Nickel-chromium-aluminum alloy having good processability, creep resistance and corrosion resistance
09657373 ยท 2017-05-23
Assignee
Inventors
Cpc classification
C22C19/007
CHEMISTRY; METALLURGY
C22C19/053
CHEMISTRY; METALLURGY
International classification
Abstract
A nickel-chromium-aluminum-iron alloy includes (in wt.-%) 24 to 33% chromium, 1.8 to 4.0% aluminum, 0.10 to 7.0% iron, 0.001 to 0.50% silicon, 0.005 to 2.0% manganese, 0.00 to 0.60% titanium, 0.0002 to 0.05% each of magnesium and/or calcium, 0.005 to 0.12% carbon, 0.001 to 0.050% nitrogen, 0.0001 to 0.020% oxygen, 0.001 to 0.030% phosphorus, 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+Al28 (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-aluminum alloy with (in % by wt) greater than 25 to less than 30% chromium, 1.8 to 3.2% aluminum, 0.10 to 7.0% iron, 0.001 to 0.50% silicon, 0.005 to 2.0% manganese, 0.00 to 0.60% titanium, 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, 0.0001-0.020% oxygen, 0.001 to 0.030% phosphorus, 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+Al28(2a)
and Fp36.6 with(3a)
Fp=Cr+0.272*Fe+2.36*Al+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 wt.
2. Alloy according to claim 1, with an iron content of 0.1 to 4.0%.
3. Alloy according to claim 1, with a silicon content of 0.001-0.20%.
4. Alloy according to claim 1, with a manganese content of 0.005 to 0.50%.
5. Alloy according to claim 1, with a titanium content of 0.001-0.60%.
6. Alloy according to claim 1, with a carbon content of 0.01 to 0.10%.
7. Alloy according to claim 1, further containing yttrium with a content of 0.01 to 0.20%.
8. Alloy according to claim 1, further containing lanthanum with a content of 0.001 to 0.20%.
9. Alloy according to claim 1, further containing cerium with a content of 0.001 to 0.20%.
10. Alloy according to claim 1, further containing cerium mixed metal with a content of 0.001 to 0.20%.
11. Alloy according to claim 1, further containing zirconium with a content of 0.01 to 0.20%.
12. Alloy according to claim 1, in which the zirconium is substituted completely or partly by 0.001 to 0.2% hafnium.
13. Alloy according to claim 1, further containing boron with a content of 0.0001 to 0.008%.
14. Alloy according to claim 1, further containing 0.0 to 5.0% cobalt.
15. Alloy according to claim 1, further containing at most 0.5% copper, wherein Formula 4a is supplemented by a term with Cu:
Fp=Cr+0.272*Fe+2.36*Al+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, Mo, W and C are the concentrations of the elements in question in % by wt.
16. Alloy according to claim 1, further containing at most 0.5% vanadium.
17. 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.
18. Alloy according to claim 1, wherein the following formulas are satisfied:
Fa60(5a)
with 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 wt.
19. Alloy according to claim 1, wherein the following formula is satisfied:
Fk45(7a)
with Fk=Cr+19*Ti+34.3*Nb+10.2*Al+12.5*Si+98*C+2245*B(8a) where Cr, Ti, Nb, Al, Si, C and B are the concentrations of the elements in question in % by wt.
Description
DESCRIPTION OF THE PROPERTIES
(1) In addition to an excellent metal dusting resistance, the alloy according to the invention should also have the following properties: a good phase stability a good processability a good corrosion resistance in air, similar to that of Alloy 602CA (N06025) a good heat resistance/creep resistance.
Phase Stability
(2) In the nickel-chromium-aluminum-iron system with additions of Ti and/or Nb, various embrittling TCP phases such as, for example, the Laves phases, sigma phases or the -phases or also the embrittling -phase or -phases can be formed, depending on alloying contents (see, for example, Ralf Brgel, Handbook of High-Temperature Materials Engineering [in German], 3rd Edition, Vieweg Verlag, Wiesbaden, 2006, page 370-374). The calculation of the equilibrium phase fractions as a function of temperature, for example of the batch 111389 of N06690, (see Table 2, typical compositions) shows theoretically the formation of -chromium with a low content of Ni and/or Fe(BCC phase in
(3) This is the case in particular when the following formula is satisfied:
Fp39.9 with(3a)
Fp=Cr+0.272*Fe+2.36*Al+2.22*Si+2.48*Ti+0.374*Mo+0.538*W11.8*C(4a)
where Cr, Al, Fe, Si, Ti, Mo, W and C are the concentrations of the elements in question in % by mass.
(4) The Table 2 with the alloys according to the prior art shows that Fp for Alloy 8, Alloy 3 and Alloy 2 is >39.9 and for Alloy 10 is exactly 39.9. For all other alloys with T.sub.s BCC939 C., Fp is 39.9.
(5) Processability
(6) The formability will be considered here as an example of processability.
(7) An alloy can be hardened by several mechanisms, so that it has a high heat resistance or creep resistance. Thus the alloying addition of another element brings about a more or less large increase of the strength (solid-solution hardening), depending on element. An increase of the strength by fine particles or precipitates (precipitation hardening) is far more effective. This may take place, for example, by the -phase, which is formed by additions of Al and further elements, such as, for example: Ti to a nickel alloy, or by carbides, which are formed by addition of carbon to a chromium-containing nickel alloy (see, for example, Ralf Burgel, Handbook of High-Temperature Materials Engineering, 3rd Edition, Vieweg Verlag, Wiesbaden, 2006, page 358-369).
(8) The increase of the content of elements forming the -phase, or of the C content, indeed increases the heat resistance, but increasingly impairs the formability, even in the solution-annealed condition.
(9) For a very readily formable material, elongations A5 of 50% but at least 45% are desired in the tension test at room temperature.
(10) This is achieved in particular when the following relationship between the elements Cr, Nb, Ti and C forming the carbide is satisfied:
Fa60 with(5a)
Fa=Cr+6.15*Nb+20.4*Ti+201*C(6b)
where Cr, Nb, Ti and C are the concentrations of the elements in question in % by mass.
(11) Heat resistance/creep resistance
(12) At the same time, the yield strength or the tensile strength at higher temperatures should reach at least the values of Alloy 601 (see Table 4).
600 C.: yield strength R.sub.p0.2>150 MPa; tensile strength R.sub.m>500 MPa(9a, 9b)
800 C.: yield strength R.sub.p0.2>130 MPa; tensile strength R.sub.m>135 MPa(9c, 9d)
(13) It would be desirable for the yield strength or the tensile strength to lie at least in the range of the values Alloy 602CA (see Table 4). At least 3 of the 4 following relationships should be satisfied:
600 C.: yield strength R.sub.p0.2>230 MPa; tensile strength R.sub.m>550 MPa(10a, 10b)
800 C.: yield strength R.sub.p0.2>180 MPa; tensile strength R.sub.m>190 MPa(10c, 10d)
(14) This is achieved in particular when the following relationship between the mainly hardening elements is satisfied:
Fk45 with(7a)
Fk=Cr+19*Ti+34.3*Nb+10.2*Al+12.5*Si+98*C+2245*B(8b)
where Cr, Ti, Nb, Al, Si, C and B are the concentrations of the elements in question in % by mass.
Corrosion Resistance:
(15) The alloy according to the invention should have a good corrosion resistance in air similar to that of Alloy 602CA (N06025).
EXAMPLES
(16) Manufacture:
(17) 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.
(18) 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 prepared from these sheets.
(19) 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.
(20) All alloy variants typically had a grain size of 70 to 300
(21) 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
(22) For the batches 2297 to 2308 and 250060 to 250149 smelted on the laboratory scale, but especially for the batches according to the invention marked with E (2301, 250129, 250132, 250133, 250134, 250137, 250138, 250147, 250148), the Formula (2a) Al+Cr28 is satisfied. They therefore satisfy the requirement that has been imposed on the metal dusting resistance.
(23) 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 therefore 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 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 in Table 3a and 3b satisfy the criterion Fp39.9.
(24) 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.
(25) 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 (E) 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.
(26) The exemplary batch 156658 of the alloy according to the prior art, Alloy 601 in Table 4, is an example of the minimum requirements on yield strength and tensile strength at 600 C. and 800 C., whereas the exemplary batches 156817 and 160483 of the alloy according to the prior art, Alloy 602 CA, are examples of very good values of yield strength and tensile strength at 600 C. and 800 C. Alloy 601 represents a material that exhibits the minimum requirements on heat resistance and creep resistance, which are described in Formulas 9a to 9d, Alloy 602 CA a material that exhibits an outstanding heat resistance and creep resistance, which are described in the Formulas 10a to 10d. For both alloys, the value of Fk is much larger than 45, and for Alloy 602 CA it is additionally even much higher than the value of Alloy 601, which reflects the elevated strength values of Alloy 602 CA. The alloys according to the invention (E) all exhibit a yield strength and tensile strength at 600 C. and 800 C. in the range of or considerably above that of Alloy 601, and have therefore satisfied the Formulas 9a to 9d. They lie in the range of the values of Alloy 602 CA and also satisfy the desirable requirements, in other words 3 of the 4 Formulas 10a to 10d. Fk is also greater than 45 for all alloys according to the invention in the examples in Table 4, and in fact is even mostly greater than 54 and thus in the range which is characterized by a good heat resistance and creep resistance. Among the laboratory batches not according to the invention, batches 2297 and 2300 are an example wherein the Formulas 9a to 9d are not satisfied and also an Fk<45 is obtained.
(27) 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 specific gross change in mass, the specific net change in mass and the specific change in mass of the spalled oxides after 1056 h are indicated in Table 5. The exemplary batches of the alloys according to the prior art, Alloy 601 and Alloy 690, exhibited a much higher gross change in mass than Alloy 602 CA, that of Alloy 601 being even many times greater than that of Alloy 690. Both form a chromium oxide layer that grows faster than an aluminum oxide layer. Alloy 601 still contains approximately 1.3% Al. This content is too low yet to form an aluminum oxide layer that is even only partly closed, and so the aluminum in the interior of the metallic material underneath the oxide layer oxidizes (internal oxidation), which results in a greater mass increase in comparison with Alloy 690. Alloy 602 CA has approximately 2.3% aluminum. Thus an at least partly closed aluminum oxide layer can form underneath the chromium oxide layer in this alloy. This reduces the growth of the oxide layer markedly and thus also the specific increase in mass. All alloys according to the invention (E) contain at least 2% aluminum and therefore have a gross increase in mass that is small, similar to that of Alloy 602 CA, or smaller. Also, all alloys according to the invention, similarly to the exemplary batches of Alloy 602 CA, exhibit spallings in the range of the measurement accuracy, while Alloy 601 and Alloy 690 exhibit great spallings.
(28) The claimed limits for the alloy E according to the invention can therefore be substantiated in detail as follows:
(29) Too low Cr contents mean that the Cr concentration at the oxide-metal interface sinks very rapidly below the critical limit during use of the alloy in a corrosive atmosphere, and so a closed pure chromium oxide can no longer be formed in case of a damage to the oxide layer, although other less protective oxides can form. Therefore 24% Cr is the lower limit for chromium. Too high Cr contents impair the phase stability of the alloy, especially at the high aluminum contents of 1.8%. Therefore 33% Cr must be regarded as the upper limit.
(30) The formation of an aluminum oxide layer underneath the chromium oxide layer reduces the rate of oxidation. Below 1.8% Al, the aluminum oxide layer being formed has too many gaps in order to develop its effect completely. Too high Al contents impair the processability of the alloy. Therefore an Al content of 4.0% constitutes the upper limit.
(31) 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. With increase of the iron content, the phase stability decreases (formation of embrittling phases), especially at high chromium and aluminum contents. Therefore 7% Fe is a practical upper limit for ensuring the phase stability of the alloy according to the invention.
(32) 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 aluminum and chromium contents. The Si content is therefore limited to 0.50%.
(33) 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.
(34) Titanium increases the high-temperature resistance. From 0.60%, the oxidation behavior can be greatly impaired, and so 0.60% is the maximum value.
(35) Even very low Mg 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%.
(36) 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.
(37) 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.
(38) 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%.
(39) The content of phosphorus should be lower than or equal to 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%.
(40) 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.
(41) Molybdenum is limited to at most 2.0%, since this element reduces the oxidation resistance.
(42) Tungsten is limited to at most 2.0%, since this element also reduces the oxidation resistance.
(43) The following relationship between Cr and Al must be satisfied, in order that sufficient resistance to metal dusting is achieved:
Cr+Al28(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 sufficient metal dusting resistance.
(44) 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*Al+2.22*Si+2.48*Ti+0.374*Mo+0.538*W11.8*C(4a)
where Cr, Fe, Al, Si, Ti, 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 text.
(45) 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.
(46) 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%.
(47) 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%.
(48) 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%.
(49) 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%.
(50) If necessary, niobium may be added, since niobium also increases the high-temperature resistance. Higher contents raise the costs very greatly. The upper limit is therefore set at 1.10%.
(51) 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.
(52) 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.
(53) 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.
(54) 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.
(55) Cobalt may be present in this alloy up to 5.0%. Higher contents reduce the oxidation resistance markedly.
(56) Copper is limited to at most 0.5%, since this element reduces the oxidation resistance.
(57) Vanadium is limited to at most 0.5%, since this element likewise reduces the oxidation resistance.
(58) Pb is limited to at most 0.002%, since this element reduces the oxidation resistance. The same is true for Zn and Sn.
(59) Furthermore, the following relationship, which describes a particularly good processability, may be optionally satisfied for carbide-forming elements Cr, Ti and C:
Fa60 with(5a)
Fa=Cr+20.4*Ti+201*C(6a)
where Cr, Ti 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 text.
(60) Furthermore, the following relationship, which describes a particularly good heat resistance or creep resistance, with respect to the strength-increasing elements may be optionally satisfied:
Fk45 with(7a)
Fk=Cr+19*Ti+10.2*Al+12.5*Si+98*C(8a)
where Cr, Ti, 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 text.
(61) 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 Si S Ti P Zr Y B N Ce Alloy 600- 72.0 14.0- 6.0- 1.0 0.15 0.5 max 0.5 0.015 N06600 min 17.0 10.0 max max max max Alloy 601- 58.0- 21.0- Rest 1.0 1.0- 0.10 0.5 max 0.5 0.015 N06601 63.0 25.0 max 1.7 max max max Alloy 617- 44.5 20.0- 10.0- 8.0- 3.0 1.0 0.8- 0.05- 1.0 max 0.5 0.015 0.6 0.006 N06617 min 24.0 15.0 10.0 max max 1.5 0.15 max max max max Alloy 690- 58.0 27.0- 7.0- 0.5 0.05 0.5 max 1.0 0.015 N06690 min 31.0 11.0 max max max max Alloy 693- Rest 27.0- 0.5- 2.5- 1.0 2.5- 0.15 0.5 max 0.5 0.01 1.0 N06693 31.0 2.5 6.0 max 4.0 max max max max Alloy Rest 24.0- 8.0- 0.15 1.8- 0.15- 0.1 max 0.5 0.010 0.1- 0.020 0.01- 0.05- 602CA- 26.0 11.0 max 2.4 0.25 max max 0.2 max 0.10 0.12 N06025 Alloy 45- 45 26.0- 21.0- 1.0 0.05- 0.3 max 2.5- 0.010 0.020 0.03- N06046 min 29.0 25.0 max 0.12 3.0 max max 0.09 Alloy 603- Rest 24.0- 8.0- 0.15 2.4- 0.20- 0.50 max 0.5 0.010 0.01- 0.020 0.01- 0.01- N06603 26.0 11.0 max 3.0 0.40 max max 0.25 max 0.10 0.15 Alloy 696- Rest 28.0- 1.0- 2.0- 1.0 0.15 1.5-3.0 1.0- 0.010 1.0 N06696 32.0 3.0 6.0 max max 2.5 max max
(62) TABLE-US-00002 TABLE 2 Typical compositions of some alloys according to ASTM B 168-11 (prior art). All values in % by mass *) Alloy composition from U.S. Pat. No. 4,882,125 Table 1 Alloy Batch C S Cr Ni Mn Si Mo Ti Nb Cu Alloy 164310 0.07 0.002 15.75 73.77 0.28 0.32 0.2 0.01 600 N06600 Alloy 156656 0.053 4.0016 22.95 59.58 0.72 0.24 0.47 0.04 601 N06601 Alloy 111389 0.022 0.002 28.45 61.95 0.12 0.32 0.29 0.01 690 N06690 Alloy Alloy 0.015 0.01 29.42 60.55 0.014 0.075 0.02 1.04 0.03 693 10 *) N06693 Alloy Alloy 0.007 0.01 30.00 60.34 0.11 0.38 0.23 1.13 0.03 693 8 *) N06693 Alloy Alloy 0.009 0.01 30.02 57.79 0.01 0.14 0.02 2.04 0.03 693 3*) N06693 Alloy Alloy 0.006 0.01 30.01 60.01 0.12 0.14 0.01 0.54 0.03 693 2 *) N06693 Alloy 163968 0.170 0.01 25.39 62.12 0.07 0.07 0.13 0.01 602 N06025 Alloy 52475 0.225 0.002 25.20 61.6 0.09 0.03 0.16 0.01 0.01 603 N06603 Alloy UNS 0.080 0.01 30.00 61.20 0.1 1.5 2 0.1 2 696 average N06696 T.sub.s BCC Cr + Alloy Batch Fe P Al Zr Y B in C. Al Fp Alloy 164310 9.42 0.009 0.16 0.001 15.9 19.1 600 N06600 Alloy 156656 14.4 0.008 1.34 0.015 0 0.001 669 24.3 31.2 601 N06601 Alloy 111389 8.45 0.005 0.31 0 0 720 28.8 32.7 690 N06690 Alloy Alloy 5.57 3.2 0.002 939 32.6 39.9 693 10 *) N06693 Alloy Alloy 4.63 3.08 0.002 979 33.1 41.3 693 8 *) N06693 Alloy Alloy 5.57 4.3 0.002 1079 34.3 44.5 693 3*) N06693 Alloy Alloy 5.80 3.27 0.002 948 33.3 40.3 693 2 *) N06693 Alloy 163968 9.47 0.008 2.25 0.08 0.08 0.005 690 27.6 31.8 602 N06025 Alloy 52475 9.6 0.007 2.78 0.07 0.08 0.003 707 28.0 32.2 603 N06603 Alloy UNS 3 792 30.0 35.1 696 average N06696
(63) 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 T G Alloy 602 CA 156817 0.171 0.036 25.2 62.1 0.06 0.07 0.01 0.17 T G Alloy 602 CA 160483 0.172 0.025 25.7 62.0 0.06 0.05 0.02 0.14 T G Alloy 601 156656 0.053 0.018 23.0 59.6 0.72 0.24 0.04 0.47 T G Alloy 690 80116 0.010 0.025 27.8 62.8 0.18 0.15 0.01 0.31 T G Alloy 690 111389 0.022 0.024 28.5 62.0 0.12 0.32 <0.01 0.29 L Cr30Al1La 2297 0.018 0.023 29.9 68.0 0.25 0.09 <0.01 <0.01 L Cr30Al1LaT 2300 0.019 0.021 30.2 67.5 0.25 0.08 <0.01 <0.01 L Cr30Al1TiLa 2298 0.018 0.022 29.9 67.5 0.25 0.08 <0.01 0.3 L Cr30Al1TiNbLa 2308 0.017 0.028 30.1 67.1 0.25 0.08 <0.01 0.31 L Cr30Al1CLaTi 2299 0.060 0.021 30.1 67.6 0.25 0.09 <0.01 0.01 L Cr30Al1CLa 2302 0.049 0.02 30.1 67.1 0.26 0.09 <0.01 <0.01 E L Cr30Al2La 2301 0.015 0.021 30.2 66.6 0.25 0.08 <0.01 <0.01 L Cr30Al1Ti 250060 0.017 0.027 29.6 67.9 0.24 0.11 <0.01 0.31 L Cr30Al1Ti 250063 0.017 0.024 29.9 67.4 0.25 0.10 <0.01 0.31 L Cr30Al1TiNb 250066 0.016 0.022 29.9 67.1 0.24 0.09 <0.01 0.31 L Cr30Al1TiNb 250065 0.017 0.025 30.3 67.1 0.24 0.10 0.01 0.3 L Cr30Al1TiNbZr 250067 0.019 0.020 29.7 67.2 0.25 0.10 0.02 0.31 L Cr30Al1TiNb 250068 0.017 0.024 29.8 66.6 0.25 0.09 0.01 0.31 E L Cr28Al2 250129 0.018 0.025 28.2 68.3 0.25 0.10 <0.01 <0.01 E L Cr28Al2Y 250130 0.022 0.022 28.1 68.6 0.25 0.07 <0.01 <0.01 E L Cr28Al2YC1 250132 0.059 0.022 28.3 68.2 0.27 0.06 <0.01 <0.01 E L Cr28Al2Nb.5C1 250133 0.047 0.022 28.3 67.7 0.25 0.06 0.01 <0.01 E L Cr28Al2Nb.5C1 250148 0.049 0.019 27.9 67.9 0.26 0.07 <0.01 <0.01 E L Cr28Al2Nb1C1 250134 0.048 0.026 28.2 67.1 0.26 0.09 0.02 <0.01 E L Cr28Al2Nb1C1 250147 0.045 0.017 28.4 67.5 0.27 0.07 0.02 <0.01 E L Cr28Al2Nb1C1Y 250149 0.054 0.020 27.9 67.2 0.27 0.06 0.01 <0.01 E L Cr28Al2TiC1 250137 0.063 0.024 28.2 67.7 0.27 0.09 <0.01 0.15 E L Cr28Al2TiC1 250138 0.053 0.018 28.3 68.4 0.27 0.05 <0.01 0.16 T.sub.s BCC Cr + Name Batch Nb Cu Fe Al W in C. Al Fp T G Alloy 602 CA 156817 <0.01 0.01 9.6 2.36 683 27.6 31.9 T G Alloy 602 CA 160483 0.01 0.01 9.4 2.17 683 27.8 31.8 T G Alloy 601 156656 0.01 0.04 14.4 1.34 0.01 669 24.3 31.2 T G Alloy 690 80116 <0.01 0.01 8.5 0.14 683 27.9 31.4 T G Alloy 690 111389 0.01 0.01 8.5 0.31 720 28.8 32.7 L Cr30Al1La 2297 <0.01 <0.01 0.56 1.04 <0.01 737 30.9 32.5 L Cr30Al1LaT 2300 <0.01 <0.01 0.54 1.3 <0.01 737 31.5 33.3 L Cr30Al1TiLa 2298 <0.01 <0.01 0.55 1.28 <0.01 759 31.2 33.8 L Cr30Al1TiNbLa 2308 0.28 <0.01 0.53 1.25 0.01 772 31.4 34.3 L Cr30Al1CLaTi 2299 <0.01 <0.01 0.54 1.25 0.01 730 31.3 32.7 L Cr30Al1CLa 2302 <0.01 <0.01 0.57 1.65 <0.01 730 31.8 33.6 E L Cr30Al2La 2301 <0.01 <0.01 0.54 2.25 <0.01 809 32.4 36.6 L Cr30Al1Ti 250060 <0.01 <0.01 0.54 1.16 0.01 759 30.8 33.3 L Cr30Al1Ti 250063 <0.01 <0.01 0.53 1.39 <0.01 759 31.3 34.2 L Cr30Al1TiNb 250066 0.31 <0.01 0.50 1.42 0.01 772 31.3 34.6 L Cr30Al1TiNb 250065 0.31 <0.01 0.05 1.41 0.01 768 31.7 34.8 L Cr30Al1TiNbZr 250067 0.31 <0.01 0.53 1.47 0.01 776 31.1 34.4 L Cr30Al1TiNb 250068 0.88 <0.01 0.53 1.43 0.02 799 31.2 35.2 E L Cr28Al2 250129 <0.01 0.01 0.57 2.51 <0.01 740 30.7 34.3 E L Cr28Al2Y 250130 <0.01 <0.01 0.51 2.61 <0.01 766 30.7 34.3 E L Cr28Al2YC1 250132 0.01 0.02 0.60 2.61 0.02 762 30.9 34.1 E L Cr28Al2Nb.5C1 250133 0.50 0.02 0.52 2.76 0.02 800 31.1 35.2 E L Cr28Al2Nb.5C1 250148 0.56 0.03 0.48 2.62 0.01 779 30.5 34.5 E L Cr28Al2Nb1C1 250134 1.06 0.03 0.48 2.64 0.02 830 31.1 36.1 E L Cr28Al2Nb1C1 250147 0.90 0.02 0.43 2.15 0.02 774 30.5 34.3 E L Cr28Al2Nb1C1Y 250149 1.04 0.03 0.45 2.64 <0.01 800 30.6 35.1 E L Cr28Al2TiC1 250137 <0.01 0.03 0.5 2.88 <0.01 788 31.0 34.9 E L Cr28Al2TiC1 250138 <0.01 0.03 0.45 2.62 0.01 774 30.9 34.5
(64) 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 0.010 0.002 0.09 0.04 T G Alloy 601 158656 0.002 0.008 0.012 <0.01 0.03 0.015 0.04 T G Alloy 690 80116 0.002 0.006 0.030 0.0009 <0.002 0.02 T G Alloy 690 111389 0.002 0.005 <0.001 0.0005 0.01 L Cr30Al1La 2297 0.004 0.003 0.015 <0.01 <0.01 <0.002 L Cr30Al1LaT 2300 0.003 0.002 0.014 <0.01 <0.01 <0.002 <0.001 L Cr30Al1TiLa 2298 0.004 0.002 0.016 <0.01 <0.01 <0.002 <0.001 L Cr30Al1TiNbLa 2308 0.002 0.002 0.014 <0.01 <0.01 <0.002 L Cr30Al1CLaTi 2299 0.003 0.002 0.015 <0.01 <0.01 <0.002 <0.001 L Cr30Al1CLa 2302 0.003 0.002 0.013 <0.01 <0.01 <0.002 0.001 E L Cr30Al2La 2301 0.003 0.002 0.015 <0.01 <0.01 <0.002 <0.001 L Cr30Al1Ti 250060 0.003 0.002 0.009 <0.01 <0.01 <0.002 <0.001 L Cr30Al1Ti 250063 0.003 0.003 0.012 <0.01 <0.01 <0.002 <0.001 L Cr30Al1TiNb 250066 0.002 0.002 0.012 <0.01 <0.01 <0.002 <0.001 L Cr30Al1TiNb 250065 0.002 0.002 0.012 <0.01 <0.01 <0.002 <0.001 L Cr30Al1TiNbZr 250067 0.003 0.002 0.010 <0.01 <0.01 0.069 <0.001 L Cr30Al1TiNb 250068 0.002 <0.002 0.010 <0.01 <0.01 <0.002 <0.001 E L Cr28Al2 250129 0.004 0.003 0.011 0.0002 <0.01 <0.002 E L Cr28Al2Y 250130 0.003 0.003 0.013 <0.0002 <0.01 <0.002 E L Cr28Al2YC1 250132 0.003 0.004 0.009 0.0012 0.01 0.003 <0.01 E L Cr28Al2Nb.5C1 250133 0.005 0.003 0.009 0.0012 <0.01 0.004 0.01 E L Cr28Al2Nb.5C1 250148 0.004 0.004 0.010 0.0005 0.01 <0.01 E L Cr28Al2Nb1C1 250134 0.006 0.002 0.009 0.0009 <0.01 0.006 0.01 E L Cr28Al2Nb1C1 250147 0.002 0.002 0.010 0.0005 <0.01 0.01 0.01 E L Cr28Al2Nb1C1Y 250149 0.004 0.005 0.013 <0.0005 <0.01 0.006 <0.01 E L Cr28Al2TiC1 250137 0.005 0.004 0.008 0.0002 <0.01 0.004 <0.01 E L Cr28Al2TiC1 250138 0.005 0.004 0.010 0.0002 <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 158656 0.001 0.0001 T G Alloy 690 80116 0.002 0.0005 T G Alloy 690 111389 0.001 L Cr30Al1La 2297 <0.001 0.062 <0.001 <0.001 <0.005 0.001 0.0001 L Cr30Al1LaT 2300 <0.001 0.051 <0.001 <0.001 <0.005 0.001 0.0001 L Cr30Al1TiLa 2298 <0.001 0.058 <0.001 <0.001 <0.005 0.001 0.002 L Cr30Al1TiNbLa 2308 <0.001 0.093 <0.001 <0.001 <0.005 0.001 0.002 L Cr30Al1CLaTi 2299 <0.001 0.064 <0.001 <0.001 <0.005 0.001 0.002 L Cr30Al1CLa 2302 <0.001 0.057 <0.001 <0.001 <0.005 0.001 0.0001 E L Cr30Al2La 2301 <0.001 0.058 <0.001 <0.001 <0.005 0.001 0.002 L Cr30Al1Ti 250060 <0.001 <0.001 <0.001 <0.001 <0.005 <0.001 0.003 L Cr30Al1Ti 250063 <0.001 <0.001 <0.001 <0.001 <0.005 <0.001 0.003 L Cr30Al1TiNb 250066 <0.001 <0.001 <0.001 <0.001 <0.005 <0.001 0.004 L Cr30Al1TiNb 250065 <0.001 <0.001 <0.001 <0.001 <0.005 <0.001 0.005 L Cr30Al1TiNbZr 250067 <0.001 <0.001 <0.001 <0.001 <0.005 <0.001 0.003 L Cr30Al1TiNb 250068 <0.001 <0.001 <0.001 <0.001 <0.005 <0.001 0.004 E L Cr28Al2 250129 <0.0005 0.001 E L Cr28Al2Y 250130 0.063 <0.0005 0.001 E L Cr28Al2YC1 250132 0.07 0.001 0.001 E L Cr28Al2Nb.5C1 250133 0.01 0.001 E L Cr28Al2Nb.5C1 250148 <0.01 0.003 E L Cr28Al2Nb1C1 250134 0.01 <0.0005 0.003 E L Cr28Al2Nb1C1 250147 0.01 0.0012 0.001 E L Cr28Al2Nb1C1Y 250149 0.08 0.0012 0.002 E L Cr28Al2TiC1 250137 <0.01 0.0012 0.001 E L Cr28Al2TiC1 250138 <0.01 0.0012 0.004
(65) 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. KG in R.sub.p0,2 in R.sub.m in A.sub.5 in R.sub.p0,2 in MPa R.sub.m in MPa A.sub.5 in % R.sub.p0,2 in MPa R.sub.m in MPa Name Batch M MPa RT MPa RT % RT 600 C. 600 C. 600 C. 800 C. 800 C. Fa Fk T Alloy 602 CA 156817 76 292 699 36 256 578 41 186 198 63.0 76.9 T Alloy 602 CA 160483 76 340 721 42 254 699 69 186 197 62.2 79.6 T Alloy 601 156656 136 238 645 53 154 509 54 133 136 43.3 56.3 T Alloy 690 80116 92 279 641 56 195 469 48 135 154 36.2 41.6 T Alloy 690 111389 72 285 630 50 188 465 51 36.8 43.6 Cr30Al1La 2297 233 221 637 67 131 460 61 134 167 33.5 43.4 Cr30Al1LaT 2300 205 229 650 71 131 469 65 132 160 33.9 46.3 Cr30Al1TiLa 2298 94 351 704 59 228 490 31 149 161 39.7 51.5 Cr30Al1TiNbLa 2308 90 288 683 55 200 508 39 174 181 41.6 61.0 Cr30Al1CLaTi 2299 253 258 661 62 212 475 59 181 185 42.3 50.0 Cr30Al1CLa 2302 212 353 673 59 233 480 59 189 194 40.0 52.9 E Cr30Al2La 2301 155 375 716 66 298 504 49 275 277 33.2 55.6 Cr30Al1Ti 250060 114 252 662 67 183 509 62 143 154 39.3 60.4 Cr30Al1Ti 250063 118 252 659 70 176 510 57 148 152 39.6 52.9 Cr30Al1TiNb 250066 121 240 666 67 186 498 66 245 255 41.4 63.6 Cr30Al1TiNb 250065 132 285 685 61 213 521 58 264 265 41.8 64.0 Cr30Al1TiNbZr 250067 112 287 692 67 227 532 65 280 280 41.6 64.2 Cr30Al1TiNb 250068 174 261 666 69 205 498 65 297 336 44.9 83.2 E Cr28Al2 250129 269 334 674 66 191 224 31.8 56.8 E Cr28Al2Y 250130 167 322 693 63 252 522 53 220 244 32.6 57.9 E Cr28Al2YC1 250132 189 301 669 65 226 226 40.2 64.0 E Cr28Al2Nb.5C1 250133 351 399 725 67 334 522 33 285 353 40.8 78.9 E Cr28Al2Nb.5C1 250148 365 353 704 60 284 523 58 259 344 41.2 79.5 E Cr28Al2Nb1C1 250134 384 448 794 59 410 579 28 343 377 44.4 99.4 E Cr28Al2Nb1C1 250147 350 372 731 57 306 547 49 309 384 43.0 89.1 E Cr28Al2Nb1C1Y 250149 298 415 784 53 339 528 27 340 400 45.1 99.2 E Cr28Al2TiC1 250137 142 379 745 59 327 542 29 311 314 44.0 70.4 E Cr28Al2TiC1 250138 224 348 705 61 278 510 46 247 296 42.2 66.5
(66) TABLE-US-00006 TABLE 5 Results of the oxidation tests at 1000 C. in air after 1056 h m.sub.gross m.sub.net in uum.sub.spell Name Batch Test No. in g/m.sup.2 g/m.sup.2 in g/m.sup.2 T Alloy 602 CA 160483 412 8.66 7.83 0.82 T Alloy 602 CA 160483 425 5.48 5.65 0.18 T Alloy 601 156125 403 51.47 38.73 12.74 T Alloy 690 111389 412 23.61 7.02 16.59 T Alloy 690 111389 421 30.44 5.70 36.14 T Alloy 690 111389 425 28.41 0.68 29.09 Cr30Al1La 2297 412 36.08 7.25 43.33 Cr30Al1LaT 2300 412 41.38 2.48 43.86 Cr30Al1TiLa 2298 412 49.02 30.59 79.61 Cr30Al1TiNbLa 2306 412 40.43 16.23 24.20 Cr30Al1CLaTi 2308 412 42.93 15.54 58.47 Cr30Al1CLa 2299 412 30.51 0.08 30.44 Cr30Al2La 2302 412 27.26 9.57 17.68 E Cr30Al1Ti 2301 412 8.43 6.74 1.69 Cr30Al1Ti 250060 421 43.30 19.88 63.17 Cr30Al1TiNb 250063 421 32.81 22.15 54.96 Cr30Al1TiNb 250066 421 26.93 16.36 43.28 Cr30Al1TiNbZr 250065 421 25.85 24.27 50.12 Cr30Al1TiNb 250067 421 41.59 15.56 57.16 Cr28Al2 250068 421 42.69 39.26 61.95 E Cr28Al2Y 250129 425 3.72 3.55 0.16 E Cr28Al2YC1 250130 425 4.68 4.90 0.23 E Cr28Al2Nb.5C1 250132 425 3.94 5.01 1.07 E Cr28Al2Nb.5C1 250133 425 2.56 3.98 1.42 E Cr28Al2Nb1C1 250148 425 3.16 3.21 0.07 E Cr28Al2Nb1C1 250134 425 3.34 4.23 0.89 E Cr28Al2Nb1C1Y 250147 425 2.72 2.62 0.10 E Cr28Al2TiC1 250149 425 3.44 3.84 0.40 E Cr28Al2TiC1 250137 425 3.62 4.24 0.62 E Cr30Al1La 250138 425 3.87 4.28 0.41
LIST OF REFERENCE NUMBERS
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