Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/58—Processes for obtaining metallic images by vapour deposition or physical development
• • 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%
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
  • G03C8/02—Photosensitive materials characterised by the image-forming section
  • G03C8/04—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of inorganic or organo-metallic compounds derived from photosensitive noble metals
  • G03C8/06—Silver salt diffusion transfer

Definitions

• nickel base alloy application of particular interest is the cast form of the alloy.
• known nickel base alloys in cast forms either are relatively weak or unstable during longtime operation or have insufficient resistance in hot corrosive atmospheres particularly in the l,500 F.-l,800 range.
• a more specific object is to provide such an alloy of improved stability and having a stress rupture life in the as-cast condition of at least 25 hours under a stress condition of 27,500 psi. at l,800 F.
• a cast nickel base alloy having an improved combination of high-temperature stability and hot corrosion resistance along with a stress rupture life of at least 25 hours under stress of 27,500 p.s.i. at Cr; F. can be attained through (1) the control of the type of precipitation of strengthening phases first with carbon, and second with the elements titanium and aluminum in a nickel matrix, (2) the control of the solution-strengthening mechanisms as a result of the presence of W and M in particular portions to precipitate desirable carbides, along with (3) the substantial elimination of the well-known embrittling and weakening phases such as sigma and eta.
• the composition which defines such an alloy consists essentially of, by weight, 0.l-0.3% C; greater than 13% but less than 15.6% Cr; 4-6% Ti; 2-4%Al; 0.0050.02%B; 3-6%W; 2.55%M0; greater than 5% up to Co; up to 0.1% Zr; with the balance nickel and incidental impurities provided that the ratio of Ti to A1 is greater than I but less than 3:1, the sum of Ti and Al is 7.5-9% Mo-l: w/2 is 5-7%.
• caTbon preferably in the range of about 0.l50.2 percent provides for carbide formation which leads to improved strength particularly at high temperatures.
• lnsufficientcarbon for example at about 0.08 percent is insufficient for high-temperature strength whereas an overabundance of carbon, for example, above about 0.3 percent results in lower life and embrittlcment at lower temperatures as a result of excessive carbide formation in the grain boundaries.
• the element chromium provides oxidation and hot corrosion resistance. However, in amounts of less than 13 percent there is insufficient hot corrosion resistance provided in the temperature range of about 1,500-l,800 F. Cr in amountsgreater t han ir ziaarrresds'mse formation orsrgiirssna other deleterious phases without proper phase control. Accordingly, the preferred Cr range is 13.5-14.5 percent to assure such phase control.
• Co in excessive amounts can result in sigma phase formation.
• Co adds to the gamma prime solubility and affects ductility of the alloy.
• Ti/Al ratio must be greater than 1 to provide such improved hot corrosion resistance but less than 3:] to prevent the formation of the weakening eta (Ni Ti) phase.
• Al is preferably included in the range of about 2.5-3.5 percent because for one reason it can result in the formation of sigma phase somewhat more readily than does Ti; Al ties up more nickel from the matrix to form the Ni ',(Al,Ti), sometimes referred to as gamma prime. This occurs because of the lower atomic weight of aluminum compared with titanium. As the gamma prime content increases, there is less nickel available in the gamma matrix. Therefore, there is a greater tendency for sigma. phase formation due to the relatively larger amounts of Cr, Co, Mo, and W in the matrix. Accordingly, it is an objective to keep as much nickel as possible in the gamma matrix.
• the present invention recognizes the criticality of United States patent of aluminum and titanium not only from the standpoint of the ratio of aluminum and described above but also that at least 7.5 weight percent of the two elements is required but no more than 9 weight percent can be tolerated without seriously depleting the practiced matrix.
• the proper amount of Al stabilizes the gamma prime phase and prevents the Ni Ti formation. With too much Ti, the Ni (Al,Ti) is metastable and breaks down to form the weakening Ni Ti.
• iron has been included or tolerated in certain relatively large amounts in known nickel base alloys, the present invention recognizes that iron tends to form deleterious phases. Therefore, it is preferred that no iron be present although slight adjustment such as in the solid solutionstrengthening elements can be made to tolerate small amounts of Fe.
• Boron is included within the range of 0.005-0.02 percent for its beneficial effect on rupture strength and ductility.
• alloy forms representative of those melted within the scope of the present invention are shown in the following table TABLE 1 [Composition in weight percent] Alloy includes 0.0140.016% B; 0.03%I Zr, balancev Ni and incidental C Or M0 W Ti Al Other alloys made and tested during the evaluation of the alloy of the present invention include those shown in the following tabie 11, outside the scope of the present invention.
• the alloy of the present invention identifies a different kind of alloy which inhibits original sigma phase formation and results in the improved combination of higher temperature strength and stability along with hot corrosion resistance as a result of a different surface reaction product.
• Alloy includes 0.0140.017% B; 0.03 0.04% Zr with the balance Ni and incidental impurities 2 C Cr 00 Mo W Ti Al 'Ii/Al Ti+A1 Mo+Wl
• the improved characteristics of the present invention are particularly measured by combination of high-temperature stress rupture life and stability along with hot corrosion resistance. This improvement as it relates to longtime stability is related to the suppression of the formation of such embrittling phases as sigma and eta. These phases are greatly suppressed or are entirely eliminated according to the alloy of the present invention. When certain known case alloys are exposed to elevated temperatures, the gamma phase and carbides, which are found in the primary gamma prime phase, agglomerate.
• alloy 14 With respect to the chromium variation shown in table 111, the detrimental effect of the formation of heavy amounts of sigma on longtime stability is shown by alloy 14 at 15.6 percent Cr.
• the identification of large amounts of sigma shows alloy 14 to be of a different kind than that of alloy 6 within the scope of the present invention.
• Alloy at 13 percent Cr and only 0.9 percent lower than alloy 6, shows a reduction in strength even though all the elements of alloy 15 are within the range of the present invention. Therefore, the alloy of the present invention includes less than 15.6 percent but greater than 13 percent Cr.
• the elements Ti and Al contribute to the alloy of the present invention in several ways. This invention recognizes that the proper amount and interrelationship between these elements can control the short time strength, the alloy stability through sigma phase inhibition and, very importantly, provide hot corrosion resistance.
• hot corrosion resistance involves resistance to sulfidation in the range ofabout l,500- 1 ,800 Above and below that range, hot corrosion resistance is not as significant a problem in the type of alloys to which the present invention relates because such alloys include the element aluminum. Aluminum oxide which forms on the surface as a reaction product will form a reasonably protective oxidation resistant barrier. The problem of oxidation resistance is different from that of hot corrosion resistance. Normally for oxidation resistance it would be better to have a Ti/Al ratio of greater than 1. The higher ratio is desirable because TiO, is formed on the surface. The more TiO available. the better is the hot corrosion resistance. However, Ti in amounts which would produce a Ti/Al ratio of about 3:1 or more, cannot be tolerated in the alloy of the present invention.
• alloy l9 even with Mo as high as 6.1 percent, there is in sufficient strengthening to provide adequate high-temperature stress rupture strength. More importantly, however, is the fact that the total amount of Mo and W is sufiiciently high to result in sigma phase formation as measured by the atomic relation ship between those elements of(Mo+W/2)of as high as the 7.6 percent
• the present invention contemplates that relationship to be within the range of 57 percent to inhibit sigma phase formation and precipitation of the proper carbides as described before.
• Alloy 20, a different kind of alloy and outside the scope of the present invention includes Mo and W within the invention range but with the improper relationship one to the other as shown by the(Mo+W/2)of 7.4 percent.
• alloys 5, 1 l and 12 include about the same amount of the sum of titanium and aluminum, it should be noted that alloy 5 forms no sigma phase whereas alloys 1 l and 12 form medium to large amounts of sigma phase. This can be attributed to the improper relationship between the two elements.
• the fact that different kinds of alloys are formed between alloy 5 and alloys 11 and 12 is further substantiated by the stress rupture life, particularly the stability data represented by the l,500 F. tests.
• the alloy 13, although having the proper ratio between Ti and A l does not have sufficient amounts of these elements to provide the required strength. Therefore, the alloy of the present invention defines the relationship between Ti and Al such that the sum of those elements is in the range of about 7.59 percent and that the Ti/Al ratio is greater than one but less than 3:1.
• Alloys include .0l.02 B, balance Ni and incidental impurities C Cr Mo W Ti Al Zr Others 6.0 7. 2.0 6.0 1.0 5. 5 l. 3 9 TB, 0.5 Hf, 0.5 Cb,
• n 30/36/39 3 5 about 0. 15-03 percent C, said carbon percentage being greater than that required for deoxidation and in addition Expressed as l/2 (surface loss/avg. penetration/max. penetration). being sufficient for forming grain boundary carbides; d spec'men corroded 'hroughwt' greater than 13 percent but less than 15.6 percent Cr; From table Vll, it is easily seem that at all temperatures greater than 5 p to 15 P C0; tested, alloy 2 within the scope of the present invention is re 40 Percent markably more resistant to hot corrosion than are all of the P f other tested known alloys, most of which are presently in use Percent in the hot section of gas turbine engines. Percent Another measure of hot corrosion resistance involved a 0-O050s02 P B;
• the W is 3.5-4.5 percent; r the Ti is 4.5-5.5 percent;
• Alloy 10 within the scope of the present invention shows significant and remarkable resistance to weight loss after 500 hours at l,700 F. as compared with alloys known or outside the Al is 2.5-3.5 percent; the B is 0.01-0.02 percent;
• the ls l P f and the Ti/Al ratio is 1.1-2.1
• alloy of the present invention is based on the fact that it is a the Cr is 3 7 4 3 percent; different kind of alloy.
• a different kind of reaction h c i 9.10 percent; product is formed on the surface of the alloy of the present inh M i 3 7 4 3 percent; vention under oxidizing conditions than is formed on the surh w i 1743 ent; faces of certain known nickel base alloys intended for the the Ti is 4.8-5.2 percent; same purpose.
• an X-ray difthe Al is 2.8-3.2 percent;' and fraction study was made on such surfaces after exposure for the Zr is 0.02-0.04 percent.

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Cited By (28)

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• 1968
  • 1968-11-01 US US772796A patent/US3615376A/en not_active Expired - Lifetime
• 1969
  • 1969-10-15 IL IL33198A patent/IL33198A/en unknown
  • 1969-10-16 GB GB50900/69A patent/GB1256017A/en not_active Expired
  • 1969-10-21 DE DE1952877A patent/DE1952877C3/de not_active Expired
  • 1969-10-22 CH CH1578269A patent/CH533683A/de not_active IP Right Cessation
  • 1969-10-25 ES ES372869A patent/ES372869A1/es not_active Expired
  • 1969-10-28 BE BE740895D patent/BE740895A/xx unknown
  • 1969-10-28 SE SE14719/69A patent/SE357983B/xx unknown
  • 1969-10-29 FR FR6937172A patent/FR2022356A1/fr not_active Withdrawn
  • 1969-10-31 FR FR6937503A patent/FR2022386A1/fr not_active Withdrawn
  • 1969-10-31 DK DK576669AA patent/DK124893B/da unknown

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