EP0194392A1 - Nickel-base superalloys especially useful as compatible protective environmental coatings for advanced superalloys - Google Patents
Nickel-base superalloys especially useful as compatible protective environmental coatings for advanced superalloys Download PDFInfo
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- EP0194392A1 EP0194392A1 EP85400478A EP85400478A EP0194392A1 EP 0194392 A1 EP0194392 A1 EP 0194392A1 EP 85400478 A EP85400478 A EP 85400478A EP 85400478 A EP85400478 A EP 85400478A EP 0194392 A1 EP0194392 A1 EP 0194392A1
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- tungsten
- chromium
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- 229910000601 superalloy Inorganic materials 0.000 title claims abstract description 59
- 230000007613 environmental effect Effects 0.000 title abstract description 15
- 230000001681 protective effect Effects 0.000 title abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 40
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 33
- 239000000956 alloy Substances 0.000 claims abstract description 33
- 230000005496 eutectics Effects 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims description 77
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 49
- 239000011651 chromium Substances 0.000 claims description 28
- 239000012535 impurity Substances 0.000 claims description 27
- 229910052782 aluminium Inorganic materials 0.000 claims description 26
- 229910052804 chromium Inorganic materials 0.000 claims description 25
- 229910052715 tantalum Inorganic materials 0.000 claims description 25
- 229910052721 tungsten Inorganic materials 0.000 claims description 25
- 229910052759 nickel Inorganic materials 0.000 claims description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- 229910052750 molybdenum Inorganic materials 0.000 claims description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 21
- 229910052796 boron Inorganic materials 0.000 claims description 21
- 229910052702 rhenium Inorganic materials 0.000 claims description 21
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 20
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 20
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 20
- 239000010937 tungsten Substances 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 229910017052 cobalt Inorganic materials 0.000 claims description 19
- 239000010941 cobalt Substances 0.000 claims description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 19
- 229910052735 hafnium Inorganic materials 0.000 claims description 19
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 18
- 239000011733 molybdenum Substances 0.000 claims description 18
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 17
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 17
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000010955 niobium Substances 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 238000007711 solidification Methods 0.000 claims description 7
- 230000008023 solidification Effects 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 238000005260 corrosion Methods 0.000 claims description 5
- 230000007797 corrosion Effects 0.000 claims description 5
- 230000003014 reinforcing effect Effects 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 4
- 238000000034 method Methods 0.000 description 17
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- 238000009792 diffusion process Methods 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- -1 mo bdenum Chemical compound 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
-
- 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
- This invention pertains generally to nickel-base superalloys useful in the manufacture of hot-section components of aircraft gas turbine engines, e.g., vanes and rotating blades, and more particularly to compatible coatings especially useful for the enhancement of the environmental resistance of such hot-section components made from advanced nickel-base superalloys and nickel-base eutectic superalloys.
- Advanced nickel-base superalloys such as the monocarbide reinforced nickel-base eutectic superalloys of the type described, for example, in U.S. Patent 4,292,076 to Gigliotti, Jr. et al., which is incorporated herein by reference, are designed for use as unidirectionally solidified anisotropic metallic bodies, primarily in the form of vanes and rotating blades in aircraft gas turbine engines.
- Patent 4,292,076 when directionally solidified (DS'd) under stringent conditions to achieve planar front solidification (PFS), result in a eutectic composite microstructure consisting of strong, reinforcing metallic carbide (MC) fibers in a 7/Y' nickel-base superalloy matrix. Because highly aligned microstructures are formed during planar front solidification, the superalloys of U.S. Patent 4,292,076 offer potential structural stability and property retention to a greater fraction of their solidification temperatures than do other materials.
- DS'd directionally solidified
- PFS planar front solidification
- the eutectic superalloys have been identified as the next generation of blade alloys beyond directionally solidified and single crystal superalloys. In order to take full temperature advantage of those superalloys, however, coatings are required to provide environmental protection at the high intended use temperatures.
- the coatings must be tightly bonded, i.e., metallurgically bonded, to the substrate and ideally must not degrade either the mechanical properties of the substrate (e.g., ductility, stress rupture strength and resistance to thermal fatigue) or the chemical properties of the substrate (e.g., oxidation resistance and hot corrosion resistance).
- the mechanical properties of the substrate e.g., ductility, stress rupture strength and resistance to thermal fatigue
- the chemical properties of the substrate e.g., oxidation resistance and hot corrosion resistance
- Examples of adverse effects to eutectic superalloys which have resulted from incompatible coatings are fiber denudation near the coating/substrate interface due to outward diffusion of carbon from the fiber into the coating and the formation of brittle precipitates in the substrate due to interdiffusion between the coating and the substrate.
- nickel-base superalloy which is mechanically and chemically compatible with advanced nickel-base superalloys and nickel-base eutectic superalloys, and which possesses excellent resistance to high temperature oxidation.
- the alloy of the invention is, therefore, particularly useful as a protective environmental coating for the external surfaces of hot stage aircraft gas turbine engine components, e.g., rotating blades and stationary vanes, made from advanced nickel-base superalloys and nickel-base eutectic superalloys.
- the superalloy of the invention consists essentially of about, by weight, 1 to 10% cobalt, 6 to 12% chromium, 5 to 8% aluminum, 1 to 10% tantalum, 1 to 10% tungsten, 0 to 3% rhenium, 0 to 2% molybdenum, 0.1 to 2% hafnium, 0.005 to 0.1% boron, 0.005 to 0.25% carbon, the balance being nickel and incidental impurities.
- novel superalloy will be applied most frequently as a protective environmental coating to comprise at least a portion of the outer surface of gas turbine engine components and articles
- novel alloy of this invention is useful as a thicker, built-up deposit applied to selected regions of substrates, such as aircraft gas turbine engine components, for repair purposes, or as the tip portion of rotating blades.
- substrates such as aircraft gas turbine engine components
- Such applications contemplate composite articles of manufacture : having as a substrate an article, such as a gas turbine. engine airfoil, made of a nickel-base superalloy or .
- nickel-base eutectic superalloy and one or more thick, built-up regions contiguous with, i.e., joined to and forming an integral part of, the substrate wherein the one or more regions comprise at least a portion of the outer surface of the composite article and are of the above-described novel superalloy composition.
- the present invention relates to a nickel-base superalloy which is mechanically and chemically compatible with advanced nickel-base superalloys and nickel-base eutectic superalloys and which possesses excellent resistance to high temperature oxidation.
- the superalloy of the invention consists essentially of cobalt, chromium, aluminum, tantalum, tungsten, rhenium, mo bdenum, hafnium, boron and carbon in the percentages by weight) set forth in Table I below, the balance vide nickel and incidental impurities.
- the present alloy is particularly useful as a protective environmental coating, of between about 0.002 and 0.1 inches in thickness, for the external surfaces of solid and hollow, fluid-cooled gas turbine engine components, e.g., rotating blades and stationary vanes, operating in the hot stage sections of such turbines and made from advanced nickel-base superalloys and nickel-' se eutectic superalloys. While it is contemplate that the novel alloy herein described will most frequenaly be applied as protective environmental coatings to provide at least a portion of the outer surface of gas turbine engine components and articles, it has also been found that the superalloy of the invention is also useful as one or more thicker, built-up deposits applied to selected regions of such articles or component-like substrates.
- the utilization of plasma spray techniques to deposit the alloy of the invention is preferred. Most preferred is the technique, sometimes referred to as low pressure plasma deposition (LPPD), described in U.S. Patent 3,839,618 - Muehlberger, which patent is incorporated herein by reference. Alloys in accordance with the present invention produce very dense coatings or deposits after plasma spraying and especially after plasma spraying by the above-mentioned LPPD process whereby as-deposited densities of 95% and greater are readily obtained.
- LPPD low pressure plasma deposition
- 6 0. series of coatings, hereinafter referred to as the "6 " or 6M-type coatings by way of designation, were produced by low pressure plasma deposition of an alloy of the invention, i.e., one consisting essentially of, nominally by weight within normal melting tolerances, 4% Co, 8.5% Cr, 6% Al, 5% Ta, 4.5% W, 1.5% Re, 1.5% Mo, 0.9% Hf, 0.01% B, and 0.09% C, the balance nickel and incidental impurities, onto flat plate-like substrates and pin-like substrates for environmental testing.
- an alloy of the invention i.e., one consisting essentially of, nominally by weight within normal melting tolerances, 4% Co, 8.5% Cr, 6% Al, 5% Ta, 4.5% W, 1.5% Re, 1.5% Mo, 0.9% Hf, 0.01% B, and 0.09% C, the balance nickel and incidental impurities, onto flat plate-like substrates and pin-like substrates for environmental testing.
- NiCoCrAlY Ni-23Co-18Cr-12.5Al-0.3Y
- All coatings of the NiCoCrAlY type were deposited by a commercial vendor using the physical vapor deposition (PVD) process described in the aforementioned 3,928,026. patent.
- the B-type substrates Prior to coating deposition, the B-type substrates were solution treated at 2325° F for two hours and the N-type substrates were solution treated at 2310° F for two hours irrespective of the coating to be applied.
- the process of applying the NiCoCrAlY type coatings has been described above.
- the 6M coatings were applied by the above-described LPPD plasma spray process.
- a commercially available standard internal feed plasma spray gun and the process parameters of Table II were used.
- the N-type substrates a commercially available standard external feed plasma spray gun and the process parameters of fable III were used.
- the structure of the B-type substrate is one of an aligned eutectic (TaC) fibrous reinforcing phase in a ⁇ / ⁇ ' matrix while the structure of the N-type substrate is one of y' precipitates in ay matrix.
- TaC aligned eutectic
- Table IV presents the results of cyclic oxidation tests on pin-like specimens conducted under the conditions shown in the table using a natural gas flame at the velocities shown in the table.
- the specimens were rotated for uniform exposure and cycled out of the flame 1 or 6 times per hour to cool the specimens to about 800° F. Failure is defined as penetration of the coating to the extent that (substrate) oxidation begins to occur.
- Hot corrosion testing was conducted at 1700° F using a JP-5 fuel-fired flame with 5 ppm salt added to the combustion products. The specimens were rotated for uniform exposure and cycled out of the flame once every hour.
- the alloy of the invention as a coating provides good protection to both substrates, and particularly to the B-type substrate.
- the oxidation resistance provided by the alloy of the invention is somewhat greater than would be expected based on a study of its overall composition.
- the alloy of the invention as a coating provides acceptable environmental protection against hot corrosion, i.e., greater than 540 hours life on B-type substrates (test terminated prior to failure) and 1000 hours on N-type substrates.
- the coated specimens were evaluated metallographically to determine the extent of interaction between the coatings and the substrate.
- the results are given in Table V which lists the extent, if any, of the denuded and platelet formation zones, the sum of which comprise the interaction zone, following exposure in the oxidation tests at the temperatures and for the times shown.
- Platelets such as those shown in Figures 3 and 7 for NiCoCrAlY on the B and N-type substrates, respectively, are a result of the interdiffusion of elements between the coating and the substrate, i.e., a chemical incompatibility between the coating and the substrate. The platelets are undesirable due to their needle-like morphology and brittleness.
- the denuded zone also shown in Figures 3 and 7, is a zone which has been depleted of ⁇ ' due to - the diffusion of elements from the substrate to the coating, leaving a weakened, primarily ⁇ matrix.
- the alloy of the invention also possesses high temperature strength superior to NiCoCrAlY. Elevated temperature tensile tests on very thick (-1/2 inch) deposits of the NiCoCrAlY and 6M-type alloys showed that at 1800° F the ultimate tensile strength (UTS) of the materials was about 7 and 30 ksi, respectively, while at 2000° F the UTS of the materials was about 3 and 7, respectively. The higher strength of the 6M-type alloy is expected to result in greatly improved resistance to thermal/mechanical fatigue cracking.
- the difference in the coefficient of thermal expansion (a) between the alloy of the invention and nickel-base superalloy substrates is less than that between NiCoCrAlY and the same superalloy substrates.
- the smaller difference in a reduces the stresses imposed on a coating alloy in service, and thereby reduces the propensity for coating spallation and thermal fatigue cracking.
- the low propensity of the alloy of the invention to form interaction zones, and particularly its low propensity to form platelets, plus its higher strength and thermal expansion compatibility with superalloy substrates makes the alloy of the invention a coating which is truly chemically and physically compatible with nickel-base superalloy substrates, in addition to providing the environmental resistance required in severe high pressure, high temperature turbine environments.
- the novel alloys of this invention are useful as thicker, built-up deposits applied to selected regions of aircraft gas turbine engine components, such as the tip portions of rotating blades or stationary vanes, or for purposes of repairing nicked or damaged regions as typically occur on such components as airfoils.
- the alloys of the invention are more in the nature of a superalloy from which components are made, e.g., structural or weight-carrying alloys, and less in the nature of coatings.
- the changes required in the plasma spraying process to effect the build-up of thicker deposits, as opposed to thin coatings, are well within the knowledge and expertise of those ordinarily skilled in the plasma spraying arts.
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Abstract
Description
- The Government has rights in this invention pursuant to Contract No. F33615-77-C-5200 awarded by the United States Department of the Air Force.
- The invention disclosed and claimed herein is related to the invention disclosed and claimed in patent application Serial No. 13DV-8334, filed of even date herewith.
- This invention pertains generally to nickel-base superalloys useful in the manufacture of hot-section components of aircraft gas turbine engines, e.g., vanes and rotating blades, and more particularly to compatible coatings especially useful for the enhancement of the environmental resistance of such hot-section components made from advanced nickel-base superalloys and nickel-base eutectic superalloys.
- Advanced nickel-base superalloys such as the monocarbide reinforced nickel-base eutectic superalloys of the type described, for example, in U.S. Patent 4,292,076 to Gigliotti, Jr. et al., which is incorporated herein by reference, are designed for use as unidirectionally solidified anisotropic metallic bodies, primarily in the form of vanes and rotating blades in aircraft gas turbine engines. The superalloys of U.S. Patent 4,292,076, when directionally solidified (DS'd) under stringent conditions to achieve planar front solidification (PFS), result in a eutectic composite microstructure consisting of strong, reinforcing metallic carbide (MC) fibers in a 7/Y' nickel-base superalloy matrix. Because highly aligned microstructures are formed during planar front solidification, the superalloys of U.S. Patent 4,292,076 offer potential structural stability and property retention to a greater fraction of their solidification temperatures than do other materials.
- The eutectic superalloys have been identified as the next generation of blade alloys beyond directionally solidified and single crystal superalloys. In order to take full temperature advantage of those superalloys, however, coatings are required to provide environmental protection at the high intended use temperatures.
- Stringent requirements are placed on the coatings and the coating/substrate composite. For example, the coatings must be tightly bonded, i.e., metallurgically bonded, to the substrate and ideally must not degrade either the mechanical properties of the substrate (e.g., ductility, stress rupture strength and resistance to thermal fatigue) or the chemical properties of the substrate (e.g., oxidation resistance and hot corrosion resistance).
- Examples of adverse effects to eutectic superalloys which have resulted from incompatible coatings are fiber denudation near the coating/substrate interface due to outward diffusion of carbon from the fiber into the coating and the formation of brittle precipitates in the substrate due to interdiffusion between the coating and the substrate.
- While many coatings and barrier/coating systems have been proposed and tried, there has been a general inability in the past to specify coatings or barrier/coating systems which are truly compatible with the substrate, i.e., offer improved environmental protection and produce good metallurgical bonds with the substrate yet not degrade the mechanical or chemical properties of the substrate, especially when the substrate is of an alloy of the type described in U.S. Patent 4,292,076.
- Therefore, there exists a need for protective environmental coatings which are truly compatible with the newest generation of superalloys, particularly those designed for use as vanes and rotating blades in aircraft gas turbine engines, such as the directionally solidified monocarbide reinforced nickel-base eutectic superalloys of the type described in U.S. Patent 4,292,076.
- There is provided by the present invention a nickel-base superalloy which is mechanically and chemically compatible with advanced nickel-base superalloys and nickel-base eutectic superalloys, and which possesses excellent resistance to high temperature oxidation. The alloy of the invention is, therefore, particularly useful as a protective environmental coating for the external surfaces of hot stage aircraft gas turbine engine components, e.g., rotating blades and stationary vanes, made from advanced nickel-base superalloys and nickel-base eutectic superalloys.
- Broadly, the superalloy of the invention consists essentially of about, by weight, 1 to 10% cobalt, 6 to 12% chromium, 5 to 8% aluminum, 1 to 10% tantalum, 1 to 10% tungsten, 0 to 3% rhenium, 0 to 2% molybdenum, 0.1 to 2% hafnium, 0.005 to 0.1% boron, 0.005 to 0.25% carbon, the balance being nickel and incidental impurities.
- While it is contemplated that the above-described novel superalloy will be applied most frequently as a protective environmental coating to comprise at least a portion of the outer surface of gas turbine engine components and articles, it has also been found that the novel alloy of this invention is useful as a thicker, built-up deposit applied to selected regions of substrates, such as aircraft gas turbine engine components, for repair purposes, or as the tip portion of rotating blades. Such applications then, contemplate composite articles of manufacture : having as a substrate an article, such as a gas turbine. engine airfoil, made of a nickel-base superalloy or . nickel-base eutectic superalloy and one or more thick, built-up regions contiguous with, i.e., joined to and forming an integral part of, the substrate wherein the one or more regions comprise at least a portion of the outer surface of the composite article and are of the above-described novel superalloy composition.
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- FIGURE 1 is a photomicrograph at 200X of a NiCoCrAlY type coating as-deposited on a B-type nickel-base eutectic superalloy substrate;
- FIGURE 2 is a photomicrograph at 250X of the alloy of the invention as-deposited as a coating on a B-type substrate by the low pressure plasma deposition (LPPD) process;
- FIGURE 3 is a photomicrograph at 200X of a NiCoCrAlY the coating on a B-type substrate following exposure of .0 hours at 2100° F in a Mach 0.05 gas velocity oxidation test, in which the specimens were cycled to 800° F six times per hour;
- FIGURE 4 is a photomicrograph at SOOX of the alloy of the invention on a B-type substrate after exposure of 500 hours in the same oxidation test described above for Figure 3;
- FIGURE 5 is a photomicrograph at 500X of a NiCoCrAlY type coating as-deposited on an N-type nickel-base single crystal superalloy substrate;
- FIGURE 6 is a photomicrograph at 500X of the alloy of the invention as-deposited as a coating on an N-type substrate by the LPPD process;
- FIGURE 7 is a photomicrograph at 200X of a NiCoCrAlY type coating on an N-type substrate following exposure of 400 hours at 2075° F in a Mach 0.05 gas velocity oxidation test, in which the specimens were cycled to 800° F six times per hour; and
- FIGURE 8 is a photomicrograph at 200X of the alloy of the invention on an N-type substrate following exposure of 550 hours at 2075° F in the same oxidation test described above for Figure 7.
- As set forth in the foregoing summary, the present invention relates to a nickel-base superalloy which is mechanically and chemically compatible with advanced nickel-base superalloys and nickel-base eutectic superalloys and which possesses excellent resistance to high temperature oxidation. The superalloy of the invention consists essentially of cobalt, chromium, aluminum, tantalum, tungsten, rhenium, mo bdenum, hafnium, boron and carbon in the percentages by weight) set forth in Table I below, the balance bei nickel and incidental impurities.
- The present alloy is particularly useful as a protective environmental coating, of between about 0.002 and 0.1 inches in thickness, for the external surfaces of solid and hollow, fluid-cooled gas turbine engine components, e.g., rotating blades and stationary vanes, operating in the hot stage sections of such turbines and made from advanced nickel-base superalloys and nickel-' se eutectic superalloys. While it is contemplate that the novel alloy herein described will most frequenaly be applied as protective environmental coatings to provide at least a portion of the outer surface of gas turbine engine components and articles, it has also been found that the superalloy of the invention is also useful as one or more thicker, built-up deposits applied to selected regions of such articles or component-like substrates.
- Whether the novel alloy is deposited as coatings or thicker, built-up deposits, the utilization of plasma spray techniques to deposit the alloy of the invention is preferred. Most preferred is the technique, sometimes referred to as low pressure plasma deposition (LPPD), described in U.S. Patent 3,839,618 - Muehlberger, which patent is incorporated herein by reference. Alloys in accordance with the present invention produce very dense coatings or deposits after plasma spraying and especially after plasma spraying by the above-mentioned LPPD process whereby as-deposited densities of 95% and greater are readily obtained.
- The wide differences in the evaporation rates (or vapor pressures) between high vapor pressure elements like chromium, manganese or aluminum and low vapor pressure elements like tantalum or tungsten make the deposition and composition control of coatings of the novel alloy of this invention by other processes such as vacuum physical vapor deposition difficult, if not impossible. It will be appreciated, however, that process improvements or modifications in methods such as physical vapor deposition or ion plating could make coating by these methods possible, and the use of these methods is therefore contemplated. Additionally, techniques like sputtering, slurry sintering, or others may also be considered.
- To illustrate the practice of the present invention, 0. series of coatings, hereinafter referred to as the "6 " or 6M-type coatings by way of designation, were produced by low pressure plasma deposition of an alloy of the invention, i.e., one consisting essentially of, nominally by weight within normal melting tolerances, 4% Co, 8.5% Cr, 6% Al, 5% Ta, 4.5% W, 1.5% Re, 1.5% Mo, 0.9% Hf, 0.01% B, and 0.09% C, the balance nickel and incidental impurities, onto flat plate-like substrates and pin-like substrates for environmental testing.
- A nickel-base superalloy conforming to U.S. Patent 4,292,076, i.e., one consisting essentially of about, on a weight basis, at least an amount in excess of an impurity amount up to 0.02% of B, 0 to 9% Re, 0 to <0.8% Ti, 0 to 20% Cr, 0 to 10% Al, 3 to 15% Ta, 0.1 to 1% C, 0 to 20% Co, 0 to 20% W, 0 to 7% V, 0 to 10% Mo, 0 to 3% Cb, 0 to 3% Hf, 0 to 1.5% Zr, the balance being nickel and incidental impurities, but having a nominal composition of about, by weight, 0.01% B, 6.44% Re, 3.84% Cr, 5.34% Al, 11.37% Ta, 0.43% C, 3.8% Co, 4.33% W, 3.01% Mo, balance nickel and incidental impurities, and hereinafter referred to as the "B" or B-type substrate for purposes of designation, was provided as one substrate.
- A nickel-base superalloy capable of being cast as a single crystal by directional solidification and conforming to that described in copending, co-assigned patent application Serial No. 307,819, filed October 2, 1981, i.e., consisting essentially of, by weight, 7 to 12% Cr, 1 to 5% Mo, 3 to 5% Ti, 3 to 5% Al, 5 to 15% Co, 3 to 12% W, 2 to 6% Ta, up to 10% Re, up to 2% Cb, up to 3% V, up to 2% Hf, balance nickel and incidental impurities, further characterized by the substantial absence of B, and Zr and wherein the Al:Ti ratio is maintained the range of about 0.5 to about 1 while maintaining the Cr:Al ratio in the range of about 1.5 to 4 was provided as a second substrate and is hereinafter referred to as the "N" or N-type substrate for purposes of designation. More specifically, the composition of the second substrate material was, nominally, by weight, 9.3% Cr, 7.5% Co, 3.7% Al, 4% Ta, 4.2% Ti, 1.51 Mo, 6% W, 0.5% Nb, the balance nickel plus incidental impurities.
- For comparison, separate substrates of the above-described B-type and N-type were also provided with a coating typically used heretofore to enhance the resistance of such substrates to environmental degradation. In this case, the coating material selected was a NiCoCrAlY (Ni-23Co-18Cr-12.5Al-0.3Y) of the type described in U.S. Patent 3,928,026, which patent is herein incorporated by reference. All coatings of the NiCoCrAlY type were deposited by a commercial vendor using the physical vapor deposition (PVD) process described in the aforementioned 3,928,026. patent.
- Prior to coating deposition, the B-type substrates were solution treated at 2325° F for two hours and the N-type substrates were solution treated at 2310° F for two hours irrespective of the coating to be applied. The process of applying the NiCoCrAlY type coatings has been described above. The 6M coatings were applied by the above-described LPPD plasma spray process. For the B-type substrates, a commercially available standard internal feed plasma spray gun and the process parameters of Table II were used. For the N-type substrates, a commercially available standard external feed plasma spray gun and the process parameters of fable III were used.
- To optimize the properties of the substrates, all coated substrates were subjected to a post-deposition heat treatment which typically consisted of a first age at 1975° F for 2-8 hours followed by a second age at 16500 F for 4-16 hours. At this stage, the coatings are referred to as "as-deposited" coatings. The structure of the B-type substrate is one of an aligned eutectic (TaC) fibrous reinforcing phase in a γ/γ' matrix while the structure of the N-type substrate is one of y' precipitates in ay matrix.
- Table IV presents the results of cyclic oxidation tests on pin-like specimens conducted under the conditions shown in the table using a natural gas flame at the velocities shown in the table. The specimens were rotated for uniform exposure and cycled out of the flame 1 or 6 times per hour to cool the specimens to about 800° F. Failure is defined as penetration of the coating to the extent that (substrate) oxidation begins to occur. Hot corrosion testing was conducted at 1700° F using a JP-5 fuel-fired flame with 5 ppm salt added to the combustion products. The specimens were rotated for uniform exposure and cycled out of the flame once every hour.
- It may be seen from Table IV that the alloy of the invention as a coating provides good protection to both substrates, and particularly to the B-type substrate. The oxidation resistance provided by the alloy of the invention is somewhat greater than would be expected based on a study of its overall composition. These unexpected properties are attributed to the absence of titanium and the presence of hafnium in combination with the slightly higher-than-usual aluminum content (6%) and a proper balance of carbon and the other refractory elements. This balance of elements helps form and maintain a protective alumina scale when exposed in air. Although having lower resistance to hot corrosion than NiCoCrAlY, the alloy of the invention as a coating provides acceptable environmental protection against hot corrosion, i.e., greater than 540 hours life on B-type substrates (test terminated prior to failure) and 1000 hours on N-type substrates.
- The coated specimens were evaluated metallographically to determine the extent of interaction between the coatings and the substrate. The results are given in Table V which lists the extent, if any, of the denuded and platelet formation zones, the sum of which comprise the interaction zone, following exposure in the oxidation tests at the temperatures and for the times shown. Platelets,
- Reference to Figures 2 and 6 show that in the as-deposited condition there is virtually no interaction zone formed between the 6M coating and either the B-type or N-type substrates. A slight interaction zone, however, is evident in Figures 1 and 5 between the NiCoCrAlY coating and both the B-type and N-type substrates.
- Reference to Figures 3 and 4, and Table V, shows that after 500 hours exposure at 2100° F in the oxidation test an interaction zone has formed between the NiCoCrAlY coating and the B-type substrate which is about three times deeper than the interaction zone formed between the 6M coating and the B-type substrate. Further, about 45% of the interaction zone in the NiCoCrAlY/B pair is of the deleterious platelet phase.
- Similarly, reference to Figures 7 and 8, and Table V, shows that after 400 hours exposure at 2075° F in the oxidation test an interaction zone has formed between the NiCoCrAlY coating and the N-type substrate which is deeper than about four times the interaction zone formed between the 6M coating and the N-type substrate, even though the 6M/N pair was tested for about a 40% longer period of time. About 70% of the interaction zone in the NiCoCrAlY/N pair is of the deleterious platelet phase.
- In addition to the unique combination of reduced diffusional interaction and good environmental resistance, the alloy of the invention also possesses high temperature strength superior to NiCoCrAlY. Elevated temperature tensile tests on very thick (-1/2 inch) deposits of the NiCoCrAlY and 6M-type alloys showed that at 1800° F the ultimate tensile strength (UTS) of the materials was about 7 and 30 ksi, respectively, while at 2000° F the UTS of the materials was about 3 and 7, respectively. The higher strength of the 6M-type alloy is expected to result in greatly improved resistance to thermal/mechanical fatigue cracking.
- Since the alloy of the invention is itself a superalloy, the difference in the coefficient of thermal expansion (a) between the alloy of the invention and nickel-base superalloy substrates is less than that between NiCoCrAlY and the same superalloy substrates. The smaller difference in a reduces the stresses imposed on a coating alloy in service, and thereby reduces the propensity for coating spallation and thermal fatigue cracking.
- Thus, the low propensity of the alloy of the invention to form interaction zones, and particularly its low propensity to form platelets, plus its higher strength and thermal expansion compatibility with superalloy substrates makes the alloy of the invention a coating which is truly chemically and physically compatible with nickel-base superalloy substrates, in addition to providing the environmental resistance required in severe high pressure, high temperature turbine environments.
- It has also been found that the novel alloys of this invention are useful as thicker, built-up deposits applied to selected regions of aircraft gas turbine engine components, such as the tip portions of rotating blades or stationary vanes, or for purposes of repairing nicked or damaged regions as typically occur on such components as airfoils. In that respect, the alloys of the invention are more in the nature of a superalloy from which components are made, e.g., structural or weight-carrying alloys, and less in the nature of coatings. The changes required in the plasma spraying process to effect the build-up of thicker deposits, as opposed to thin coatings, are well within the knowledge and expertise of those ordinarily skilled in the plasma spraying arts.
- It will be understood that various changes and modifications not specifically referred to herein may be made in the invention herein described, and to its : uses herein described, without departing from the spirit of the invention particularly as defined in the. following claims.
- What is desired to be secured by Letters Patent of the United States is the following.
Claims (18)
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP19850400478 EP0194392B1 (en) | 1985-03-13 | 1985-03-13 | Nickel-base superalloys especially useful as compatible protective environmental coatings for advanced superalloys |
DE8585400478T DE3572512D1 (en) | 1985-03-13 | 1985-03-13 | Nickel-base superalloys especially useful as compatible protective environmental coatings for advanced superalloys |
SG63390A SG63390G (en) | 1985-03-13 | 1990-08-01 | Nickel-base superalloys especially useful as compatible protective environmental coatings for advanced superalloys |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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EP19850400478 EP0194392B1 (en) | 1985-03-13 | 1985-03-13 | Nickel-base superalloys especially useful as compatible protective environmental coatings for advanced superalloys |
Publications (2)
Publication Number | Publication Date |
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EP0194392A1 true EP0194392A1 (en) | 1986-09-17 |
EP0194392B1 EP0194392B1 (en) | 1989-08-23 |
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Application Number | Title | Priority Date | Filing Date |
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EP19850400478 Expired EP0194392B1 (en) | 1985-03-13 | 1985-03-13 | Nickel-base superalloys especially useful as compatible protective environmental coatings for advanced superalloys |
Country Status (3)
Country | Link |
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EP (1) | EP0194392B1 (en) |
DE (1) | DE3572512D1 (en) |
SG (1) | SG63390G (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5273712A (en) * | 1989-08-10 | 1993-12-28 | Siemens Aktiengesellschaft | Highly corrosion and/or oxidation-resistant protective coating containing rhenium |
US5401307A (en) * | 1990-08-10 | 1995-03-28 | Siemens Aktiengesellschaft | High temperature-resistant corrosion protection coating on a component, in particular a gas turbine component |
US5582635A (en) * | 1990-08-10 | 1996-12-10 | Siemens Aktiengesellschaft | High temperature-resistant corrosion protection coating for a component in particular a gas turbine component |
DE3719902A1 (en) * | 1986-01-02 | 1997-05-22 | United Technologies Corp | Columnar grain nickel superalloy compsn. |
US6924046B2 (en) | 2001-10-24 | 2005-08-02 | Siemens Aktiengesellschaft | Rhenium-containing protective layer for protecting a component against corrosion and oxidation at high temperatures |
EP1837412A2 (en) * | 2006-03-24 | 2007-09-26 | United Technologies Corporation | Coating suitable for use as a bondcoat in a thermal barrier coating system |
US8025984B2 (en) | 2003-10-17 | 2011-09-27 | Siemens Aktiengesellschaft | Protective layer for protecting a component against corrosion and oxidation at high temperatures, and component |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1780294A1 (en) | 2005-10-25 | 2007-05-02 | Siemens Aktiengesellschaft | Alloy, protective coating for protecting a structural member against corrosion and oxidation at high temperatures and structural member |
Citations (4)
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US3896547A (en) * | 1974-05-02 | 1975-07-29 | Sterndent Corp | Prosthetic article and method for manufacture |
FR2457907A1 (en) * | 1979-05-29 | 1980-12-26 | Howmet Turbine Components | COATING COMPOSITION FOR PROTECTION AGAINST HIGH TEMPERATURE OXIDATION OF SUPER-ALLOYS AND COMPONENTS OF SUPER-ALLOYS THUS COATED |
FR2503189A1 (en) * | 1981-03-31 | 1982-10-08 | Howmet Turbine Components | COATING COMPOSITION FOR SUPERALLIAGES RESISTANT TO OXIDATION AT HIGH TEMPERATURE AND COATED SUPERALLIAGES OF THIS COMPOSITION |
US4459160A (en) * | 1980-03-13 | 1984-07-10 | Rolls-Royce Limited | Single crystal castings |
-
1985
- 1985-03-13 DE DE8585400478T patent/DE3572512D1/en not_active Expired
- 1985-03-13 EP EP19850400478 patent/EP0194392B1/en not_active Expired
-
1990
- 1990-08-01 SG SG63390A patent/SG63390G/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US3896547A (en) * | 1974-05-02 | 1975-07-29 | Sterndent Corp | Prosthetic article and method for manufacture |
FR2457907A1 (en) * | 1979-05-29 | 1980-12-26 | Howmet Turbine Components | COATING COMPOSITION FOR PROTECTION AGAINST HIGH TEMPERATURE OXIDATION OF SUPER-ALLOYS AND COMPONENTS OF SUPER-ALLOYS THUS COATED |
US4459160A (en) * | 1980-03-13 | 1984-07-10 | Rolls-Royce Limited | Single crystal castings |
FR2503189A1 (en) * | 1981-03-31 | 1982-10-08 | Howmet Turbine Components | COATING COMPOSITION FOR SUPERALLIAGES RESISTANT TO OXIDATION AT HIGH TEMPERATURE AND COATED SUPERALLIAGES OF THIS COMPOSITION |
Non-Patent Citations (1)
Title |
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THIN SOLID FILMS, vol. 84, 6th-10th April 1982, pages 49-58, Metallurgical and protective coatings, Conference on Metallurgical Coatings, San Francisco, CA, US, Elsevier, Netherlands; F.J. PENNISI et al.: "Improved plasma-sprayed Ni-Co-Cr-Al-Y and Co-Cr-Al-Y coatings for aircraft gas turbine applications" * |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3719902A1 (en) * | 1986-01-02 | 1997-05-22 | United Technologies Corp | Columnar grain nickel superalloy compsn. |
DE3719902C2 (en) * | 1986-01-02 | 2001-11-08 | United Technologies Corp | Nickel-based superalloy with columnar crystal grain shape |
US5273712A (en) * | 1989-08-10 | 1993-12-28 | Siemens Aktiengesellschaft | Highly corrosion and/or oxidation-resistant protective coating containing rhenium |
US5401307A (en) * | 1990-08-10 | 1995-03-28 | Siemens Aktiengesellschaft | High temperature-resistant corrosion protection coating on a component, in particular a gas turbine component |
US5582635A (en) * | 1990-08-10 | 1996-12-10 | Siemens Aktiengesellschaft | High temperature-resistant corrosion protection coating for a component in particular a gas turbine component |
US5599385A (en) * | 1990-08-10 | 1997-02-04 | Siemens Aktiengesellschaft | High temperature-resistant corrosion protection coating for a component, in particular a gas turbine component |
US6924046B2 (en) | 2001-10-24 | 2005-08-02 | Siemens Aktiengesellschaft | Rhenium-containing protective layer for protecting a component against corrosion and oxidation at high temperatures |
US8025984B2 (en) | 2003-10-17 | 2011-09-27 | Siemens Aktiengesellschaft | Protective layer for protecting a component against corrosion and oxidation at high temperatures, and component |
EP1837412A2 (en) * | 2006-03-24 | 2007-09-26 | United Technologies Corporation | Coating suitable for use as a bondcoat in a thermal barrier coating system |
EP1837412A3 (en) * | 2006-03-24 | 2011-03-16 | United Technologies Corporation | Coating suitable for use as a bondcoat in a thermal barrier coating system |
Also Published As
Publication number | Publication date |
---|---|
DE3572512D1 (en) | 1989-09-28 |
SG63390G (en) | 1990-09-07 |
EP0194392B1 (en) | 1989-08-23 |
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