PCT swonmagypnncams OD Inemations! Butea INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (61) International Patent Classification 6 : (11) International Publication Number: ‘WO 97/05297 c2C 19907 AL (43) International Publication Date: 13 February 1997 (13.02.97) (@1) International Application Number: __PCT/LUS96(09765 | (61) Designated States: CA, CN, JP, KR, MX, European patent (AT, BE, CH, DE, DK, ES, Fl, FR, GB, GR, TE, IT, LU, (22) International Fling Date: 10,June 1996 (10.06.96) MC, NL, PT, SE). (0) Priority Data: Published (08508 857 28 July 1995 (28.07.95) us With international search report (71) Applicant: WESTINGHOUSE ELECTRIC CORPORATION [US/US]; 11 Stanwix Stret, Pitsburgh, PA 15222-1384 (ws. (72) Inventor: CHERUVU, Narayana, S; 3638 Jericho Drive, Casselbery, FL 32707 (US). (74) Agents: PANIAN, Michael, G. et al; Westinghouse Electric Corporation, 11 Stanwix Stee, Pitsburgh, PA 15222-1384 ws), (64) Title: COBALT ALLOY (57) Abstract ‘There is provided by the invention a cobalt-based alloy comprising the following elements in weight percent: Carbon 0.35 to 05S ‘Tantalum 3.00 to 4.50; Columbium 0,00 to 0.75; Chromium 22.0 to 25.0; Nickel 9.0 to 11.0; Titanium 0.15 to 050; Tungsten 65 to 7. ‘Aluminum 0.10 to 0.25; Zirconium 0.0 to 0.05; and Cobalt balance. The cobalt-based alloy of the invention ean extend component If high temperature applications with exposure to frequent heating and cooling cycles, suchas combustion turbine fist stage vanes.FOR THE PURPOSES OF INFORMATION ONLY (Codes used to identify States pany to the PCT on the front pages of pamphlets publishing international applications under the PCT. aM (0B Usted Kings Mates at GE Gomis, Meso av ON Goer Nie a GR Gece Neterands Be HU Hungry Nowway = Te end New Zend 26 Tr tay Plan w Plan Pau! mR Ke ken Roms " KG km usa eerie CA Cats KP Denar People's Repbe Sule (CF Cental Ata Repaic of Kors Seeten CG Congo XR Reale of Kone Sipe CH Seinrind KL Kankhaan Sten Cl Cee dhe Lh Leche Strata CM Cameron 1k SéLnte Seep Gime 1R Lhe Swans CS Cashsloakia tus eu CL Cath Reb CO asembous Tor DE Geary Ly Lava ‘Tacsan DK Denn MC Momco ‘Tidal ad Tobago HE sors MD Repub of Meio isle ES Spain MG Malas Up Filed ML Ma Uses Ste of Ameren FR mee MN Monga stein GA Gib MR Mouraia Vet Nan10 15 20 wo 97708297 PCT/US96/09765 =a COBALT ALLOY EIELD OF THE INVENTION This invention relates to the field of cobalt-based alloys. More particularly, the invention relates to a cobalt- based alloy that extends component life in high temperature applications involving exposure to frequent heating and cooling cycles, such as combustion turbine first stage vanes. BACKGROUND OF THE INVENTION Service life of high temperature components, such as gas turbine blades and vanes, depends upon the material's creep strength and upon its low cycle fatigue strength. Low cycle fatigue strength, in turn, depends upon ductility. However, strength and ductility are inversely related Properties. In some applications, such as the combustion turbine first stage, vanes are exposed to thermal stresses during frequent heating and cooling cycles, making material with high ductility essential. Insufficient ductility results in cracking (from low cycle fatigue) and reduced service life. That is, the components are not sufficiently ductile to withstand repeated thermal shocks from alternate heating and cooling as the turbines are cycled on and off. With higher gas turbine inlet temperatures expected in the future, thermal stresses will significantly increase, thus further reducing service life of high’ temperature components. Hence, for10 15 20 25 30 35 WO 97/05297 PCTIUS96/09765 -2- improved reliability and availablity, the engines of the future will demand a material with high ductility. U.S. Patent 3,432,294, which patent is incorporated by reference as if fully set forth herein, discloses a carbide-hardened cobalt based alloy (hereinafter referred to as the "MAR-M 509 alloy"). The MAR-M 509 alloys as taught by U.S. Patent 3,432,294 consists essentially of, in weight Percent, about 0.4% to about 0.7% carbon, about 18% to about 24% chromium, about 7% to about 15% nickel, about 6% to about 9% tungsten, about 2% to about 5% tantalum, about 0.1% to about 0.5% titanium and relatively high levels of zirconium at about 0.1% to about 1% with the balance being essentially cobalt together with impurities and incidental elements normally associated with cobalt-based alloys. Among the incidental elements disclosed to be present in U.S. 3,432,294 are up to about 3% iron, up to about 0.5% each of manganese and silicon, up to about 0.1% boron, up to about 0.2% of columbium and up to about 2% of molybdenum. With the MAR-M alloy, there is has been reported difficulty in effectively applying protective coatings due to the mold metal reaction. U.S. Patent 4,082,548, which patent is incorporated by reference as if fully set forth herein, teaches a cobalt- based alloy (hereinafter referred to as the "ECY-768 alloy") having a minimum practicable of zirconium so that detrimental inter-dendritic carbide oxidation is suppressed and to alleviate the surface integrity and mold metal reaction problens of the prior art alloy MAR-M 509. The ECY-768 alloys as taught by U.S. Patent 4,082,548 consist essentially of, in weight percent, 0.55% to 0.65% carbon, 22.5% to 24.25% chromium, 9% to 11% nickel, 6.5% to 7.5% tungsten, 3% to 4% tantalum, 0.1% to 0.5% titanium and relatively low levels of zirconium at 0.0% to 0.05% with the balance being essentially cobalt together with 0.10% to 0.20% aluminum, 0.0% to 1.5% iron, 0.0% to 0.01% boron, 0.0% to 0.4% silicon and 0.0% to 0.1% manganese.10 15 20 25 30 a5 wo 9708297 PCTIUS96/09765 3 While the strength of is MAR-M 509 and ECY-768 are increased by thermal exposures during coating treatments or by exposure to service, the ductility of existing vanes made of these alloys is lowered. Accordingly, there remains a need for improved cobalt-based alloys which extend the service life of high temperature components, such as combustion turbine first stage vanes, which are exposed to frequent heating and cooling cycles. SUMMARY OF THE INVENTION The invention provides a novel cobalt-based alloy having optimized levels of carbon, while maintaining a minimum practicable zirconium level, which stabilizes the microstructure of components made of such alloys thereby reducing ductility loss caused by thermal treatment or long term service. The alloy of the invention, inter alia, extends component life, and improves reliability of combustion turbine vanes. There is provided by the invention a novel cobalt- based alloy comprising the following elements in weight percent: Carbon 0.35 to 0.55; Tantalum 3.00 to 4.50; Columbium 9.00 to 0.75; Chromium 22.0 to 25.0; Nickel 9.0 to 11.0; Titanium 0.15 to 0.50; Tungsten 6.5 to 7.5; Aluminum 0.10 to 0.25; Zirconium 0.00 to 0.05; and Cobalt balance. Further provided by the invention are novel cast components, such as gas turbine vanes, cast from the alloy of the invention. Other objects and advantages will become apparent from the following description taken in conjunction with the drawings. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1A and 1B are photomicrographs (1000X) of an ECY-768 alloy component from Westinghouse Electric Corporation, Pittsburgh, PA; as cast, before thermal treatment (A); and after thermal treatment for 30 hours at 1900°F, or about 1038°C (B). The arrows in Fig. 1B denote carbon precipitates formed after thermal treatment.10 a5 20 25 30 35 wo 9708297 PCT/US96/09765 a Fig. 2A and 2B are photomicrographs (400X and 1000x respectively) of an alloy of the invention (M4); as cast, before thermal treatment (A); and after thermal treatment at 1900°F, or about 1038°C (B). No significant precipitation of carbides was seen after thermal treatment. Fig. 3 is a graph comparing ductility of two alloys of the invention (M3 and M4) with an EcY-768 alloy after exposure to a thermal cycle (~ 30 hours) at 1900°F (about 1038°C). Fig. 4 is a graph comparing tensile strength of two alloys of the invention (M3 and M4) with an ECY-768 alloy after exposure to a thermal cycle (~ 30 hours) at 1900°F (about 1038°c). DETAILED DESCRIPTION OF THE INVENTION Generally speaking, the present invention is directed to a cobalt-based alloy comprising the following elements in weight percent: Carbon 0.35 to 0.55; Tantalum 3,00 to 4.50; Columbium 0.00 to 0.75; Chromium 22.0 to 25.0; Nickel 9.0 to 11.0; Titanium 0.15 to 0.50; Tungsten 6.5 to 7.5; Aluminum 0.10 to 0.25; Zirconium 0.00 to 0.05; and the balance being substantially Cobalt. Of course the alloy of the invention may further comprise impurities and incidental elements generally associated with cobalt-based alloys. Among the incidental elements which may be present in the alloy of the invention are, for example, Iron 0.0 to 1.5; Boron 0.00 to 0.01; Silicon 0.00 to 0.40; and Manganese 0.00 to 0.10. All element amounts disclosed herein are in weight percent unless otherwise indicated. The disclosed alloy of the invention is an improvement over the ECY-768 alloy now in use. This disclosed chemical modification includes removing the excess carbon believed to be the agent of lowered ductility, while maintaining minimal practicable levels of zirconium, thereby stabilizing the vane microstructure during the coating thernal treatment or long-term service. Total carbon content was lowered from a nominal 0.6% to between 0.375% and 0.55%. Thus, the original excess 0.1% carbon is substantially no10 15 20 25 30 35 Wo 97105297 PCTIUS96/09765 =ho longer available in solution in the matrix for precipitation during the coating thermal cycles and/or service. The alloy of the invention additionally comprises the element columbiun in the range from 0.0 to 0.75 and a range for tantalum of 3 to 4.5. The amounts of columbium and tantalum can be varied in the alloy of the invention depending on the amount of carbon employed as one function of both the columbium and tantalum is to help minimize carbide formation by tying up carbon as tantalum or columbium carbide. Thus, the amount of these elements are readily selected by those skilled in the art to reduce carbide formation-during thermal exposure and extended service. Material analysis reveals that ductility of existing ECY vanes (made of the Westinghouse ECY-768 alloy) is lowered by thermal exposure during coating treatments and/or by exposure to service. Coating processes generally include two thermal cycles: 1800-1900°F (about 982-1038°c) for six hours maximum (cycle 1); and 1825-1900°F (about 996-1038°c) for thirty hours maximum (cycle 2). Studies of a MAR-M 509, an alloy of the Martin Marietta Co., New York, NY, and studies of ECY-768 an alloy of the Westinghouse Electric Co., Pittsburgh, PA have shown that the coating thermal cycles or service exposure increases strength and lowers ductility. Table I tabulates the effects of coating thermal treatment on the strength and ductility of an alloy ECY-768 (ductility as measured by percentage elongation and by reduction of area). "Before Treatment" tensile properties (i.e., before coating thermal cycles, or "as cast") are compared with “After Treatment" tensile properties (i.e., after coating thermal cycles). For example, in carrot or test bar #1, YS (yield strength) increased slightly from 51.2 before treatment to 59.3 after treatment while RA (% reduction of area) drops dramatically from 12.0 before treatment to 2.9 after treatment and EL (¢ elongation) drops from 9 to 2.5. Overall, the average ductility loss is R75%. The effects of coating thermal cycles on tensile strength and ductility, as measured by ASTM-E8, in ECY-768 are shown in Table I.5 10 15 20 25 30 35 wo 97105297 PCTIUS96/09765 eo TABLE I TENSILE PROPERTIES OF ECY-768 BEFORE AND AFTER COATING THERMAL TREATMENT STRENGTH’ DUCTILITY’ STRENGTH DUCTILITY CARROT BEFORE_TREATMENT ys UTS EL RA YS UTS. EL RA ksi ksi 8% ksi_ksit x * 1 51.2 83.5 9.0 12.0 59.3 98.3 2.98 2 47.9 92.3 4.5 3.5 65.8 81.5 4.0 3 39.4 82.6 10.7 12.5 60.8 97.0 3.4 4 51.8 92.0 4.6 6.7 48.4 90.6 4.7 5 52.4 92.9 5.3 7.4 52.8 89.1 4.9 3.3 6 52.8 94.8 5.0 6.8 50.7 89.7 4.4 7 53.5 94.8 4.0 4.9 50.8 94.0 5.2 8 39.2 93.5 15.1 16.0 57.6 93.9 2.7 3.2% 9 48.9 67.6 6.4 8.3 65.9 80.6 2.88 10 44.9 69.3 6.8 9.9 60.6 81.7 3.3 3.5 a 40.6 66.2 8.2 6.8 61.8 82.3 2.1 2.5% 12 41.7 67.8 7.2 6.2 59.1 80.6 2.5% 13 40.4 67.5 6.6 8.7 62.9 83.2 2.0 2.4% 14 37.7 67.0 8.2 8.5 65.5 83.9 2.0 2.7% 15 41.0 69.8 8.9 13.0 63.6 82.3 2.1 2.6* 16 42.3 69.0 6.0 7.5 60.8 81.9 2.1 2.4 uv 39.6 66.9 7.3 9.0 61.8 82.3 2.2 3.7 18 39.9 68.7 10.3 11.9 60.7 82.1 2.2 2.3 19 38.6 67.7 8.4 8.4 49.8 70.3 2.0 1.4 20 43.6 71.5 8.5 8.1 62.377.5 1.9 1.9 2a 41.8 71.7 8.2 13.2 64.583.5 2.1 2.5 22 42.9 70.2 8.2 9.3 62.880.3 2.1 2.1 23 42.5 70.9 7.9 9.4 62.1 82.7 2.6 1.8 *Average of two tests. Carrot bars were taken at random. * STRENGTH Ys = yield strength ® pucrrnrry: urs EL RA ultimate tensile strength elongation reduction of area10 as 20 25 30 a5 wo 9708297 PCT/US96/09765 -7- The microstructural change responsible for lowering ductility is believed to be the precipitation of carbides from the matrix during the coating thermal cycles. Figures 1A and 1B are optical micrographs (power 1000x) of the ECY-768 microstructure that compare a sample "Before Treatment" with a sample "After Treatment". A precipitation of carbides has taken place during the thermal cycles and is clearly shown in Fig. 1B. It is this additional carbide precipitation during the coating thermal treatment that is believed responsible for the increased tensile and yield strengths and decreased ductility. The ECY-768 matrix, and the carbides present, were further analyzed before and after thermal exposure. Results showed that in the "as cast" structure, most of the carbon Precipitated as primary MC carbides (Tantalum Carbide and Tungsten Carbide) and as a smaller amount of MC; Where total carbon content was nominally 0.6%, these carbides together accounted for 0.5%. Thus, 0.1% carbon remained in solution in the matrix to precipitate during the coating treatment. Carbon remaining in solution in the “as cast" matrix (0.1%) was determined to be the carbon that later Precipitated as carbides (M,,C,) during the coating thermal cycles. further, the 75% decrease in ductility (shown in Table I) is believed to be primarily caused by the precipitation of this excess 0.1% carbon during heating. Figures 2A, 2B, 3 and 4 show results of tests on sample bars made of alloys of the invention (M3 and M4): Figure 2A and 2B show optical micrographs of an alloy of the invention (M4) that compare the microstructure "as cast" or “Before Treatment" (power 400X) with the microstructure "After Treatment" (after coating thermal cycles) (power 1000X). Note that no significant additional carbides precipitated from the M4 matrix during the coating thermal cycles. Figures 3 and 4 compare ductility and tensile strength of alloys of the invention (M3 an M4) with ECY-768 after exposure to thermal cycles. Ductility (EL, RA) increased significantly in the M3, M4 alloys: by = +300 to10 1s 20 25 30 35 wo 97105297 PCTIUS96/09765, -~a- 400%. Strength (YS, UTS) is surprisingly maintained in the M3, M4 alloys: at = -10%. In addition, creep rupture test results (data not shown) showed M3 and M4 to be comparable to ECY-768. (That is, under creep loading, service life is not reduced with M3 and M4.) Thus, alloys of the invention, such as the alloy referred to herein as "WES-100", chemistry as shown below, has increased ductility without adversely affecting the tensile and/or creep strength. The disclosed chemistry for WES-100, described as a range including M3 and M4 is as follows in weight percent: ELEMENT M3. ~__M4(wtt) ND not determined c 0.39 - 0.50 BAL = balance si 0.06 - = ND (% remaining) Mn a ND cr 22.99 = 22.01 Fe 0.08 - ND Ti 0.19 - 0.19 Al 0.18 = 0.21 co —— BAL Ni 9.91 = 10.03 Ww 6.84 = 6.83 ar <.01 - ND cb bd ae 0.42 Ta 3.11 - 3.84 s 0.0013- ND The alloy of the invention is produced by methods known to those in the art and the alloy is particularly suitable to be formed by casting into components useful at elevated temperatures such as are encountered by gas turbine vanes. Benefits of the alloy of this invention include extended component life by increasing material ductility without compromising tensile strength. Additionally, the alloy of the invention is believed to improve reliability of combustion turbine vanes currently cast of the ECY-768 alloy. The alloy of the invention thus provides a benefit both in gas turbine vanes and in other applications such as aircraft turbines.10 15 20 ‘wo 97105297 PCT/US96/09765 CLAIMS: 1. A cobalt-based alloy comprising the following elements in weight percent: carbon Tantalum Columbium chromium Nickel Titanium Tungsten Aluminum Zirconium Cobalt following Iron Boron silicon Manganese according component 0.35 to 0.55; 3.00 to 4.50; 0.00 to 0.75; 22.0 to 25. 9.0 to 11.0; 0.15 to 0.51 6.5 to 7.5; 0.10 to 0.25; 0.00 to 0.05; and balance. 2. The alloy of claim 1 further comprising the elements in weight percent: 0.0 to 1.57 0.00 to 0.0: 0.00 to 0.40; and 0.00 to 0.10. 3. A cast alloy component made of the alloy to claim 1. 4. The cast alloy component of claim 3 wherein said is a gas turbine vane.10 15 20 Wo 97108297 PCT/US96/09765 = 10 - 5. A gas turbine having a plurality of vanes, at least some of said vanes being made from an alloy comprising the following elements in weight percent: carbon 0.35 to 0.55; Tantalum 3.00 to 4.50; Columbium 0.00 to 0.75; Chromium 22.0 to 25.0; Nickel 9.0 to 11.07 Titanium 0.15 to 0.50; Tungsten 6.5 to 7.57 Aluminum 0.10 to 0.25; Zirconium 0.00 to 0.05; and Cobalt balance. 6. The gas turbine of claim 5 wherein said at least some of said vanes further comprises the following elements in weight percent: Iron 0.0 to 1.57 Boron 0.00 to 0.01; Silicon 0.00 to 0.40; Manganese 0.00 to 0.10.wo 97/08297 PCT/US96/09765 1/4 FIG. 1A FIG. IB SUBSTITUTE SHEET (RULE 26)WO 97108297 PCTIUS96109765 2/4 FIG. 2A FIG. 2B SUBSTITUTE SHEET (RULE 26)PCT/US96/09765Tn _senal Appleton No INTERNATIONAL SEARCH REPORT PCT/US 96/09765 re ae PCG C22c19/07 Accoring to Intrsional Patent Gsaiaton (1°) of tthnatonl elation and IPC B. FIELDS SEARCHED ‘Miran documetauon seared (Castcazon em flowed By Ganon HDT) IPC 6 C22C ‘Davaneiaton searched ober Gan Tania Sosanenaon We FH Gat Reh Soca ae Ind Be arch ‘less dt base conned ring te ierstonl Search (bane ala bse andy Whee prec, watch el) ‘C. DOCUMENTS CONSIDERED TO BE RELEVANT. ‘Caeory* | Caton of document, wh indcaton, where appropriate relevant pasages Relevant wo aim No x US,A,4 082 548 (KLEEMANN WILLI ET AL) 4 1-6 Apri} 1978 cited in the application see claim 1 x USzA,3 960 552 (MOULDS MICHAEL J) 1 June 1-6 see claim 1 A PATENT ABSTRACTS OF JAPAN 1 vol. 012, no. 252 (C-512), 15 July 1988 4 OP,A,63 038562 (MITSUBISHI HEAVY IND LTD), 19 February 1988, see abstract yee X] Parte documents ae ised in he contusion of box C. Dk] Pate fly member ae ited in ae. 7 Spec eaegone of ced docamens "AY doctmant defining te general sae of he at which mat ‘ouidered tobe 6 paricaar relevance “*E eater document but ube ono ater he iterations! ing Se *L docament neh may troy Guts on pry dint) or Wich ced to exch he pusienon a of nthe! Stabe o oer seca reo (Speed) 0° document refering wan orl dicen, we, otiion ot ‘er mean "P documest published pir woe ition fing dt at {Serta ep ee cn Z “Tt eaten seeps i array ates se seems at Setanta ey ea = “Se tpt ee edt en ‘Sino be ctaered novel or canner be eonadered Seite se mecerce am “Sime ste owe Set en Sec eerereeromet SUSaeiaocan “Se te tiny ‘Dit of he aca omleton of ie eran Ra 7 October 1996 ‘Dis of ang of earner Ba pO 24, 10.96 "Name and maling adres of Ge A ‘European Patent Office, PB StL Patenann 2 NCB HV Rew ek (731-1) 30-3000, Tx. 31651 epo a, a (23-0) 3003016 taraed oe Gregg, NV Foon PCTISATIO pce et Day) page 1 of 2INTERNATIONAL SEARCH REPORT Thea Applicaton No PCT/US 96/69765 TiConseaaten) DOCUMENTS CONSIDERED TO BE RELEVANT ‘Gazape" | Craton of dana wit neato, wee appopraty oT Be SAAN PSE Raleants dam Nos A PATENT ABSTRACTS OF JAPAN vol. 016, no. 383 (C-0974), 17 August 1992 & JP,A,04 124238 (TOSHIBA CORP), 24 April 1992, see abstract A PATENT ABSTRACTS OF JAPAN vol. 015, no. 496 (C-0894), 16 Decenber 1991, & JP,A,03 215644 (MITSUBISHI HEAVY IND LTD), 20 September 1991, see abstract A US,A,3 432 294 (WHEATON HAROLD L) 11 March 1969 cited in the application 1 Fem POTISAZIO saan me ec) Ua page 2 of 2INTERNATIONAL SEARCH REPORT Infomasn on pata arly member Ty onal Applicaton No PCT/US 96/9765 01-06-76 11-03-69 2545100 2288791 1526832 51064417 Patent document Publication Patent family Publication cited in search report ate member(s) ‘se US~A-4082548 04-04-78 843575 29-12-76 1059796 07-08-79 625835 15-10-81 2630833 «03-02-77 2318236 = 11-02-77 1552187 12-69-79 1273236 11-07-85 52011122 27-01-77 59053340 24-12-84 7606050 18-01-77 430077 «17-10-83 7607868 = 15-01-77 22-04-76 21-05-76 04-10-78 03-06-76 Fam TEA a omy Oy)