EP0187573A2 - Nickel base alloy - Google Patents
Nickel base alloy Download PDFInfo
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- EP0187573A2 EP0187573A2 EP85402397A EP85402397A EP0187573A2 EP 0187573 A2 EP0187573 A2 EP 0187573A2 EP 85402397 A EP85402397 A EP 85402397A EP 85402397 A EP85402397 A EP 85402397A EP 0187573 A2 EP0187573 A2 EP 0187573A2
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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%
Definitions
- the present invention relates to a nickel-based alloy hardening by precipitation of a gamma-prime phase.
- Cobalt is one of the typical elements of superalloys. It has been and still is of great importance for producers of superalloys and is moreover considered as a strategic element whose supply has been difficult and could very well become it again. It was and still is an addition to super alloys for many reasons such as: solid solution hardening properties of phase stability, increased ductility and resistance to hot corrosion.
- the present invention relates to a nickel-based superalloy with a lower cobalt content than that usually encountered in superalloys.
- a very elaborate selection and a rigorous balance between the various elements allowed the realization of an alloy with low cobalt content, presenting a judicious distribution of the contents of chromium, molybdenum, tungsten, vanadium, aluminum, titanium, carbon and boron.
- the alloy is characterized by the highly sought-after combination of property of resistance to creep rupture, resistance to corrosion, to oxidation, phase stability and ductility. It is particularly suitable for molding articles such as rotor blades and turbine stators.
- the object of the present invention relates to the development of a nickel-based alloy, hardening by precipitation of gamma prime phase and low in cobalt content.
- the alloy is characterized by the following composition in weight proportions: from 14 to 18% of chromium, from 0.3 to 3% of molybdenum, from 4 to 8% of tungsten, from 0.01 to 1 , 0% vanadium, up to 0.05% tantalum, up to 0.05% niobium, 3.5 to 5.5% aluminum, 1 to 4% titanium, 3 to 7% cobalt, up to 2% iron, 0.01-0.05% carbon, 0.035-0.1 boron, up to 0.1% zirconium, up to 0.01 % nitrogen, up to 0.5% copper, up to 0.12% manganese, up to 3% elements of the rhenium-ruthenium group, up to 0.2% elements rare earth not lowering the starting melting temperature below the gamma-prime phase solvus temperature in the alloy, up to 0.15% of elements of the magnesium-calcium-strontium-barium group, up to 0.1% hafnium and the complement to 100 being essentially nickel, said boron content
- the components of the alloy must balance so as to give a stable alloy, in particular free of sigma phase and other topologically compact phases.
- a weight percentage of chromium of 14 to 18% is provided in the alloy.
- a content of at least 14% is necessary to ensure protection against corrosion.
- the alloy becomes unstable at contents higher than 18%.
- the preferred content is within a range of 15 to 17%.
- a molybdenum weight percentage of 0.3 to 3.0% is provided in the alloy, with a preferred range of 0.8 to 1.8%. Molybdenum is added to harden the solid solution. An excess of molybdenum is detrimental because it tends to prevent the formation of a well adherent oxide layer and as a result it will decrease the corrosion resistance. It is however beneficial to corrosion resistance in a content of less than 3%.
- a weight percentage of tungsten of 4 to 8% is provided in the alloy. Like molybdenum, it contributes to the hardening of the solid solution. Excess tungsten can be detrimental for the same reasons as excess molybdenum. Additions of tungsten, however, are advantageous in that they tend to give the alloy more homogeneous properties. Tungsten tends to segregate in the areas of dendritic nuclei while molybdenum tends to segregate in the interdendritic areas of the alloy. A preferred content of tungsten is between 5 and 7%.
- a weight percentage of vanadium of 0.01 to 1.0% is provided in the alloy, with a preferred content of 0.3 to 0.7%. Vanadium improves the resistance to creep rupture of the alloy, but can be detrimental, in case of excess, resistance to hot corrosion and oxidation, as well as to the stability of the alloy.
- tantalum and niobium there is a maximum limit of 0.05% tantalum and niobium. Higher amounts of tantalum and niobium tend to cause detrimental formation of topologically compact phases. These elements also form large, stable carbides which cannot be dissolved during heat treatments. These large carbides are the sites of initiation of fatigue cracks.
- An aluminum weight percentage of 3.5 to 5.5% is provided in the alloy. It forms the gamma prime phase, the basic mechanism for hardening the alloy and is also necessary to ensure correct resistance to oxidation. Too much aluminum causes excess gamma prime eutectic phase detrimental to the strength of the alloy.
- the preferred aluminum content is between 4 and 5%.
- titanium forms the gamma prime phase. Titanium also increases the hot corrosion resistance of the alloy; its usual proportion is 1.3 to 3.7%. With an excess of titanium, an eta phase (Ni 3 Ti) tends to form. The eta phase lowers the ductility of the alloy.
- the preferred content of titanium is between 1.5 and 2.5%.
- a weight percentage of cobalt of 3 to 7% is provided in the alloy.
- a minimum of 3% is essential for the hardening effect.
- the alloy tends to become structurally unstable when the content becomes greater than 7%.
- the preferred cobalt content is between 4 and 6%.
- a maximum limit of 2% iron is tolerated. Iron tends to alter the mechanical properties of the alloy at high temperatures. The maximum preferred content is 0.5%.
- Carbon and boron are present in the alloy in the respective weight proportions of 0.01 to 0.05% and 0.035 to 0.1%. They together form carbo-borides and borides. In the best conditions of rupture creep resistance and ductility, the alloys have indicated contents of boron and carbon, the content of boron being greater than the carbon content. The resistance drops to 900 ° C with an excess of carbon. It also results from an excess of boron the formation of too many borides at the grain boundaries which adversely affect the ductility and the strength.
- the preferred carbon content is between 0.02 and 0.04%, the preferred boron content is between 0.06 and 0.09%.
- zirconium Up to 0.1% zirconium can be added to the alloy since the zirconium strengthens the grain boundaries and counteracts the influence of sulfur. Higher quantities of zirconium would tend to form a harmful Ni 5Zr phase at the grain boundaries which would contribute to the embrittlement of the alloy. In general, zirconium is present in the alloy, with a minimum content of 0.015%.
- the maximum percentages of the elements of the magnesium-calcium-strontium-barium group is usually 0.05%.
- the presence of hafnium is usually tolerated in an amount equal to or less than 0.05%.
- Hafnium tends to form carbides insensitive to heat treatments.
- Alloy B contains vanadium under the conditions defined for the present invention while alloy A does not contain it. Alloy A is free of vanadium.
- the Md values of alloys A and B are respectively 0.961 and 0.968. A study of the microstructures of the two alloys, however, revealed their instability although alloys whose Md value is less than or equal to 0.97 generally fall within the present invention.
- the value Md of the alloy A is incompatible with the value of the data, that of B is located in a poorly defined zone.
- the value of Md should preferably be equal to or less than 0.967 for the invention.
- alloys A and B demonstrate the effects of vanadium.
- Alloy B which contains vanadium has a higher Md value than alloy A which does not contain it. Therefore, the vanadium content must be carefully controlled so as to comply with the maximum value of 1.0% of the invention and, preferably, a maximum value of 0.7%.
- Alloy D has a cobalt content within the range of the invention, while alloy C does not contain it.
- the respective values Md of the alloys C and D are 0.966 and 0.963. A study of the microstructures of these alloys revealed their stability. In the present invention, the Md value of the alloys is less than or equal to 0.970.
- alloys H and I in carbon and boron remain within the limits of the present invention.
- the carbon contents of alloys E and G are excessive; (> 0.05% carbon).
- the boron contents of E and F are too low (less than 0.035% boron).
- the boron content of F is not greater than the carbon content.
- the study of the microstructures of each of these alloys has shown their stability.
- the alloys according to the present invention have a value of Md less than or equal to 0.970.
- Table IX very clearly shows that the alloy of the present invention has advantageous and combined characteristics of breaking strength and ductility.
- Alloy J was subjected to an oxidation test lasting 500 hours at a temperature of 1000 ° C. This test was carried out in one hour cycles at the end of which the samples are cooled to room temperature and then reheated to 1000 ° C. The results were very positive, no change in weight was observed. Oxidation only occurred at a depth of 50 mm on a first test piece and 80 / mm on a second.
- Alloy K is in accordance with the present invention while alloy L is not because it comprises tantalum.
- the alloys M and N agree with the data of the present invention.
- the study of their microstructure has demonstrated their stability and their respective Md values are 0.963 and 0.969.
- Alloy specimens M and N were heated to the temperature of 850 ° C. under an atmosphere resulting from the combustion of kerosene loaded with sulfur and air loaded with sodium chloride. This ambient environment is analogous to that encountered in gas turbines. Three times a day the test pieces are cooled to room temperature and then reheated to 850 ° C.
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Abstract
Alliage à matrice à base de nickel, à durcissement par précipitation de phase gamma-prime, caractérisé par une combinaison très advantageuse de propriétés, en particulier "temps de rupture / résistance à la corrosion à chaud et à l'oxydation / stabilité et ductilité". L'alliage contient de 14 à 18% de chrome, de 0,3 à 3% de molybdène, de 4 à 8% de tungstène, de 0,01 à 1,0% de vanadium, de 3,5 à 5,5% d'aluminium, de 1 à 4% de titane, de 3 à 7% de cobalt, de 0,01 à 0,05% de carbone et de 0,035 à 0,1% de bore.Nickel base matrix alloy, hardening by gamma-prime phase precipitation, characterized by a very advantageous combination of properties, in particular "breaking time / resistance to hot corrosion and to oxidation / stability and ductility" . The alloy contains 14-18% chromium, 0.3-3% molybdenum, 4-8% tungsten, 0.01-1.0% vanadium, 3.5-5.5 % aluminum, 1 to 4% titanium, 3 to 7% cobalt, 0.01 to 0.05% carbon and 0.035 to 0.1% boron.
Description
La présente invention concerne un alliage à base de nickel à durcissement par précipitation d'une phase gamma-prime.The present invention relates to a nickel-based alloy hardening by precipitation of a gamma-prime phase.
Le cobalt est l'un des éléments typique des super-alliages. Il a été et est encore d'une grande importance pour les producteurs de super-alliages et est de plus considéré comme un élément stratégique dont l'approvisionnement a été difficile et pourrait très bien le redevenir. Il a été et est encore un élément d'addition aux super alliages pour de multiples raisons telles que : propriétés de durcissement en solution solide de stabilité de phase, augmentation de ductilité et résistance à la corrosion à chaud.Cobalt is one of the typical elements of superalloys. It has been and still is of great importance for producers of superalloys and is moreover considered as a strategic element whose supply has been difficult and could very well become it again. It was and still is an addition to super alloys for many reasons such as: solid solution hardening properties of phase stability, increased ductility and resistance to hot corrosion.
La présente invention concerne un super-alliage à base de nickel avec un taux de cobalt inférieur à celui habituellement rencontré dans les super-alliages. Une sélection très élaborée et un équilibre rigoureux entre les divers éléments a permis la réalisation d'un alliage à faible teneur en cobalt, présentant une répartition judicieuse des teneurs en chrome, molybdène, tungstène, vanadium, aluminium, titane, carbone et bore.The present invention relates to a nickel-based superalloy with a lower cobalt content than that usually encountered in superalloys. A very elaborate selection and a rigorous balance between the various elements allowed the realization of an alloy with low cobalt content, presenting a judicious distribution of the contents of chromium, molybdenum, tungsten, vanadium, aluminum, titanium, carbon and boron.
Selon la présente invention, l'alliage est caractérisé par la combinaison très recherchée de propriété de résistance au fluage rupture, de résistance à la corrosion, à l'oxydation, de stabilité de phase et de ductilité. Il est particulièrement adapté au moulage d'articles tels que aubes de rotor et de stator de turbine.According to the present invention, the alloy is characterized by the highly sought-after combination of property of resistance to creep rupture, resistance to corrosion, to oxidation, phase stability and ductility. It is particularly suitable for molding articles such as rotor blades and turbine stators.
De nombreux documents décrivent des super-alliages à base de nickel incluant la liste des brevets américains suivante : 2 515 185, 2 570 193, 2 793 108, 2 809 110, 2 975 051, 3 093 476, 3 164 465, 3 260 505, 3 561 955, 3 677 747, 3 890 816, 3 941 590, 3 976 480, 4 039 330, 4 078 951, 4 083 704, 4 093 476, 4 140 555, US-Re 29 920 et la demande déposée sous le n° 270 745 du 6 décembre 1981.Numerous documents describe nickel-based superalloys including the following list of US patents: 2,515,185, 2,570,193, 2,793,108, 2,809,110, 2,975,051, 3,093,476, 3,164,465, 3,260 505, 3561 955, 3,677,747, 3,890,816, 3,941,590, 3,976,480, 4,039,330, 4,078,951, 4,083,704, 4,093,476, 4,140,555, US-Re 29,920 and the application filed under No. 270 745 of December 6, 1981.
Aucun de ces documents ne divulgue l'alliage de.la présente invention, ni ses fourchettes de composition très spécifiques. L'objet de la présente invention a trait à l'élaboration d'un alliage à base de nickel, à durcissement par précipitation de phase gamma prime et à faible teneur en cobalt.None of these documents discloses the alloy of the present invention, nor its very specific composition ranges. The object of the present invention relates to the development of a nickel-based alloy, hardening by precipitation of gamma prime phase and low in cobalt content.
Selon l'invention, l'alliage est caractérisé par la composition suivante en proportions pondérales : de 14 à 18% de chrome, de 0,3 à 3% de molybdène, de 4 à 8% de tungstène, de 0,01 à 1,0% de vanadium, jusqu'à 0,05% de tantale, jusqu'à 0,05% de niobium, de 3,5 à 5,5% d'aluminium, de 1 à 4% de titane, de 3 à 7% de cobalt, jusqu'à 2% de fer, de 0,01 à 0,05% de carbone, de 0,035 à 0,1 de bore, jusqu'à 0,1% de zirconium, jusqu'à 0,01% d'azote, jusqu'à 0,5% de cuivre, jusqu'à 0,12% de manganèse, jusqu'à 3% d'éléments du groupe rhénium- ruthénium, jusqu'à 0,2% d'éléments de terre rare n'abaissant pas la température de fusion commençante au-dessous de la température de solvus de la phase gamma-prime dans l'alliage, jusqu'à 0,15% d'éléments du groupe magnésium-calcium-strontium-baryum, jusqu'à 0,1% de hafnium et le complément à 100 étant essentiellement en nickel, ladite teneur en bore étant toujours supérieure à ladite teneur en carbone. A titre d'exemple, les éléments de terre rare sont le cerium et le lanthane.According to the invention, the alloy is characterized by the following composition in weight proportions: from 14 to 18% of chromium, from 0.3 to 3% of molybdenum, from 4 to 8% of tungsten, from 0.01 to 1 , 0% vanadium, up to 0.05% tantalum, up to 0.05% niobium, 3.5 to 5.5% aluminum, 1 to 4% titanium, 3 to 7% cobalt, up to 2% iron, 0.01-0.05% carbon, 0.035-0.1 boron, up to 0.1% zirconium, up to 0.01 % nitrogen, up to 0.5% copper, up to 0.12% manganese, up to 3% elements of the rhenium-ruthenium group, up to 0.2% elements rare earth not lowering the starting melting temperature below the gamma-prime phase solvus temperature in the alloy, up to 0.15% of elements of the magnesium-calcium-strontium-barium group, up to 0.1% hafnium and the complement to 100 being essentially nickel, said boron content always being greater than said carbon content. For example, the rare earth elements are cerium and lanthanum.
Les composants de l'alliage doivent s'équilibrer de manière à donner un alliage stable, en particulier exempt de phase sigma et autres phases topologiquement compactes.The components of the alloy must balance so as to give a stable alloy, in particular free of sigma phase and other topologically compact phases.
Le présent alliage a une valeur Md est inférieure ou égale à 0,97, de préférence 0,967. La valeur Md est calculée au moyen de la formule suivante :
- Md = 0,717(MNi) + 0,777(MCo) + 2,271(MTi)
- + 1,900(MAl) + 1,655(MW) + 1,550(MMo)
- + 1,142(MCr) + 1,543(MV) + 2,944(MZr)
- Md = 0.717 (M Ni ) + 0.777 (M Co ) + 2.271 (M Ti )
- + 1,900 (M Al ) + 1,655 (M W ) + 1,550 (M Mo )
- + 1.142 (M Cr ) + 1.543 (M V ) + 2.444 (M Zr )
Les hypothèses suivantes sont retenues pour déterminer la contribution des éléments présents dans les phases borures, carbures et gamma :
- a) en supposant que 70% des atomes de bore entrent en combinaison pour former des borures de stoechiométrie suivante (Cr0,72 W0,1 Mo0,11 Ti0,02 V O,02 Ni0.02)B2 la matrice se trouve allégée de la quantité de chaque élément utilisé ;
- b) en supposant que 30% des atomes de bore entrent en combinaison pour former un borure de stoechiométrie suivante (Cr0,87 W0,07 Mo0,06)23 (B,C)6 dans laquelle (B,C) représente la quantité de bore restante et tout le carbone disponible ; la matrice se trouve allégée de la quantité de chaque élément utilisé ;
- c) les coefficients de partage ci-dessous sont utilisés pour calculer la répartition des éléments de la phase gamma :
- Aluminium RAl = 0,727 PAl
- Titane RTi O,412 P Ti
- Chrome RCr = 1,619 PCr
- Tungstène RW = 0,484 Pw
- Cobalt RCo = 1,487 PCo
- Zirconium RZr = 1,818 P Zr
- Molybdène RMo = 1,818 PMo
- Vanadium Rv = 1,818 PV
- Nickel RNi = 0,863 PNi
dans lesquels,- Ri = la quantité de l'élément i dans la phase gamma
- Pi = la quantité de l'élément i dans l'alliage après formation des borures. La formule
permet le calcul du pourcentage atomique Mi de chaque élément dans la phase gamma.
- a) assuming that 70% of the boron atoms enter into combination to form borides of the following stoichiometry (Cr 0.72 W 0.1 Mo 0.11 Ti 0.02 V O , 02 Ni 0.02 ) B 2 the matrix finds reduced the amount of each element used;
- b) assuming that 30% of the boron atoms enter into combination to form a boride with the following stoichiometry (Cr 0.87 W 0.07 Mo0.06) 23 (B, C) 6 in which (B, C) represents the remaining boron and all available carbon; the matrix is reduced by the quantity of each element used;
- c) the following partition coefficients are used to calculate the distribution of the elements of the gamma phase:
- Aluminum R Al = 0.727 P Al
- Titanium R Ti O, 412 P T i
- Chrome R Cr = 1,619 P Cr
- Tungsten R W = 0.484 P w
- Cobalt R Co = 1.487 P Co
- Zirconium R Zr = 1.818 P Z r
- Molybdenum R Mo = 1.818 P Mo
- Vanadium R v = 1.818 P V
- Nickel R Ni = 0.863 P Ni
wherein,- R i = the quantity of element i in the gamma phase
- P i = the quantity of element i in the alloy after formation of the borides. The formula
allows the calculation of the atomic percentage M i of each element in the gamma phase.
Un pourcentage pondéral de chrome de 14 à 18% est prévu dans l'alliage. Une teneur d'au moins 14% est nécessaire pour assurer la protection contre la corrosion. L'alliage devient instable à des teneurs supérieures à 18%. La teneur préférée est comprise dans une fourchette de 15 à 17%.A weight percentage of chromium of 14 to 18% is provided in the alloy. A content of at least 14% is necessary to ensure protection against corrosion. The alloy becomes unstable at contents higher than 18%. The preferred content is within a range of 15 to 17%.
Un pourcentage pondéral de molybdène de 0,3 à 3,0% est prévu dans l'alliage, avec une fourchette préférée de 0,8 à 1,8%. Le molybdène est ajouté pour obtenir un durcissement de la solution solide. Un excès de molybdène est préjudiciable, car il tend à empêcher la formation d'une couche d'oxyde bien adhérente et en conséquence, il diminuera la résistance à la corrosion. Il est toutefois bénéfique à la résistance à la corrosion dans une teneur inférieure à 3%.A molybdenum weight percentage of 0.3 to 3.0% is provided in the alloy, with a preferred range of 0.8 to 1.8%. Molybdenum is added to harden the solid solution. An excess of molybdenum is detrimental because it tends to prevent the formation of a well adherent oxide layer and as a result it will decrease the corrosion resistance. It is however beneficial to corrosion resistance in a content of less than 3%.
Un pourcentage pondéral de tungstène de 4 à 8% est prévu dans l'alliage. Ainsi que le molybdène, il concourt au durcissement de la solution solide. L'excès de tungstène peut être préjudiciable pour les même raisons que l'excès de molybdène. Les additions de tungstène sont toutefois avantageuses, dans la mesure où elles tendent à donner à l'alliage des propriétés plus homogènes. Le tungstène tend à se ségréger dans les aires de noyaux dendritiques tandis que le molybdène tend à se segréger dans les aires interdendritiques de l'alliage. Une teneur préférée de tungstène se situe entre 5 et 7%.A weight percentage of tungsten of 4 to 8% is provided in the alloy. Like molybdenum, it contributes to the hardening of the solid solution. Excess tungsten can be detrimental for the same reasons as excess molybdenum. Additions of tungsten, however, are advantageous in that they tend to give the alloy more homogeneous properties. Tungsten tends to segregate in the areas of dendritic nuclei while molybdenum tends to segregate in the interdendritic areas of the alloy. A preferred content of tungsten is between 5 and 7%.
Un pourcentage pondéral de vanadium de 0,01 à 1,0% est prévu dans l'alliage, avec une teneur préférée de 0,3 à 0,7%. Le vanadium améliore la résistance au fluage rupture de l'alliage, mais peut être préjudiciable, en cas d'excès, à la résistance à la corrosion à chaud et à l'oxydation, aussi bien qu'à la stabilité de l'alliage.A weight percentage of vanadium of 0.01 to 1.0% is provided in the alloy, with a preferred content of 0.3 to 0.7%. Vanadium improves the resistance to creep rupture of the alloy, but can be detrimental, in case of excess, resistance to hot corrosion and oxidation, as well as to the stability of the alloy.
Une limite maximale de 0,05% de tantale et de niobium est prévue. Des quantités supérieures de tantale et de niobium tendent à provoquer la formation préjudiciable de phases topologiquement compactes. Ces éléments forment également des carbures stables de grande dimension ne pouvant être mis en solution lors des traitements thermiques. Ces carbures de grande dimension sont les sites d'amorçage des criques de fatigue.There is a maximum limit of 0.05% tantalum and niobium. Higher amounts of tantalum and niobium tend to cause detrimental formation of topologically compact phases. These elements also form large, stable carbides which cannot be dissolved during heat treatments. These large carbides are the sites of initiation of fatigue cracks.
Un pourcentage pondéral d'aluminium de 3,5 à 5,5% est prévu dans l'alliage. Il forme la phase gamma prime, mécanisme de base du durcissement de l'alliage et est aussi nécessaire pour assurer une résistance correcte à l'oxydation. Une quantité trop importante d'aluminium provoque un excès de phase gamma prime eutectique préjudiciable à la résistance de l'alliage. La teneur préférée en aluminium est comprise entre 4 et 5%.An aluminum weight percentage of 3.5 to 5.5% is provided in the alloy. It forms the gamma prime phase, the basic mechanism for hardening the alloy and is also necessary to ensure correct resistance to oxidation. Too much aluminum causes excess gamma prime eutectic phase detrimental to the strength of the alloy. The preferred aluminum content is between 4 and 5%.
Un pourcentage pondéral de titane de 1 à 4% est prévu dans l'alliage. Comme l'aluminium, le titane forme la phase gamma prime. Le titane augmente aussi la résistance à la corrosion à chaud de l'alliage ; sa proportion habituelle est de 1,3 à 3,7%. Avec un excès de titane, une phase êta (Ni3Ti) tend à se former. La phase êta abaisse la ductilité de l'alliage. La teneur préférée de titane est comprise entre 1,5 et 2,5%.A weight percentage of titanium of 1 to 4% is provided in the alloy. Like aluminum, titanium forms the gamma prime phase. Titanium also increases the hot corrosion resistance of the alloy; its usual proportion is 1.3 to 3.7%. With an excess of titanium, an eta phase (Ni 3 Ti) tends to form. The eta phase lowers the ductility of the alloy. The preferred content of titanium is between 1.5 and 2.5%.
Un pourcentage pondéral de cobalt de 3 à 7% est prévu dans l'alliage. Un minimum de 3% est indispensable à l'effet de durcissement. L'alliage tend à devenir structurellement instable quand la teneur devient supérieure à 7%. La teneur préférée en cobalt est comprise entre 4 et 6%.A weight percentage of cobalt of 3 to 7% is provided in the alloy. A minimum of 3% is essential for the hardening effect. The alloy tends to become structurally unstable when the content becomes greater than 7%. The preferred cobalt content is between 4 and 6%.
Une limite maximale de 2% de fer est tolérée. Le fer tend à altérer les propriétés mécaniques de l'alliage à haute température. La teneur préférée maximale est de 0,5%.A maximum limit of 2% iron is tolerated. Iron tends to alter the mechanical properties of the alloy at high temperatures. The maximum preferred content is 0.5%.
Le carbone et le bore sont présents dans l'alliage dans les proportions pondérales respectives de 0,01 à 0,05% et 0,035 à 0,1%. Ils forment ensemble des carbo-borures et des borures. Dans les meilleures conditions de résistance en fluage rupture et de ductilité, les alliages présentent des teneurs indiquées de bore et de carbone, la teneur en bore étant supérieure à la teneur en carbone. La résistance chute à 900°C avec un excès de carbone. Il résulte par ailleurs d'un excès de bore la formation de trop de borures aux joints de grains qui affectent défavorablement la ductilité et la résistance. La teneur préférée en carbone est comprise entre 0,02 et 0,04%, la teneur préférée en bore est comprise entre 0,06 à 0,09%.Carbon and boron are present in the alloy in the respective weight proportions of 0.01 to 0.05% and 0.035 to 0.1%. They together form carbo-borides and borides. In the best conditions of rupture creep resistance and ductility, the alloys have indicated contents of boron and carbon, the content of boron being greater than the carbon content. The resistance drops to 900 ° C with an excess of carbon. It also results from an excess of boron the formation of too many borides at the grain boundaries which adversely affect the ductility and the strength. The preferred carbon content is between 0.02 and 0.04%, the preferred boron content is between 0.06 and 0.09%.
Jusqu'à 0,1% de zirconium peut être ajouté à l'alliage puisque le zirconium renforce les joints de grains et contrebalance l'influence du soufre. Des quantités supérieures de zirconium tenderaient à former une phase néfaste Ni 5Zr aux joints de grains qui contribuerait à la fragilisation de l'alliage. En général, le zirconium est présent dans l'alliage, avec une teneur minimale de 0,015%.Up to 0.1% zirconium can be added to the alloy since the zirconium strengthens the grain boundaries and counteracts the influence of sulfur. Higher quantities of zirconium would tend to form a harmful Ni 5Zr phase at the grain boundaries which would contribute to the embrittlement of the alloy. In general, zirconium is present in the alloy, with a minimum content of 0.015%.
On admet un maximum de 0,01% d'azote qui tend à former des nitrures de titane et d'autres nitrures nuisibles qui sont à l'origine de criques de fatigue.We admit a maximum of 0.01% of nitrogen which tends to form titanium nitrides and other harmful nitrides which are at the origin of fatigue cracks.
Dans les limites définies ci-dessus, divers autres éléments peuvent être incorporés à l'alliage. Les pourcentages maximaux des éléments du groupe magnésium-calcium-strontium-baryum est habituellement de 0,05%. La présence d'hafnium est habituellement tolérée dans une proportion égale ou inférieure à 0,05%. L'hafnium tend à former des carbures insensibles aux traitements thermiques.Within the limits defined above, various other elements can be incorporated into the alloy. The maximum percentages of the elements of the magnesium-calcium-strontium-barium group is usually 0.05%. The presence of hafnium is usually tolerated in an amount equal to or less than 0.05%. Hafnium tends to form carbides insensitive to heat treatments.
Les exemples suivants illustrent plusieurs aspects de l'invention.The following examples illustrate several aspects of the invention.
Deux alliages (A et B) ont été élaborés suivant les procédés courants de la fusion par induction sous vide. La composition chimique de chacun de ces alliages figure au tableau I ci-dessous.
L'alliage B contient du vanadium dans les conditions définies pour la présente invention alors que l'alliage A n'en contient pas. L'alliage A est dépourvu de vanadium.Alloy B contains vanadium under the conditions defined for the present invention while alloy A does not contain it. Alloy A is free of vanadium.
Ces alliages ont été coulés et ont subi les traitements thermiques énoncés ci-dessous
- 1163°C (2125°F) = 2 heures + refroidissement à l'air
- 927°C (1700°F) = 16 heures + refroidissement à l'air
et testés en fluage rupture dans les conditions suivantes :
- 982°C (1800°F)/152 MPa (22ksi)
- 760°C (1400°F)/620 MPa (90ksi)
- 1163 ° C (2125 ° F) = 2 hours + air cooling
- 927 ° C (1700 ° F) = 16 hours + air cooling
and tested for creep rupture under the following conditions:
- 982 ° C (1800 ° F) / 152 MPa (22ksi)
- 760 ° C (1400 ° F) / 620 MPa (90ksi)
Le résultat des essais figure au tableau II ci-dessous :
L'effet bénéfique du vanadium est nettement démontré au tableau II. Le temps de rupture de l'alliage B qui contient du vanadium est sensiblement supérieur à celui de l'alliage A qui n'en contient pas quand les deux alliages sont soumis aux mêmes conditions d'essai.The beneficial effect of vanadium is clearly demonstrated in Table II. The rupture time of alloy B which contains vanadium is significantly greater than that of alloy A which does not contain it when the two alloys are subjected to the same test conditions.
Les valeurs Md des alliages A et B sont respectivement de 0,961 et 0,968. Une étude des microstructures des deux alliages a toutefois révélé leur instabilité bien que des alliages dont la valeur de Md est inférieur ou égale à 0,97 entrent généralement dans la présente invention. La valeur Md de l'alliage A est incompatible avec la valeur des données, celle de B se situe dans une zone mal définie. La valeur de Md doit être de préférence égale ou inférieure à 0,967 pour l'invention.The Md values of alloys A and B are respectively 0.961 and 0.968. A study of the microstructures of the two alloys, however, revealed their instability although alloys whose Md value is less than or equal to 0.97 generally fall within the present invention. The value Md of the alloy A is incompatible with the value of the data, that of B is located in a poorly defined zone. The value of Md should preferably be equal to or less than 0.967 for the invention.
Les valeurs Md des alliages A et B démontrent les effets du vanadium. L'alliage B qui contient du vanadium a une valeur Md plus élevée que l'alliage A qui n'en contient pas. De ce fait, la teneur en vanadium doit être soigneusement contrôlée de manière à respecter la valeur maximale de 1,0% de l'invention et, de préférence, une valeur maximale de 0,7%.The Md values of alloys A and B demonstrate the effects of vanadium. Alloy B which contains vanadium has a higher Md value than alloy A which does not contain it. Therefore, the vanadium content must be carefully controlled so as to comply with the maximum value of 1.0% of the invention and, preferably, a maximum value of 0.7%.
Deux autres alliages (C et D) ont été élaborés suivant les procédés courants de la fusion par induction sous vide. La composition chimique de chacun de ces alliages figure au tableau III ci-après :
L'alliage D présente une teneur en cobalt comprise dans la fourchette de l'invention alors que l'alliage C n'en contient pas.Alloy D has a cobalt content within the range of the invention, while alloy C does not contain it.
Ces alliages ont été coulés et ont subi les traitements thermiques énoncés ci-dessous :
- 1163°C (2125°F) = 2 heures + refroidissement à l'air
- 927°C (1700°F) = 16 heures + refroidissement à l'air ,
et testés en fluage rupture dans les conditions suivantes :
- 982°C (1800°F)/152MPa (22ksi)
- 760°C (1400°F)/620MPa (90ksi).
- 1163 ° C (2125 ° F) = 2 hours + air cooling
- 927 ° C (1700 ° F) = 16 hours + air cooling,
and tested for creep rupture under the following conditions:
- 982 ° C (1800 ° F) / 152MPa (22ksi)
- 760 ° C (1400 ° F) / 620MPa (90ksi).
Les résultats de ces essais figurent au tableau IV ci-après :
L'effet bénéfique du cobalt est nettement démontré par le tableau IV. Le temps de rupture de l'alliage D qui contient du cobalt est sensiblement supérieur à celui de l'alliage C qui n'en contient que quelques traces quand les deux alliages sont soumis aux mêmes essais.The beneficial effect of cobalt is clearly demonstrated in Table IV. The rupture time of alloy D which contains cobalt is appreciably longer than that of alloy C which contains only a few traces when the two alloys are subjected to the same tests.
Les valeurs respectives Md des alliages C et D sont de 0,966 et 0,963. Une étude des microstructures de ces alliages a révélé leur stabilité. Dans la présente invention, la valeur Md des alliages est inférieure ou égale à 0,970.The respective values Md of the alloys C and D are 0.966 and 0.963. A study of the microstructures of these alloys revealed their stability. In the present invention, the Md value of the alloys is less than or equal to 0.970.
Cinq autres alliages (E,F,G,H et I) ont été élaborés suivant les procédés courants de la fusion par induction sous vide. La composition chimique de ces alliages figure au tableau V ci-après :
Les teneurs des alliages H et I en carbone et en bore restent dans les limites de la présente invention. Les teneurs en carbone des alliages E et G sont excessives ; ( > 0,05% de carbone). Les teneurs en bore de E et F sont trop faibles (moins de 0,035% de bore). En outre , la teneur en bore de F n'est pas supérieure à la teneur en carbone.The contents of alloys H and I in carbon and boron remain within the limits of the present invention. The carbon contents of alloys E and G are excessive; (> 0.05% carbon). The boron contents of E and F are too low (less than 0.035% boron). In addition, the boron content of F is not greater than the carbon content.
Ces alliages ont été coulés et ont subi les traitements thermiques suivants :
- 1163°C (2125°F) = 2 heures + refroidissement à l'air 927°C (1700°F) = 16 heures + refroidissement à l'air
et testés en fluage rupture et ductilité dans les conditions suivantes :
- 982°C (1800°F) / 152MPa (22ksi)
- 760°C (1400°F) / 620MPa (90ksi)
- 1163 ° C (2125 ° F) = 2 hours + air cooling 927 ° C (1700 ° F) = 16 hours + air cooling
and tested for rupture creep and ductility under the following conditions:
- 982 ° C (1800 ° F) / 152MPa (22ksi)
- 760 ° C (1400 ° F) / 620MPa (90ksi)
Les résultats des essais figurent au tableau VI ci-après :
Dans le tableau VI les effets bénéfiques du carbone et du bore apparaissent nettement dans la limite des fourchettes de teneurs définies dans la présente invention. Les alliages H et I y présentent la meilleure combinaison temps de rupture/ductilité et leurs teneurs en bore et carbone sont dans les fourchettes de l'invention. Dans les autres cas, les teneurs en carbone et/ou bore sortent de ces fourchettes.In Table VI the beneficial effects of carbon and boron appear clearly within the limits of the ranges of contents defined in the present invention. Alloys H and I present the best combination rupture time / ductility and their boron and carbon contents are within the ranges of the invention. In the other cases, the carbon and / or boron contents leave these ranges.
Les valeurs Md des alliages E, F, G, H et I figurent au tableau VII ci-après :
L'étude des microstructures de chacun de ces alliages a montré leur stabilité. Les alliages selon la présente invention ont une valeur de Md inférieure ou égale à 0,970.The study of the microstructures of each of these alloys has shown their stability. The alloys according to the present invention have a value of Md less than or equal to 0.970.
Un autre alliage (J) a été élaboré suivant les procédés courants de la fusion par induction sous vide. La composition chimique de cet alliage figure au tableau VIII ci-après :
La valeur Md de l'alliage J est 0,964. Sa microstructure a été étudiée et s'est révélée stable. L'alliage J a été coulé et a subi les traitements thermiques définis ci-après :
- 1163°C (2125°F) = 2 heures + refroidissement à l'air
- 927°C (1700°F) = 16 heures + refroidissement à l'air
et testés en fluage rupture et en ductilité dans les conditions suivantes :
- 980°C (1800°F)/152MPa (22ksi)
- 760°C (1400°F)/620MPa (90ksi)
- 1163 ° C (2125 ° F) = 2 hours + air cooling
- 927 ° C (1700 ° F) = 16 hours + air cooling
and tested for rupture creep and ductility under the following conditions:
- 980 ° C (1800 ° F) / 152MPa (22ksi)
- 760 ° C (1400 ° F) / 620MPa (90ksi)
Les résultats de ces essais figurent au tableau IX ci-après :
L'alliage J a été soumis à un essai d'oxydation d'une durée de 500 heures à la température de 1000°C. Cet essai a été effectué par cycles d'une heure à l'issue desquels les échantillons sont refroidis à la température ambiante puis rechauffés à 1000°C. Les résultats ont été très positifs, aucun changement de poids n'a été observé. L'oxydation ne s'est produite que sur une profondeur de 50 Mm sur une première éprouvette et de 80 /Mm sur une seconde.Alloy J was subjected to an oxidation test lasting 500 hours at a temperature of 1000 ° C. This test was carried out in one hour cycles at the end of which the samples are cooled to room temperature and then reheated to 1000 ° C. The results were very positive, no change in weight was observed. Oxidation only occurred at a depth of 50 mm on a first test piece and 80 / mm on a second.
Deux autres alliages (K et L) ont été élaborés suivant les procédés courants de la fusion par induction sous vide. La composition chimique de ces alliages figure au tableau X ci-après :
L'alliage K est en conformité avec la présente invention tandis que l'alliage L ne l'est pas car il comporte du tantale.Alloy K is in accordance with the present invention while alloy L is not because it comprises tantalum.
Une étude de la microstructure des alliages K et L a révélé que l'alliage L est instable. D'autre part l'alliage K s'est révélé stable. L'alliage K présente une valeur Md de 0,966 . La valeur Md de l'alliage L ne peut être indiquée puisque les bases de calcul ne tiennent pas compte du tantale. L'homme du métier comprendra cependant que la valeur Md de l'alliage L excédera nettement 0,970.A study of the microstructure of the K and L alloys revealed that the L alloy is unstable. On the other hand, the alloy K was found to be stable. Alloy K has an Md value of 0.966. The value Md of the alloy L cannot be indicated since the bases of calculation do not take tantalum into account. Those skilled in the art will however understand that the value Md of the alloy L will clearly exceed 0.970.
Deux autres alliages (M et N) ont été élaborés suivant les procédés courants de la fusion par induction sous vide. La composition chimique de ces alliages figure au tableau XI ci-après :
Les alliages M et N concordent avec les données de la présente invention. L'étude de leur microstructure a démontré leur stabilité et leurs valeurs Md respectives sont 0,963 et 0,969.The alloys M and N agree with the data of the present invention. The study of their microstructure has demonstrated their stability and their respective Md values are 0.963 and 0.969.
Les alliages M et N ont été coulés et ont subi les traitements thermiques définis ci-après :
- 1163°C(2125°F) = 2 heures + refroidissement à l'air
- 927°C(1700°F) = 16 heures + refroidissement à l'air
et testés pour leur résistance à la corrosion à chaud.Alloys M and N were cast and underwent the heat treatments defined below:
- 1163 ° C (2125 ° F) = 2 hours + air cooling
- 927 ° C (1700 ° F) = 16 hours + air cooling
and tested for their resistance to hot corrosion.
Des éprouvettes d'alliage M et N ont été chauffées à la température de 850°C sous atmosphère résultant de la combustion de kérozène chargé en soufre et d'air chargé de chlorure de sodium. Ce milieu ambiant est analogue à celui rencontré dans les turbines à gaz. Trois fois par jour les éprouvettes sont refroidies à la température ambiante puis réchauffées à 850°C.Alloy specimens M and N were heated to the temperature of 850 ° C. under an atmosphere resulting from the combustion of kerosene loaded with sulfur and air loaded with sodium chloride. This ambient environment is analogous to that encountered in gas turbines. Three times a day the test pieces are cooled to room temperature and then reheated to 850 ° C.
Les résultats obtenus ont été positifs comparativement aux alliages connus. L'alliage M n'a présenté aucun signe d'écaillage d'oxyde avant 253 heures effectives etl'alliage N n'a présenté aucun signe d'effritement par oxydation après 500 heures. La cause de la supériorité des performances de l'alliage N sont bien connues ; on peut l'attribuer à une teneur supérieure en chrome et dans une certaine mesure à une teneur supérieure en molybdène.The results obtained were positive compared to known alloys. Alloy M showed no signs of oxide flaking before 253 effective hours and alloy N showed no signs of oxidative spalling after 500 hours. The cause of the superior performance of the N alloy is well known; it can be attributed to a higher chromium content and to a certain extent to a higher molybdenum content.
Il sera évident à un homme du métier que les principes définis ci-dessus, en corrélation avec les exemples spécifiques énoncés plus haut suggéreront différentes applications et modifications qui ne sortiront pas du cadre de la présente invention, la portée de la protection définie par les revendications n'étant pas par conséquent limitée aux exemples décrits.It will be obvious to a person skilled in the art that the principles defined above, in correlation with the specific examples set out above will suggest different applications and modifications which do not depart from the scope of the present invention, the scope of the protection defined by the claims. therefore not being limited to the examples described.
Claims (18)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT85402397T ATE36009T1 (en) | 1984-12-10 | 1985-12-04 | NICKEL BASED ALLOY. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US679725 | 1984-12-10 | ||
| US06/679,725 US4629521A (en) | 1984-12-10 | 1984-12-10 | Nickel base alloy |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0187573A2 true EP0187573A2 (en) | 1986-07-16 |
| EP0187573A3 EP0187573A3 (en) | 1986-07-30 |
| EP0187573B1 EP0187573B1 (en) | 1988-07-27 |
Family
ID=24728092
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP85402397A Expired EP0187573B1 (en) | 1984-12-10 | 1985-12-04 | Nickel base alloy |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US4629521A (en) |
| EP (1) | EP0187573B1 (en) |
| JP (1) | JPS61139633A (en) |
| AT (1) | ATE36009T1 (en) |
| AU (1) | AU574538B2 (en) |
| BR (1) | BR8505667A (en) |
| CA (1) | CA1255518A (en) |
| DE (1) | DE3563984D1 (en) |
| IL (1) | IL77135A (en) |
| ZA (1) | ZA858123B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2194960A (en) * | 1986-03-17 | 1988-03-23 | Stuart L Adelman | Improved superalloy compositions and articles |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5670929B2 (en) | 2012-02-07 | 2015-02-18 | 三菱マテリアル株式会社 | Ni-based alloy forging |
| JP6532182B2 (en) | 2013-08-06 | 2019-06-19 | 日立金属株式会社 | Ni-based alloy, Ni-based alloy for gas turbine combustor, gas turbine combustor member, liner member, transition piece member, liner, transition piece |
| CN105463257B (en) * | 2015-12-08 | 2018-04-24 | 南通金源智能技术有限公司 | A kind of nickel base superalloy powder |
| EP3778943A4 (en) * | 2018-04-02 | 2021-10-20 | Mitsubishi Power, Ltd. | Ni group superalloy casting material and ni group superalloy product using same |
Family Cites Families (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2515185A (en) * | 1943-02-25 | 1950-07-18 | Int Nickel Co | Age hardenable nickel alloy |
| US2570193A (en) * | 1946-04-09 | 1951-10-09 | Int Nickel Co | High-temperature alloys and articles |
| US2793108A (en) * | 1953-07-30 | 1957-05-21 | Int Nickel Co | Method of producing metal powder |
| US2809110A (en) * | 1954-08-05 | 1957-10-08 | Utica Drop Forge & Tool Corp | Alloy for high temperature applications |
| US3093476A (en) * | 1959-05-27 | 1963-06-11 | Int Nickel Co | Nickel-chromium alloys |
| US2975051A (en) * | 1959-09-29 | 1961-03-14 | Gen Electric | Nickel base alloy |
| FR1258034A (en) * | 1960-05-25 | 1961-04-07 | Mond Nickel Co Ltd | Nickel-chromium alloy refinements |
| US3164465A (en) * | 1962-11-08 | 1965-01-05 | Martin Metals Company | Nickel-base alloys |
| NL136758C (en) * | 1963-10-21 | 1900-01-01 | ||
| SU186691A1 (en) * | 1965-02-17 | 1966-10-03 | ||
| US3561955A (en) * | 1966-08-30 | 1971-02-09 | Martin Marietta Corp | Stable nickel base alloy |
| US3576681A (en) * | 1969-03-26 | 1971-04-27 | Gen Electric | Wrought nickel base alloy article |
| US4039330A (en) * | 1971-04-07 | 1977-08-02 | The International Nickel Company, Inc. | Nickel-chromium-cobalt alloys |
| US3677747A (en) * | 1971-06-28 | 1972-07-18 | Martin Marietta Corp | High temperature castable alloys and castings |
| US3869284A (en) * | 1973-04-02 | 1975-03-04 | French Baldwin J | High temperature alloys |
| JPS5631344B2 (en) * | 1973-08-08 | 1981-07-21 | ||
| US3890816A (en) * | 1973-09-26 | 1975-06-24 | Gen Electric | Elimination of carbide segregation to prior particle boundaries |
| US3976480A (en) * | 1974-09-18 | 1976-08-24 | Hitachi Metals, Ltd. | Nickel base alloy |
| US4083734A (en) * | 1975-07-18 | 1978-04-11 | Special Metals Corporation | Nickel base alloy |
| US4140555A (en) * | 1975-12-29 | 1979-02-20 | Howmet Corporation | Nickel-base casting superalloys |
| US4078951A (en) * | 1976-03-31 | 1978-03-14 | University Patents, Inc. | Method of improving fatigue life of cast nickel based superalloys and composition |
| US4093476A (en) * | 1976-12-22 | 1978-06-06 | Special Metals Corporation | Nickel base alloy |
| GB1544720A (en) * | 1977-01-13 | 1979-04-25 | Inco Europ Ltd | Nickel-base superalloys |
| JPS57149441A (en) * | 1981-03-12 | 1982-09-16 | Res Inst Electric Magnetic Alloys | Elinver type alloy for high temperature and preparation thereof |
| IL65677A0 (en) * | 1981-06-12 | 1982-08-31 | Special Metals Corp | Nickel base cast alloy |
| US4574015A (en) * | 1983-12-27 | 1986-03-04 | United Technologies Corporation | Nickle base superalloy articles and method for making |
-
1984
- 1984-12-10 US US06/679,725 patent/US4629521A/en not_active Expired - Fee Related
-
1985
- 1985-10-22 ZA ZA858123A patent/ZA858123B/en unknown
- 1985-11-11 BR BR8505667A patent/BR8505667A/en not_active IP Right Cessation
- 1985-11-22 CA CA000495994A patent/CA1255518A/en not_active Expired
- 1985-11-25 JP JP60264721A patent/JPS61139633A/en active Pending
- 1985-11-25 IL IL77135A patent/IL77135A/en not_active IP Right Cessation
- 1985-11-27 AU AU50416/85A patent/AU574538B2/en not_active Ceased
- 1985-12-04 DE DE8585402397T patent/DE3563984D1/en not_active Expired
- 1985-12-04 AT AT85402397T patent/ATE36009T1/en not_active IP Right Cessation
- 1985-12-04 EP EP85402397A patent/EP0187573B1/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2194960A (en) * | 1986-03-17 | 1988-03-23 | Stuart L Adelman | Improved superalloy compositions and articles |
| GB2194960B (en) * | 1986-03-17 | 1990-06-20 | Stuart L Adelman | Improved superalloy compositions and articles |
Also Published As
| Publication number | Publication date |
|---|---|
| CA1255518A (en) | 1989-06-13 |
| AU5041685A (en) | 1986-06-19 |
| EP0187573A3 (en) | 1986-07-30 |
| EP0187573B1 (en) | 1988-07-27 |
| ATE36009T1 (en) | 1988-08-15 |
| AU574538B2 (en) | 1988-07-07 |
| US4629521A (en) | 1986-12-16 |
| BR8505667A (en) | 1986-08-12 |
| IL77135A (en) | 1988-11-30 |
| DE3563984D1 (en) | 1988-09-01 |
| ZA858123B (en) | 1986-06-25 |
| IL77135A0 (en) | 1986-04-29 |
| JPS61139633A (en) | 1986-06-26 |
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