US3667938A - Nickel base alloy - Google Patents
Nickel base alloy Download PDFInfo
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- US3667938A US3667938A US34743A US3667938DA US3667938A US 3667938 A US3667938 A US 3667938A US 34743 A US34743 A US 34743A US 3667938D A US3667938D A US 3667938DA US 3667938 A US3667938 A US 3667938A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
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- NICKEL BASE ALLOY Filed may 5. 1970 5-Sheecs-Sheet 1 TITAN/UM, wr.
- the present invention relates to high temperature alloys and more particularly to high temperature nickel-base alloys that exhibit an optimum combination of hot corrosion resistance, strength, creep resistance, phase stability and most importantly, stress rupture life.
- Nickel-base alloys are known in the art that may be characterized by their resistance to hot corrosion, or by their high temperature strength or by their creep resistance and in some cases one of the above properties may be found in a particular alloy that also exhibits good phase stability when subjected to high temperatures for prolonged periods of time.
- the prior art is devoid of a single alloy which exhibits an optimum combination of hot corrosion resistance, strength, creep resistance and phase stability.
- FIG. 1 is an isolife graph illustrating the effect of the titanium-aluminum relationship on rupture life
- FIG. 2 is a Larson-Miller diagram which compares rupture properties of prior art alloys with alloys of the invention
- FIG. 3 is a graph of the influence of tungsten on rupture life
- FIG. 4 is a graph showing how cobalt influences rupture life
- FIG. 5 is a graph illustrating the effect of variations in carbon and boron on rupture life
- FIG. 6 is a graphical representation of the sulfidationerosion test results of the invention alloy compared with two commercial alloys
- FIG. 7 is a bar graph of sulfidation-erosion test results of the invention alloy compared with five commercial alloys.
- the present invention contemplates an alloy having a composition within the limits, by weight, of 12 to 20% chromium, 13 to 19% cobalt, 4.5 to 7% titanium, 1.3 to 3% aluminum, preferably 2 to 3% aluminum, 2 to 3.5% molybdenum, 0.5 to 2.5% tungsten, the combined molybdenum and tungsten content being 3 to 6%, 0.05 to 0.15% carbon, 0.005 to 0.03% boron, the titanium and aluminum content being balanced so as to provide a titanium to aluminum ratio within a specified relationship (ABCD of FIG.
- the alloy being essentially nickel with up to 0.75% manganese, up to 0.2% yttrium, up to 0.2% other rare earth elements such as cerium or lanthanum and up to 0.5% iron.
- the titanium content of the present invention is limited to an amount between 4.5 and 7% and the aluminum content is limited to an amount which provides a titanium to aluminum ratio within the area ABCD of FIG. 1, preferably between 2 and 3%. It is also necessary that in addition to the individual limits of the titanium and aluminum the total content of titanium plus aluminum be between 6.5% and 9.0%.
- the preferred ratio of titanium to aluminum is between 1.75:1 and 3.5:1.
- the titanium and aluminum contents have been determined to be critical in several respects. It was discovered that as the titanium to aluminum ratio increases and/or as the total titanium plus aluminum content increases the strength of the alloy increases up to that percentage of these elements at which deleterious titanium or aluminum bearing phases occur as massive or eutectic gamma prime or eta on initial heat treatment. Formation of eutectic gamma prime is enhanced when the aluminum content is high, together with a high total content of titanium plus aluminum, and formation of eta is enhanced when the titanium content is high, together 'with a high total content titanium plus aluminum. Obviously then it is necessary to limit the titanium to aluminum ratio and total content titanium plus aluminum within those ranges that give maximum effect to the strengthening properties of titanium and aluminum and yet are outside the range where deleterious titanium or aluminum bearing phases occur during solidification or on initial heat treatment.
- the titanium and aluminum content also have an indirect effect on formation of deleterious phases such as sigma or mu after prolonged exposures at elevated temperatures.
- the formation of these phases is enhanced when the total content titanium plus aluminum is high in a high chromium alloy. Therefore consideration must be given to limiting the titanium and aluminum content so as to prevent formation of these phases after prolonged exposure at elevated temperatures as well as to prevent formation of eutectic gamma prime and eta during solidification or on initial heat treatment.
- the isolife graph in FIG. 1 demonstrates the critical efiect of balancing titanium and aluminum.
- Existing commercial alloys having similar chemistrics have rupture lives, at comparable test conditions, of 30 to 40 hours.
- stress rupture lives of up to 140 hours or more are achieved.
- Alloys above line AB have shorter stress rupture life, lower workability and unduly high levels of gamma prime.
- Alloys to the left of AD have substantially poorer life as shown by the isolife curves.
- Alloys to the right of BC also have relatively poorer rupture life and lower ductility.
- Below line CD alloys have poorer rupture lives and/or are unworkable.
- the need to observe the limits ABCD is further illustrated by the stress rupture life and ductility data in Table II for compositions listed in Table I.
- the Larson-Miller diagram in FIG. 2 compares the stress rupture properties of the prior art alloys such as disclosed in US. Pat. 3,385,698 (Example A) and alloys of the invention (Examples B and C).
- Example A was tested at 1400 E. under a stress of 85 k.s.i.
- Examples B and C were tested at this temperature but at higher stress levels.
- the Larson-Miller Parameter enables direct comparison of alloys tested under dilferent stress and tempera ture conditions.
- the compositions of Example A, B, and C are given in Table 111. It can be seen that the titanium and aluminum balance is critically important in obtaining superior stress rupture life.
- the chromium content of the invention alloy embraces a range of from about 12% to about 20%. It was found that as chromium is increased the hot corrosion resistance of the alloy is increased and strength is decreased. Conversely, a reduction in chromium results in an increase in strength and a decrease in hot corrosion resistance.
- strength variation is directly related to an increase or decrease in the solvus temperature of gammaprime in gamma as chromium is reduced or increased respectively.
- a high chromium content is preferable, and the converse is true when hot corrosion resistance is secondary 'to strength.
- optimum alloy strength and hot corrosion resistance is realized when the chromium content is maintained between about 15% and about 18% and other alloying elements, particularly tungsten, are present in quantities herein stated.
- the alloy of this invention contemplates a tungsten content of from about 0.5% to about 2.5%.
- Tungsten within specific limits, has been found to increasethe strength of the alloy without enhancing the formation of deleterious phases. Its addition, therefore, overcomes the strength lost either due to a reduction of titanium and aluminum or due to an increase in chromium.
- the tungsten addition must be closely controlled, however, since it will promote formation of deleterious sigma or mu phases when present in higher percentages in a chromium rich alloy. Optimum characteristics of the invention alloy are obtained when tungsten is maintained within the range of about 1.5% to about 2.0%.
- the graph in FIG. 3 illustrates the influence of tungsten on rupture life.
- the cobalt content of the alloy of the present invention is within the limits of from about 13% to about 19%. In this respect, where strength is the prime consideration, and the additional alloying elements are present in amounts to accomplish this end, the cobalt content is effective for increasing strength proportional to the amount present within the limits stated. Conversely,-where hot corrosion resistance is of primary import, and the additional alloying elements are present in amounts to accomplish this end, no additional strengthening results from increasing amounts of cobalt.
- cobalt is present in the range of from about 13.0% to about 18.0%. The influence of cobalt is graphically shown in FIG. 4. 1
- the present invention contemplates a boron addition in the range of from about 0.005% to about 0.03% for the purpose of enhancing both the stress rupture life andthe ductility of the alloy. It was found that .the optimum combination of hot corrosion resistance, strength, creep resistance and phase stability was obtained when boron was present in the amount of from 0.018% to 0.22%
- Carbon content of the alloy of this invention is in the range of from about 0.05% to about 0.15% and has a direct effect upon stress rupture life of the alloy. As carbon increases, stress rupture life also increases, however, such increase in carbon has a concomitant eifect of decreasing the workability of the alloy. Optimum properties appear to occur when carbon lies in the range of 0.05 to 0.12%. The elfect of boron and carbon can be seen by the chart .in FIG. 5.
- Molybdenum is present in the invention alloy in quantities of from about 2.0% to about 3.5% and has an effect on alloy strength and workability. It was found, however, that if the molybdenum content goes below 1.5% there is a drastic reduction in alloy strength. Similarly, if the molybdenum content goes above 6.0% it was found that serious workability problems occur as a result of unidentified constituents appearing at the grain boundaries. While the exact limits have not been established, it was determined that molybdenum additions in the range of from about 2.0% to about 3.5% enhanced alloy strength and workability and it appears that optimum properties occur in this range.
- manganese and/or up to 0.2% yttrium or the rare earths, particularly cerium or lanthanum, may be added to enhance the oxidation resistance of the alloy.
- the alloy of this invention can be commercially melted by conventional methods and utilized in cast form or hot worked into normal mill products and heat treated to achieve desired mechanical properties.
- a suitable heat treatment to enhance the properties of the alloy at temperatures up to 1800" F. is as follows:
- the alloy of this invention has been successfully formed into about a 40-inch diameter turbine disc by TABLE VI Group I Temp. Stress Liie Elong. R.A. Heat No F.) (k.s.l.) (hrs.) (percent) (percent) 1, 350 90 272. 2 11v 6 14. 5 2735 1, 600 45 129. 9 12. 0 15.1 1, 800 20 49. 2 11.7 13.1 2858 1, 000 45 108. 4 10. 6 15. 8 1, 800 20 57. 2 12. 8 13. 8 350 90 300. 2 10. 9 15. 0 1,600 45 162. 5 7. 8 10. 3 1, 800 20 82. 2 6. 8 10. 5 1, 800 20 70. 3 13. 2 l8. 8 1, 400 92 86. 9 11. 8 l6. 9 l, 400 92 110. 8 11. 1 15. 9
- Typical creep properties of the invention are shown in Table VII showing test results of wrought samples from heat 5167 which were heat treated in the manner hereinbefore detailed and subjected to creep tests.
- the alloy can LE VI] be used for compressor discs or compressor and turbine Tem Stress buckets, and has been successfully formed into both cast m Creep data and forged turbine buckets.
- the alloy can be used I a for sheet components such as those used autglmerilted 1L5 -ttt hggetgegegt gte1.3353 0 553 5362 thrust applications.
- eet e a 0y eonga ion 2 v has been subjected to three times the deformation per re L800 iz?
- the invention alloy can be welded by the In addition to the above properties the alloy of this inert gas process.
- invention exhibits excellent hot corrosion resistance and For the purpose of giving those skilled in the art a this characteristic is optimized in the alloy class of the inbetter understanding of the invention byway of example vention having the nominal analyses of 18% chromium, a number of alloys of the general compositional range of 15% cobalt, 5% titanium, 2.5% aluminum, 3% molybthe invention were melted and tested. All mechanical test denum, 1.5% tungsten, 0.02% boron, and 0.05% carbon, samples were heat treated as above. Chemical analyses of the balance nickel.
- FIG. 6 is a plot of sample weight loss versus hours where exposure for invention alloy 2814 as compared to commercial alloys A and D when subjected to both blade cycle and vane cycle su lfidation-erosion tests.
- Blade cycle tests consist of heating a blade sample at 1550 F., for three minutes, then to 1850 F., for two minutes and then cooling it to the initial temperature of 1550 F in less than two minutes. This cycle is conducted in an oxidation-sulfidation rig in a media consisting of JPSR combustion products and sea salt.
- the vane cycle tests are identical to the blade cycle tests except that they are at temperatures 200 F. higher than those shown for the blade cycle. In each test the samples are removed about every 20 hours and Weighed. The weight loss in grams is plotted against total test time in hours.
- FIG. 7 shows blade cycle sulfidation-erosion test results for invention alloys 2814 and 2858 as compared with commercial alloys A, B, C, D and E.
- FIG. 6 An examination of FIG. 6 reveals that the invention alloy 2814 has a weight loss of .75 grams less than commercial alloy A and of 1.5 grams less than commercial alloy D in the blade cycle test and a weight loss of 1.5 grams less than commercial alloy D in the vane cycle test.
- invention alloys 2814 and 2858 have a Weight loss ranging from .75 grams to 6.0 grams less than the five commercial hot corrosion alloys used for comparison.
- the alloy of the present invention is free of deleterious sigma and mu phases after prolonged periods of exposure at elevated temperatures. Such phase stability was accomplished through utilization of an alloying for mula as follows:
- A% Atomic percent based on the proposition that formation of deleterious sigma and mu phases is a function of the number of electron vacancies (N%) in the bonding orbitals of the elements involved. It was here determined that when N of the residual matrix after precipitation of the hardening phase was equal to or less than 2.38 the alloy was free of sigma and mu phases after exposure under stress at elevated temperatures for prolonged periods of time.
- the hardening phase is assumed to be na 103 .o2)s
- each of the heats investigated has an N equal to or less than 2.38 as shown in Table ]X and each is free of deleterious sigma and mu phases when exposed for at least 1500 hours under a stress of 37,000 pounds per square inch at 1500" F.
- the alloy of this invention has an optimum combination of hot corrosion resistance, strength, creep resistance and phase stability.
- a nickel-base alloy consisting essentially of, by weight, from about 12.0% to about 20.0% chromium, from about 5% to about 7% titanium, from 1.3% to 3.0% aluminum, with the ratio of titanium to aluminum being from about 1.75 :1 to about 3.5:1, and the total content of titanium plus aluminum being from about 6.5% to about 9.0%, from about 13.0% to about 19.0% cobait, from about 2.0% to about 3.5% molybdenum, from about 0.5% to about 2.5% tungsten, from about 0.005% to about 0.03% boron, from about 0.05% to about 0.15% carbon, the balance being essentially nickel with incidental impurities, said alloy being characterized by its freedom from deleterious amounts of sigma and mu 2 phases ensuing from balancing the residual matrix composition to provide an electron vacancy (N value equal to or not greater than 2.38 in accordance with the equation:
- An alloy according to claim 1 characterized by being free of deleterious phases after exposure for at least 1500 hours under a stress of 37,000 pounds per square inch in the temperature range of 1500 F.
- An alloy according to claim 1 characterized by a rupture life of at least about 50 hours at 1800 F., under a load of 20,000 pounds per square inch.
- a nickel-base alloy according to claim 1 having about 15% to about 18% chromium, from about 5% to about 6.5% titanium, from about 2.0% to about 3.0% aluminum, with the ratio of titanium to aluminum being from about 1.75:1 to about 3.5:1 and the total content of titanium plus aluminum being from about 7.5% to about 8.5%, from about 15% to about 18% cobalt, from about 2.5% to about 3.5% molybdenum, from about 1.5% to about 2% tungsten, from about 0.018% to about 0.022% boron, from about 0.05% to about 0.12% carbon, the balance being essentially nickel with incidental impurities.
- a nickel-base alloy consisting essentially of 15 to 18% chromium, 15% to 18% cobalt, 2.5% to 3.5% molybdenum, 1.5% to 2% tungsten, 0.05% to 0.12% carbon, 0.015% to 0.022% boron, up to 0.5% manganese,
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US3474370A | 1970-05-05 | 1970-05-05 |
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Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3898109A (en) * | 1973-09-06 | 1975-08-05 | Int Nickel Co | Heat treatment of nickel-chromium-cobalt base alloys |
US4093476A (en) * | 1976-12-22 | 1978-06-06 | Special Metals Corporation | Nickel base alloy |
US4174964A (en) * | 1969-10-28 | 1979-11-20 | The International Nickel Company, Inc. | Nickel-base alloys of improved high temperature tensile ductility |
US4624716A (en) * | 1982-12-13 | 1986-11-25 | Armco Inc. | Method of treating a nickel base alloy |
FR2598439A1 (en) * | 1986-05-12 | 1987-11-13 | Exxon Production Research Co | PRECIPITATION PRECIPITATED NICKEL ALLOYS HAVING IMPROVED RESISTANCE TO CORRUGATED CORROSION CRACKING |
EP0387976A2 (en) * | 1989-03-15 | 1990-09-19 | Institute Of Metal Research Academia Sinica | New superalloys and the methods for improving the properties of superalloys |
WO1992018659A1 (en) * | 1991-04-15 | 1992-10-29 | United Technologies Corporation | Superalloy forging process and related composition |
US5476555A (en) * | 1992-08-31 | 1995-12-19 | Sps Technologies, Inc. | Nickel-cobalt based alloys |
US5725692A (en) * | 1995-10-02 | 1998-03-10 | United Technologies Corporation | Nickel base superalloy articles with improved resistance to crack propagation |
US5820700A (en) * | 1993-06-10 | 1998-10-13 | United Technologies Corporation | Nickel base superalloy columnar grain and equiaxed materials with improved performance in hydrogen and air |
US5938863A (en) * | 1996-12-17 | 1999-08-17 | United Technologies Corporation | Low cycle fatigue strength nickel base superalloys |
WO2011020976A1 (en) | 2009-08-20 | 2011-02-24 | Aubert & Duval | Nickel superalloy and parts made from said superalloy |
-
1970
- 1970-05-05 US US34743A patent/US3667938A/en not_active Expired - Lifetime
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4174964A (en) * | 1969-10-28 | 1979-11-20 | The International Nickel Company, Inc. | Nickel-base alloys of improved high temperature tensile ductility |
US3898109A (en) * | 1973-09-06 | 1975-08-05 | Int Nickel Co | Heat treatment of nickel-chromium-cobalt base alloys |
US4093476A (en) * | 1976-12-22 | 1978-06-06 | Special Metals Corporation | Nickel base alloy |
DE2752529A1 (en) * | 1976-12-22 | 1978-06-29 | Special Metals Corp | NICKEL ALLOY |
US4624716A (en) * | 1982-12-13 | 1986-11-25 | Armco Inc. | Method of treating a nickel base alloy |
FR2598439A1 (en) * | 1986-05-12 | 1987-11-13 | Exxon Production Research Co | PRECIPITATION PRECIPITATED NICKEL ALLOYS HAVING IMPROVED RESISTANCE TO CORRUGATED CORROSION CRACKING |
US4755240A (en) * | 1986-05-12 | 1988-07-05 | Exxon Production Research Company | Nickel base precipitation hardened alloys having improved resistance stress corrosion cracking |
EP0387976A2 (en) * | 1989-03-15 | 1990-09-19 | Institute Of Metal Research Academia Sinica | New superalloys and the methods for improving the properties of superalloys |
EP0387976A3 (en) * | 1989-03-15 | 1990-11-07 | Institute Of Metal Research Academia Sinica | New superalloys and the methods for improving the properties of superalloys |
WO1992018659A1 (en) * | 1991-04-15 | 1992-10-29 | United Technologies Corporation | Superalloy forging process and related composition |
US5476555A (en) * | 1992-08-31 | 1995-12-19 | Sps Technologies, Inc. | Nickel-cobalt based alloys |
US5637159A (en) * | 1992-08-31 | 1997-06-10 | Sps Technologies, Inc. | Nickel-cobalt based alloys |
US5888316A (en) * | 1992-08-31 | 1999-03-30 | Sps Technologies, Inc. | Nickel-cobalt based alloys |
US5820700A (en) * | 1993-06-10 | 1998-10-13 | United Technologies Corporation | Nickel base superalloy columnar grain and equiaxed materials with improved performance in hydrogen and air |
US5725692A (en) * | 1995-10-02 | 1998-03-10 | United Technologies Corporation | Nickel base superalloy articles with improved resistance to crack propagation |
US5788785A (en) * | 1995-10-02 | 1998-08-04 | United Technology Corporation | Method for making a nickel base alloy having improved resistance to hydrogen embittlement |
US5938863A (en) * | 1996-12-17 | 1999-08-17 | United Technologies Corporation | Low cycle fatigue strength nickel base superalloys |
WO2011020976A1 (en) | 2009-08-20 | 2011-02-24 | Aubert & Duval | Nickel superalloy and parts made from said superalloy |
US11193187B2 (en) | 2009-08-20 | 2021-12-07 | Aubert & Duval | Nickel-based superalloy and parts made from said superalloy |
US12024758B2 (en) | 2009-08-20 | 2024-07-02 | Aubert & Duval | Nickel-based superalloy and parts made from said superalloy |
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