr contents impair the phase stability of the alloy. Therefore 37% Cr must be regarded as the upper limit.

(14) A certain minimum aluminum content of 0.001% is necessary for the manufacturability of the alloy. Too high Al contents, especially in the case of very high chromium contents, impair the processability and the phase stability of the alloy. Therefore an Al content of 1.8% constitutes the upper limit.

(15) The costs for the alloy rise with the reduction of the iron content. Below 0.1%, the costs rise disproportionately, since special raw material must be used. For cost reasons, therefore, 0.1% Fe must be regarded as the lower limit.

(16) With increase of the iron content, the phase stability decreases (formation of embrittling phases), especially at high chromium contents. Therefore 7% Fe is a practical upper limit for ensuring the phase stability of the alloy according to the invention.

(17) Si is needed during the manufacture of the alloy. Thus a minimum content of 0.001% is necessary. Too high contents again impair the processability and the phase stability, especially at high chromium contents. The Si content is therefore limited to 0.50%.

(18) A minimum content of 0.005% Mn is necessary for the improvement of the processability. Manganese is limited to 2.0%, since this element reduces the oxidation resistance.

(19) Titanium increases the high-temperature resistance. From 1.0%, the oxidation behavior can be greatly impaired, and so 1.0% is the maximum value.

(20) Just as titanium, niobium increases the high-temperature resistance. Higher contents increase the costs very greatly. The upper limit is therefore set at 1.1%.

(21) Even very low Mg contents and/or Ca contents improve the processability by binding sulfur, whereby the occurrence of low-melting NiS eutectics is prevented. Therefore a minimum content of respectively 0.0002% is necessary for Mg and/or Ca. At too high contents, intermetallic NiMg phases or NiCa phases may form, which again greatly impair the processability. The Mg and/or Ca content is therefore limited to at most 0.05%.

(22) A minimum content of 0.005% C is necessary for a good creep resistance. C is limited to a maximum of 0.12%, since above that content this element reduces the processability due to the excessive formation of primary carbides.

(23) A minimum content of 0.001% N is necessary, whereby the processability of the material is improved. N is limited to at most 0.05%, since this element reduces the processability by the formation of coarse carbonitrides.

(24) The oxygen content must be 0.020%, in order to ensure manufacturability of the alloy. A too low oxygen content increases the costs. The oxygen content is therefore 0.001%.

(25) The content of phosphorus should be 0.030%, since this surface-active element impairs the oxidation resistance. A too low P content increases the costs. The P content is therefore 0.0001%.

(26) The contents of sulfur should be adjusted as low as possible, since this surface-active element impairs the oxidation resistance. Therefore 0.010% S is set as the maximum.

(27) Molybdenum is limited to at most 2.0%, since this element reduces the oxidation resistance.

(28) Tungsten is limited to at most 2.0%, since this element also reduces the oxidation resistance.

(29) The following relationship between Cr and Al must be satisfied, in order that sufficient resistance to metal dusting is achieved:
Cr+Al>30(2a)
where Cr and Al are the concentrations of the elements in question in % by mass. Only then is the content of oxide-forming elements high enough to ensure a metal dusting resistance better than Alloy 690.

(30) Furthermore, the following relationship must be satisfied, in order that sufficient phase stability is achieved:
Fp39.9 with(3a)
Fp=Cr+0.272*Fe+2.36*AI+2.22*Si+2.48*Ti+1.26*Nb+0.374*Mo+0.538*W11.8*C(4a)
where Cr, Fe, Al, Si, Ti, Nb, Mo, W and C are the concentrations of the elements in question in % by mass. The limits for Fp as well as possible incorporation of further elements have been substantiated in detail in the foregoing description.

(31) If necessary, the oxidation resistance may be further improved with additions of oxygen-affine elements. They achieve this by being incorporated in the oxide layer and blocking the diffusion paths of the oxygen at the grain boundaries therein.

(32) A minimum content of 0.01% Y is necessary, in order to obtain the oxidation-resistance-increasing effect of the Y. For cost reasons, the upper limit is set at 0.20%.

(33) A minimum content of 0.001% La is necessary, in order to obtain the oxidation-resistance-increasing effect of the La. For cost reasons, the upper limit is set at 0.20%.

(34) A minimum content of 0.001% Ce is necessary, in order to obtain the oxidation-resistance-increasing effect of the Ce. For cost reasons, the upper limit is set at 0.20%.

(35) A minimum content of 0.001% cerium mixed metal is necessary, in order to obtain the oxidation-resistance-increasing effect of the cerium mixed metal. For cost reasons, the upper limit is set at 0.20%.

(36) If necessary, the alloy may also contain Zr. A minimum content of 0.01% Zr is necessary, in order to obtain the high-temperature-resistance-increasing and oxidation-resistance-increasing effect of the Zr. For cost reasons, the upper limit is set at 0.20% Zr.

(37) If necessary, Zr may be replaced completely or partly by Hf, since this element, just as Zr, increases the high-temperature resistance and the oxidation resistance. The replacement is possible starting from contents of 0.001%. For cost reasons, the upper limit is set at 0.20% Hf.

(38) If necessary, the alloy may also contain tantalum, since tantalum also increases the high-temperature resistance. Higher contents raise the costs very greatly. The upper limit is therefore set at 0.60%. A minimum content of 0.001% is necessary in order to achieve an effect.

(39) If necessary, boron may be added to the alloy, since boron increases the creep resistance. Therefore a content of at least 0.0001% should be present. At the same time, this surface-active element impairs the oxidation resistance. Therefore 0.008% boron is set as the maximum.

(40) Cobalt may be present in this alloy up to 5.0%. Higher contents reduce the oxidation resistance markedly.

(41) Copper is limited to at most 0.5%, since this element reduces the oxidation resistance.

(42) Vanadium is limited to at most 0.5%, since this element reduces the oxidation resistance.

(43) Pb is limited to at most 0.002%, since this element reduces the oxidation resistance. The same is true for Zn and Sn.

(44) Furthermore, the following relationship, which describes a particularly good processability, may be satisfied for carbide-forming elements Cr, Ti and C:
Fa60 with(5a)
Fa=Cr+6.15*Nb+20.4*Ti+201*C(6a)
where Cr, Nb, Ti and C are the concentrations of the elements in question in % by mass. The limits for Fa have been substantiated in detail in the foregoing description.

(45) Furthermore, the following relationship, which describes a particularly good heat resistance or creep resistance, between the strength-increasing elements may be satisfied:
Fk40 with (7a)
Fk=Cr+19*Ti+34.3*Nb+10.2*Al+12.5*Si+98*C (8a)
where Cr, Ti, Nb, Al, Si and C are the concentrations of the elements in question in % by mass. The limits for Fa and the possible incorporation of further elements have been substantiated in detail in the foregoing description.

(46) TABLE-US-00001 TABLE 1 Alloys according to ASTM B 168-11 (all values in % by mass) Alloy Ni Cr Co Mo Nb Fe Mn Al C Cu Alloy 600- 72.0 14.0-17.0 6.0-10.0 1.0 0.15 0.5 max N06600 min max max Alloy 601- 58.0-63.0 21.0-25.0 Rest 1.0 1.0-1.7 0.10 0.5 max N06601 max max Alloy 617- 44.5 20.0-24.0 10.0-15.0 8.0-10.0 3.0 1.0 0.8-1.5 0.05-0.15 1.0 max N06617 min max max Alloy 690- 58.0 27.0-31.0 7.0-11.0 0.5 0.05 0.5 max N06690 min max max Alloy 693- Rest 27.0-31.0 0.5-2.5 2.5-6.0 1.0 2.5-4.0 0.15 0.5 max N06693 max max Alloy 602CA- Rest 24.0-26.0 8.0-11.0 0.15 1.8-2.4 0.15-0.25 0.1 max N06025 max Alloy 45- 45 26.0-29.0 21.0-25.0 1.0 0.05-0.12 0.3 max N06045 min max Alloy 603- Rest 24.0-26.0 8.0-11.0 0.15 2.4-3.0 0.20-0.40 0.50 max N06603 max Alloy 696- Rest 28.0-32.0 1.0-3.0 2.0-6.0 1.0 0.15 1.5-3.0 N06696 max max Alloy Si S Ti P Zr Y B N Ce Alloy 600- 0.5 0.015 N06600 max max Alloy 601- 0.5 0.015 N06601 max max Alloy 617- 0.5 0.015 0.6 0.006 N06617 max max max max Alloy 690- 1.0 0.015 N06690 max max Alloy 693- 0.5 0.01 1.0 N06693 max max max Alloy 602CA- 0.5 0.010 0.1-0.2 0.020 0.01-0.10 0.05-0.12 N06025 max max max Alloy 45- 2.5-3.0 0.010 0.020 0.03-0.09 N06045 max max Alloy 603- 0.5 0.010 0.01-0.25 0.020 0.01-0.10 0.01-0.15 N06603 max max max Alloy 696- 1.0-2.5 0.010 1.0 N06696 max max

(47) TABLE-US-00002 TABLE 2 Typical compositions of some alloys according to ASTM B 168-11 (prior art). All values in % by mass *) Alloy compositions from U.S. Pat. No. 4,882,125 Table 1 Alloy Batch C S Cr Ni Mn Si Mo Ti Nb Cu Alloy 600 164310 0.07 0.002 15.75 73.77 0.28 0.32 0.2 0.01 N06600 Alloy 601 156656 0.053 0.0016 22.95 59.58 0.72 0.24 0.47 0.04 N06601 Alloy 690 111389 0.022 0.002 28.45 61.95 0.12 0.32 0.29 0.01 N06690 Alloy 693 Alloy 10 *) 0.015 0.01 29.42 60.55 0.014 0.075 0.02 1.04 0.03 N06693 Alloy 693 Alloy 8 *) 0.007 0.01 30.00 60.34 0.11 0.38 0.23 1.13 0.03 N06693 Alloy 693 Alloy 3 *) 0.009 0.01 30.02 57.79 0.01 0.14 0.02 2.04 0.03 N06693 Alloy 693 Alloy 2 *) 0.006 0.01 30.01 60.01 0.12 0.14 0.01 0.54 0.03 N06693 Alloy 602 163968 0.170 0.01 25.39 62.12 0.07 0.07 0.13 0.01 N06025 Alloy 603 52475 0.225 0.002 25.20 61.6 0.09 0.03 0.16 0.01 0.01 N06603 Alloy 696 UNS 0.080 0.01 30.00 61.20 0.1 1.5 2 0.1 2 N06696 average T.sub.s BCC Cr + Alloy Batch Fe P Al Zr Y B in C. Al Fp Alloy 600 164310 9.42 0.009 0.16 0.001 15.9 19.1 N06600 Alloy 601 156656 14.4 0.008 1.34 0.015 0 0.001 669 24.3 31.2 N06601 Alloy 690 111389 8.45 0.005 0.31 0 0 720 28.8 32.7 N06690 Alloy 693 Alloy 10 *) 5.57 3.2 0.002 939 32.6 39.9 N06693 Alloy 693 Alloy 8 *) 4.63 3.08 0.002 979 33.1 41.3 N06693 Alloy 693 Alloy 3 *) 5.57 4.3 0.002 1079 34.3 44.5 N06693 Alloy 693 Alloy 2 *) 5.80 3.27 0.002 948 33.3 40.3 N06693 Alloy 602 163968 9.47 0.008 2.25 0.08 0.08 0.005 690 27.6 31.8 N06025 Alloy 603 52475 9.6 0.007 2.78 0.07 0.08 0.003 707 28.0 32.2 N06603 Alloy 696 UNS 3 792 30.0 35.1 N06696 average

(48) TABLE-US-00003 TABLE 3a Composition of the laboratory batches, Part 1. All values in % by mass (T: alloy according to the prior art. E: alloy according to the invention, L: smelted on the laboratory scale: G: industrially smelted) Name Batch C N Cr Ni Mn Si Mo Ti Nb T G Alloy 602 CA 156817 0.171 0.036 25.2 62.1 0.06 0.07 0.01 0.17 <0.01 T G Alloy 602 CA 160483 0.172 0.025 25.7 62.0 0.06 0.05 0.02 0.14 0.01 T G Alloy 601 156656 0.053 0.018 23.0 59.6 0.72 0.24 0.04 0.47 0.01 T G Alloy 690 80116 0.010 0.025 27.8 62.8 0.18 0.15 0.01 0.31 <0.01 T G Alloy 690 111389 0.022 0.024 28.5 62.0 0.12 0.32 <0.01 0.29 0.01 E L Cr30TiLa 2294 0.023 0.025 30.2 68.3 0.25 0.10 <0.01 0.15 <0.01 E L Cr30La 2295 0.020 0.020 30.0 68.7 0.25 0.10 <0.01 <0.01 <0.01 E L Cr30CLa 2296 0.059 0.022 30.1 68.6 0.25 0.09 <0.01 <0.01 <0.01 E L Cr30Al1TiLa 2298 0.018 0.022 29.9 67.5 0.25 0.08 <0.01 0.30 <0.01 E L Cr30Al1TiNbLa 2308 0.017 0.028 30.1 67.1 0.25 0.08 <0.01 0.31 0.28 E L Cr30Al1CLaTi 2299 0.060 0.021 30.1 67.6 0.25 0.09 <0.01 0.01 <0.01 E L Cr33La 2303 0.019 0.020 32.9 65.7 0.25 0.09 <0.01 <0.01 <0.01 E L Cr33CLa 2304 0.045 0.025 33.0 65.6 0.25 0.08 <0.01 <0.01 <0.01 E L Cr33WCLa 2314 0.054 0.026 33.1 63.7 0.25 0.12 <0.01 <0.01 <0.01 E L Cr33Al1TiLa 2305 0.018 0.030 32.9 64.4 0.25 0.09 <0.01 0.15 <0.01 E L Cr30C 250054 0.040 0.025 30.4 68.3 0.25 0.12 <0.01 <0.01 <0.01 E L Cr30C 250053 0.040 0.022 30.5 68.7 0.25 0.12 <0.01 <0.01 <0.01 E L Cr30CNLa 250056 0.045 0.045 30.2 68.5 0.25 0.10 <0.01 <0.01 <0.01 E L Cr30Al1Ti 250060 0.017 0.027 29.6 67.9 0.24 0.11 <0.01 0.31 <0.01 E L Cr30Al1Ti 250063 0.017 0.024 29.9 67.4 0.25 0.10 <0.01 0.31 <0.01 E L Cr30Al1TiNb 250066 0.016 0.022 29.9 67.1 0.24 0.09 <0.01 0.31 0.31 E L Cr30Al1TiNb 250065 0.017 0.025 30.3 67.1 0.24 0.10 0.01 0.30 0.31 E L Cr30Al1TiNbZr 250067 0.019 0.020 29.7 67.2 0.25 0.10 0.02 0.31 0.31 E L Cr30Al1TiNb 250068 0.017 0.024 29.8 66.6 0.25 0.09 0.01 0.31 0.88 E L Cr33C 250057 0.040 0.027 32.5 66.3 0.24 0.10 <0.01 <0.01 <0.01 E L Cr33AlTi 250079 0.018 0.024 32.7 64.8 0.25 0.10 <0.01 0.15 <0.01 E L Cr33C1Ti 250139 0.083 0.027 32.5 65.8 0.27 0.07 <0.01 0.17 <0.01 E L Cr33C1Zr 250140 0.081 0.028 32.7 65.7 0.26 0.07 0.01 <0.01 0.01 E L Cr33C1 250141 0.079 0.028 32.9 65.6 0.27 0.06 <0.01 <0.01 <0.01 E L Cr30C1Y 250143 0.081 0.022 30.5 68.1 0.27 0.05 <0.01 <0.01 0.01 E L Cr30Nb1YC 250150 0.091 0.023 29.6 67.7 0.27 0.06 <0.01 <0.01 1.00 T.sub.s BCC Name Batch Cu Fe Al W in C. Cr + Al Fp T G Alloy 602 CA 156817 0.01 9.56 2.36 683 27.6 31.9 T G Alloy 602 CA 160483 0.01 9.44 2.17 683 27.8 31.8 T G Alloy 601 156656 0.04 14.41 1.34 0.01 669 24.3 31.2 T G Alloy 690 80116 0.01 8.48 0.14 683 27.9 31.4 T G Alloy 690 111389 0.01 8.45 0.31 720 28.8 32.7 E L Cr30TiLa 2294 <0.01 0.56 0.26 0.01 666 30.5 31.3 E L Cr30La 2295 <0.01 0.54 0.28 <0.01 650 30.3 30.8 E L Cr30CLa 2296 <0.01 0.54 0.27 <0.01 637 30.3 30.3 E L Cr30Al1TiLa 2298 <0.01 0.55 1.28 <0.01 759 31.2 33.8 E L Cr30Al1TiNbLa 2308 <0.01 0.53 1.25 0.01 772 31.4 34.3 E L Cr30Al1CLaTi 2299 <0.01 0.54 1.25 0.01 730 31.3 32.7 E L Cr33La 2303 <0.01 0.56 0.36 <0.01 739 33.3 33.9 E L Cr33CLa 2304 <0.01 0.56 0.32 <0.01 726 33.3 33.6 E L Cr33WCLa 2314 <0.01 0.53 0.25 1.91 766 33.3 34.4 E L Cr33Al1TiLa 2305 <0.01 0.57 1.44 <0.01 846 34.4 36.8 E L Cr30C 250054 <0.01 0.53 0.25 <0.01 637 30.7 30.9 E L Cr30C 250053 <0.01 0.05 0.25 <0.01 510 30.7 30.9 E L Cr30CNLa 250056 <0.01 0.53 0.23 <0.01 620 30.4 30.5 E L Cr30Al1Ti 250060 <0.01 0.54 1.16 0.01 759 30.8 33.3 E L Cr30Al1Ti 250063 <0.01 0.53 1.39 <0.01 759 31.3 34.2 E L Cr30Al1TiNb 250066 <0.01 0.5 1.42 0.01 772 31.3 34.5 E L Cr30Al1TiNb 250065 <0.01 0.05 1.41 0.01 768 31.7 34.8 E L Cr30Al1TiNbZr 250067 <0.01 0.53 1.47 0.01 776 31.1 34.4 E L Cr30Al1TiNb 250068 <0.01 0.53 1.43 0.02 799 31.2 35.2 E L Cr33C 250057 <0.01 0.52 0.18 <0.01 726 32.7 32.8 E L Cr33AlTi 250079 <0.01 0.54 1.32 <0.01 844 34.1 36.4 E L Cr33C1Ti 250139 0.02 0.45 0.37 0.01 734 32.9 33.1 E L Cr33C1Zr 250140 0.03 0.46 0.32 0.01 744 33.1 32.8 E L Cr33C1 250141 0.02 0.65 0.29 0.01 719 33.2 32.9 E L Cr30C1Y 250143 0.02 0.46 0.32 0.02 630 30.8 30.5 E L Cr30Nb1YC 250150 0.03 0.48 0.57 <0.01 675 30.2 31.4

(49) TABLE-US-00004 TABLE 3b Composition of the laboratory batches, Part 2. All values in % by mass (The following values apply for all alloys: Pb: max. 0.002%, Zn: max. 0.002%, Sn: max. 0.002%) (see Table 3a for meanings of T, E, G, L) Name Batch S P Mg Ca V Zr Co T G Alloy 602 CA 156817 0.002 0.005 0.004 0.001 0.03 0.08 0.05 T G Alloy 602 CA 160483 <0.002 0.007 0.01 0.002 0.09 0.04 T G Alloy 601 156656 0.002 0.008 0.012 <0.01 0.03 0.015 0.04 T G Alloy 690 80116 0.002 0.006 0.03 0.0009 <0.002 0.02 T G Alloy 690 111389 0.002 0.005 0.001 0.0005 0.01 E L Cr30TiLa 2294 0.002 0.003 0.012 <0.01 <0.01 0.002 <0.001 E L Cr30La 2295 0.002 0.003 0.013 <0.01 <0.01 0.002 <0.001 E L Cr30CLa 2296 0.003 0.003 0.015 <0.01 <0.01 <0.002 <0.001 E L Cr30Al1TiLa 2298 0.006 0.002 0.016 <0.01 <0.01 <0.002 <0.001 E L Cr30Al1TiNbLa 2308 0.002 0.002 0.014 <0.01 <0.01 <0.002 0.001 E L Cr30Al1CLaTi 2299 0.003 0.002 0.015 <0.01 <0.01 <0.002 <0.001 E L Cr33La 2303 0.003 0.002 0.014 <0.01 <0.01 <0.002 0.001 E L Cr33CLa 2304 0.002 0.002 0.013 <0.01 <0.01 <0.002 0.001 E L Cr33WCLa 2314 0.001 0.003 0.009 <0.01 <0.01 <0.002 0.001 E L Cr33Al1TiLa 2305 0.003 0.002 0.018 <0.01 <0.01 <0.002 0.001 E L Cr30C 250054 0.003 0.002 0.007 <0.01 <0.01 <0.002 <0.001 E L Cr30C 250053 0.003 0.002 0.007 <0.01 <0.01 <0.002 <0.001 E L Cr30CNLa 250056 0.001 0.003 0.018 <0.01 <0.01 <0.002 <0.001 E L Cr30Al1Ti 250060 0.003 0.002 0.009 <0.01 <0.01 <0.002 <0.001 E L Cr30Al1Ti 250063 0.003 0.003 0.012 <0.01 <0.01 <0.002 <0.001 E L Cr30Al1TiNb 250066 0.002 0.002 0.012 <0.01 <0.01 <0.002 <0.001 E L Cr30Al1TiNb 250065 0.002 0.002 0.012 <0.01 <0.01 <0.002 <0.001 E L Cr30Al1TiNbZr 250067 0.003 0.002 0.010 <0.01 <0.01 0.069 <0.001 E L Cr30Al1TiNb 250068 0.002 <0.002 0.010 <0.01 <0.01 <0.002 <0.001 E L Cr33C 250057 0.004 0.002 0.008 <0.01 <0.01 <0.002 <0.001 E L Cr33AlTi 250079 0.003 0.002 0.011 <0.01 <0.01 <0.002 <0.001 E L Cr33C1Ti 250139 0.002 0.004 0.008 0.0002 <0.01 0.002 <0.01 E L Cr33C1Zr 250140 0.003 0.004 0.007 0.0002 <0.01 0.125 <0.01 E L Cr33C1 250141 0.002 0.004 0.008 0.0002 <0.01 0.007 <0.01 E L Cr30C1Y 250143 0.003 0.004 0.001 0.0002 <0.01 0.003 <0.01 E L Cr30Nb1YC 250150 0.004 0.005 0.01 <0.0005 <0.01 0.003 <0.01 Name Batch Y La B Hf Ta Ce O T G Alloy 602 CA 156817 0.060 0.003 0.001 T G Alloy 602 CA 160483 0.070 0.003 0.001 T G Alloy 601 156656 0.001 0.0001 T G Alloy 690 80116 0.002 0.0005 T G Alloy 690 111389 0.001 E L Cr30TiLa 2294 0.07 <0.005 0.001 0.0001 E L Cr30La 2295 0.06 <0.005 0.001 0.0001 E L Cr30CLa 2296 0.06 <0.005 0.001 0.0001 E L Cr30Al1TiLa 2298 <0.001 0.06 <0.001 <0.001 <0.005 0.001 0.002 E L Cr30Al1TiNbLa 2308 <0.001 0.09 <0.001 <0.001 <0.005 0.001 0.002 E L Cr30Al1CLaTi 2299 <0.001 0.06 <0.001 <0.001 <0.005 0.001 0.002 E L Cr33La 2303 <0.001 0.06 <0.001 <0.001 <0.005 0.001 0.0001 E L Cr33CLa 2304 <0.001 0.04 <0.001 <0.001 <0.005 0.001 0.0001 E L Cr33WCLa 2314 <0.001 0.05 <0.001 <0.001 <0.005 0.001 0.002 E L Cr33Al1TiLa 2305 <0.001 0.05 <0.001 <0.001 <0.005 0.001 0.0001 E L Cr30C 250054 <0.001 <0.001 <0.001 <0.005 <0.001 0.001 E L Cr30C 250053 <0.001 <0.001 <0.001 <0.005 <0.001 0.003 E L Cr30CNLa 250056 <0.001 0.03 <0.001 <0.001 <0.005 <0.001 0.002 E L Cr30Al1Ti 250060 <0.001 <0.001 <0.001 <0.005 <0.001 0.003 E L Cr30Al1Ti 250063 <0.001 <0.001 <0.001 <0.005 <0.001 0.003 E L Cr30Al1TiNb 250066 <0.001 <0.001 <0.001 <0.005 <0.001 0.004 E L Cr30Al1TiNb 250065 <0.001 <0.001 <0.001 <0.005 <0.001 0.005 E L Cr30Al1TiNbZr 250067 <0.001 <0.001 <0.001 <0.005 <0.001 0.003 E L Cr30Al1TiNb 250068 <0.001 <0.001 <0.001 <0.005 <0.001 0.004 E L Cr33C 250057 <0.005 <0.001 0.003 E L Cr33AlTi 250079 <0.005 <0.001 0.004 E L Cr33C1Ti 250139 0.01 <0.0005 0.004 E L Cr33C1Zr 250140 0.01 0.001 0.003 E L Cr33C1 250141 0.01 0.001 0.005 E L Cr30C1Y 250143 0.08 0.001 0.002 E L Cr30Nb1YC 250150 0.09 0.001 0.002

(50) TABLE-US-00005 TABLE 4 Results of the tension tests at room temperature (RT), 600 C. and 800 C. The deformation rate was 8.33 10.sup.5 1/s (0.5%/min) for R.sub.p0.2 and 8.33 10.sup.4 1/s (5%/min) for R.sub.m; KG = grain size, *) specimen defective. KG R.sub.p0.2 in A.sub.s in R.sub.p0.2 in R.sub.m in A.sub.s in R.sub.p0.2 in R.sub.m in in MPa R.sub.m in % MPa MPa % MPa MPa Name Batch m RT MPa RT RT 600 C. 600 C. 600 C. 800 C. 800 C. Fa Fk T G Alloy 602 CA 156817 76 292 699 36 256 578 41 186 198 63.0 76.9 T G Alloy 602 CA 160483 76 340 721 42 254 699 69 62.2 75.0 T G Alloy 601 156656 136 238 645 53 154 509 55 133 136 63.2 56.3 T G Alloy 690 80116 92 279 641 56 195 469 48 135 154 43.3 41.6 T G Alloy 690 111389 72 285 630 50 186 465 51 36.2 43.6 E L Cr30TiLa 2294 161 285 537 *) 170 452 29 145 171 38.0 39.6 E L Cr30La 2295 189 225 555 *) 131 358 26 110 167 34.0 36.0 E L Cr30CLa 2296 237 295 644 59 197 472 57 192 200 41.9 39.7 E L Cr30Al1TiLa 2298 94 351 704 59 228 490 31 149 161 39.7 51.6 E L Cr30Al1TiNbLa 2308 90 288 683 55 200 508 39 174 181 41.6 61.0 E L Cr30Al1CLaTi 2299 253 258 661 62 212 475 59 181 185 42.3 50.0 E L Cr33La 2303 145 272 618 *) 137 433 57 118 171 36.7 39.6 E L Cr33La 2304 278 284 640 50 171 439 65 168 209 42.1 41.7 E L Cr33WCLa 2314 298 254 644 66 143 438 67 154 212 43.9 42.4 E L Cr33Al1TiLa 2305 68 276 623 *) 224 472 41 161 166 39.6 53.3 E L Cr30C 250054 207 227 628 63 127 428 64 147 196 38.5 36.4 E L Cr30C 250053 150 215 526 55 119 426 57 128 187 38.5 38.5 E L Cr30CNLa 250056 242 234 612 55 145 440 74 144 204 39.3 38.2 E L Cr30Al1Ti 250060 114 252 662 67 183 509 62 143 154 39.3 50.4 E L Cr30Al1Ti 250063 116 252 659 70 178 510 57 148 1521 39.6 52.9 E L Cr30Al1TiNb 250066 121 240 666 67 186 498 66 245 255 41.4 63.6 E L Cr30Al1TiNb 250065 132 285 685 61 213 521 58 264 265 41.8 64 E L Cr30Al1TiNbZr 250067 112 287 692 67 227 532 65 280 280 41.6 64.2 E L Cr30Al1TiNb 250068 174 261 665 69 205 498 65 297 336 44.9 83.2 E L Cr33C 250057 191 241 638 66 127 414 54 185 197 40.6 39.5 E L Cr33AlTi 250079 101 267 665 68 190 489 56 145 164 39.4 52.0 E L Cr33C1Ti 250139 112 266 679 54 161 495 46 167 187 52.7 48.5 E L Cr33C1Zr 250140 153 269 667 60 177 447 36 164 191 49.1 47.4 E L Cr33C1 250141 302 269 645 58 157 430 62 192 214 48.8 46.6 E L Cr30C1Y 250143 195 264 650 69 166 490 60 174 195 46.8 44.9 E L Cr30Nb1YC 250150 72 287 722 53 188 577 57 181 194 54.0 81.6

(51) TABLE-US-00006 TABLE 5 Results of the oxidation tests at 1000 C. in air after 1056 h. Name Batch Test No. m.sub.gross in g/m.sup.2 m.sub.net in g/m.sup.2 m.sub.spall in g/m.sup.2 T G Alloy 602 CA 160483 412 8.66 7.83 0.82 T G Alloy 602 CA 160483 425 5.48 5.65 0.18 T G Alloy 601 156125 403 51.47 38.73 12.74 T G Alloy 690 111389 412 23.61 7.02 16.59 T G Alloy 690 111389 421 30.44 5.70 36.14 T L Alloy 690 111389 425 28.41 0.68 29.09 E L Cr30TiLa 2294 412 28.40 18.37 46.77 E L Cr30La 2295 412 19.44 0.09 19.35 E L Cr30CLa 2296 412 26.83 11.43 38.27 E L Cr30Al1TiLa 2298 412 49.02 30.59 79.61 E L Cr30Al1TiNbLa 2308 412 42.93 15.54 58.47 E L Cr30Al1CLaTi 2299 412 30.51 0.08 30.44 E L Cr33La 2303 412 25.98 8.42 34.40 E L Cr33CLa 2304 412 29.18 14.42 43.60 E L Cr33WCLa 2314 412 24.37 10.35 34.72 E L Cr33Al1TiLa 2305 412 49.96 19.36 69.32 E L Cr30C 250054 421 31.15 21.76 52.92 E L Cr30C 250053 421 31.37 26.58 57.95 E L Cr30CNLa 250056 421 23.46 9.64 33.11 E L Cr30Al1Ti 250060 421 43.30 19.88 63.17 E L Cr30Al1Ti 250063 421 32.81 22.15 54.96 E L Cr30Al1TiNb 250066 421 26.93 16.35 43.28 E L Cr30Al1TiNb 250065 421 25.85 24.27 50.12 E L Cr30Al1TiNbZr 250067 421 41.59 15.56 57.16 E L Cr30Al1TiNb 250068 421 42.69 39.26 81.95 E L Cr33C 250057 421 34.72 47.71 82.43 E L Cr33AlTi 250079 421 17.02 1.99 15.03 E L Cr33C1Ti 250139 425 57.97 49.60 107.58 E L Cr33C1Zr 250140 425 23.83 7.22 16.60 E L Cr33C1 250141 425 37.63 28.71 66.35 E L Cr30C1Y 250143 425 25.78 1.85 27.63 E L Cr30Nb1YC 250150 425 27.70 10.02 37.72

LIST OF REFERENCE NUMBERS

(52) FIG. 1 Metal loss due to metal dusting as a function of the aluminum and chromium content in a strongly carburizing gas with 37% Co, 9% H.sub.2O, 7% CO.sub.2, 46% H.sub.2, which has a.sub.c=163 and p(O.sub.2)=2.5.Math.10.sup.27. (from Hermse, C. G. M. and van Wortel, J. C.: Metal dusting: relationship between alloy composition and degradation rate. Corrosion Engineering, Science and Technology 44 (2009), p. 182-185). FIG. 2 Proportions of the phases in thermodynamic equilibrium as a function of the temperature of Alloy 690 (N06690) on the example of the typical batch 111389. FIG. 3 Proportions of the phases in thermodynamic equilibrium as a function of the temperature of Alloy 693 (N06693) on the example of Alloy 3 from Table 2. FIG. 4 Proportions of the phases in thermodynamic equilibrium as a function of the temperature of Alloy 693 (N06693) on the example of Alloy 10 from Table 2.