US3928026A - High temperature nicocraly coatings - Google Patents
High temperature nicocraly coatings Download PDFInfo
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- US3928026A US3928026A US469186A US46918674A US3928026A US 3928026 A US3928026 A US 3928026A US 469186 A US469186 A US 469186A US 46918674 A US46918674 A US 46918674A US 3928026 A US3928026 A US 3928026A
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- 238000000576 coating method Methods 0.000 title claims abstract description 99
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000011248 coating agent Substances 0.000 claims abstract description 60
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 46
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 37
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 36
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 35
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910000601 superalloy Inorganic materials 0.000 claims abstract description 14
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims abstract description 9
- 229910052776 Thorium Inorganic materials 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 9
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 9
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 46
- 239000000956 alloy Substances 0.000 claims description 46
- 239000011651 chromium Substances 0.000 claims description 44
- 229910017052 cobalt Inorganic materials 0.000 claims description 34
- 239000010941 cobalt Substances 0.000 claims description 34
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 34
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 28
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 28
- 239000008199 coating composition Substances 0.000 claims description 16
- 238000005486 sulfidation Methods 0.000 abstract description 9
- 230000007774 longterm Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 22
- 230000003647 oxidation Effects 0.000 description 18
- 238000007254 oxidation reaction Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 10
- 229910000951 Aluminide Inorganic materials 0.000 description 9
- 125000004122 cyclic group Chemical group 0.000 description 9
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- 238000005260 corrosion Methods 0.000 description 8
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- 239000000446 fuel Substances 0.000 description 6
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- 235000002639 sodium chloride Nutrition 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 238000005050 thermomechanical fatigue Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
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- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- -1 nickel-cobalt-chromium-aluminum-yttrium Chemical compound 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 229910002515 CoAl Inorganic materials 0.000 description 1
- CUDSBWGCGSUXDB-UHFFFAOYSA-N Dibutyl disulfide Chemical compound CCCCSSCCCC CUDSBWGCGSUXDB-UHFFFAOYSA-N 0.000 description 1
- 229910002543 FeCrAlY Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005270 abrasive blasting Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
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- 230000000007 visual effect Effects 0.000 description 1
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Images
Classifications
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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
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
-
- 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
- C22C19/052—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 40%
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/922—Static electricity metal bleed-off metallic stock
- Y10S428/923—Physical dimension
- Y10S428/924—Composite
- Y10S428/926—Thickness of individual layer specified
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12931—Co-, Fe-, or Ni-base components, alternative to each other
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12986—Adjacent functionally defined components
Definitions
- the present invention relates to coatings and coated articles and more particularly to coatings for the nickeland cobalt-base superalloys having high ductility while retaining desirable stability and elevated temperature oxidation and hot corrosion resistance.
- Aluminide coatings can be, for example, a source of fracture initiation in fatigue. Coating ductility has been found to be an important determinant in fatigue life since at relatively low temperatures aluminide coatings tend to crack in a brittle manner at low strains in the tensile portions of the fatigue cycle.
- the present invention relates to a nickelcobalt-chromium-aluminum-yttrium coating alloy having greatly improved ductility as well as other properties which together render it eminently suitable for use in gas turbine engine hardware and other rigorous environments.
- the invention more particularly relates to a high ductility coating alloy which possesses both oxidation-erosion and sulfidation resistance and which consists of a particular combination of nickel, cobalt, chromium, aluminum and a reactive metal selected from the group consisting of yttrium, scandium, thorium, lanthanum and the other rare earth elements.
- the invention contemplates a coating composition consisting essentially of, by weight, 1 1-48% cobalt, 1()-40% chromium, 9-15% aluminum, 0.01-1.0% of a reactive metal selected from the group consisting of yttrium, scandium, thorium, lanthanum and other rare earth elements, balance essentially nickel, the nickel content being at least about 15%.
- the coating composition consists essentially of, by weight, about 15-40% cobalt, 12-30% chromium, -15% aluminum, 001-1 .0% yttrium, balance essentially nickel, the nickel content being at least about 15%.
- the coating composition consists essentially of, by weight, about 25-40% cobalt, 14-22% chromium, 13-15% aluminum, 0.01-1.0% yttrium, balance essentially nickel.
- the coating composition consists essentially of, by weight, about 1535% cobalt, 1422% chromium, 10l3% aluminum, 0.0ll'.0% yttrium, balance essentially nickel.
- FIG. 1 is a graph which dramatically illustrates the ductility behavior of various nickel-cobalt-chromiumaluminum-yttrium coating alloys as compared to representative CoCrAlY and NiCrAlY coating alloys.
- FIG. 2 is a graph showing ductility as a function of temperature of some NiCoCrAlY coating alloys as compared to representative CoCrAlY and NiCrAlY coating alloys.
- FIG. 3 is a graph illustrating the diffusional stability of various nickel-cobalt-chromium-aluminum-yttrium coating alloys as compared to representative CoCrAlY and NiCrAlY coating alloys.
- FIG. 4 is a graph illustrating the oxidation characteristics of various nickel-cobaIt-chromium-aluminumyttrium coating alloys as compared to representative CoCrAlY and NiCrAlY coating alloys.
- FIG. 5 is a graph illustrating the sulfidation characteristics of various nickel-cobaIt-chromium-aluminumyttrium coating alloys as compared to representative CoCrAlY and NiCrAlY coating alloys.
- the CoCrAlY and NiCrAlY coatings have provided significant improvements in the lifetimes 'of the superalloys.
- NiCrAlY coatings while providing extremely high oxidation resistance and diffusional stability required improvement in sulfidation resistance
- CoCrAlY coatings while providing extremely-high sulfidation resistance required improvement in oxidation resistance and diffusional stability.
- a variety of overlay coatings was evaluated.
- NiCrAlY coatings While it had been known that certain of the useful NiCrAlY coatings exhibited a ductility higher than certain of the useful CoCrAlY coatings and it had been surmised therefore that a substitution of some nickel for the cobalt in the CoCrAlY composition might improve ductility, it was surprising and unexpected that the nickel-cobalt-chromium-aluminumyttrium system as defined above would provide a ductility improvement which was markedly superior to either the NiCrAlY or CoCrAlY.
- Correlation of coating microstructure with coating chemistry indicates that, in the nickel-cobalt-chromium-aluminum-yttrium system herein described, desirable y B microstructures are obtained at a higher aluminum content, the increased stability of the y B microstructure caused by cobalt additions to NiCrAlY being the result ofa significant reduction of the amount of y (Ni Al) and a(chromium) phases which are pre cipitated at lower temperatures.
- Parts are preferably preheated to 1750F i 50 for 5 to 6, minutes before deposition is initiated and this temperature is maintained throughout the coating operation. Deposition time varies'somewhat but is controlled to obtain the preferred coating thickness of 0003-0005 inch. Subsequent cooling to below 1000F is accomplished in a nonoxidizing atmosphere. Following the coating step, the parts may be heat treated for 1 hour at 1900F i 25 in vacuum to more fully bond the coating to the substrate and provide for easier peening.
- the coated articles may be dry glass bead peened using 0007-001 1 inch diameter beads with an intensity equivalent to 19 N.
- the peening is conducted in accordance with the provisions of the processing specification AMS 2430.
- the parts may then be heated to 1975F i 25 in dry argon, dry hydrogen or vacuum; held at heat for 4 hours;.and cooled in the protective atmosphere at a rate equivalent to air cooling. Blades and vanes so processed exhibit a coating thickness, excluding the diffused zone of 0003-0005 inch.
- FIG. 1 a graph is shown of the unexpected ductility behavior of various nickel-cobaltchromium-aluminum-yttrium coating alloys as compared to representative CoCrAlY and NiCrAlY coating alloys. The results shown therein were obtained by measuring strain to fracture of coatings deposited on tensile specimens of appropriate superalloys.
- Curve A is a plot showing the effects of substituting various amounts of cobalt for nickel in a NiCrAlY alloy having a nominal composition of, by weight, Ni- -19Cr-l4Al-O.5Y while Curve B is a plot showing the effects of substituting various amounts of cobalt for nickel in a NiCrAlY alloy having a nominal composition of, by weight, Ni-l 9Cr-l 2.5Al-0.5Y.
- Ni- CoCrAlY, or CoNiCrAlY as the case may be, coating alloys have compositional ranges consisting essentially of, by weight, 11-48% Co, l040% Cr, 9l5% Al, 0.1-1.0% reactive metal selected from the group consisting of yttrium, scandium, thorium, lanthanum and the other rare earth elements, balance essentially nickel (at least about 15%), preferably l5-40% Co, 12-30% Cr, 10l5% Al, O.ll.0% Y, balance essentially Ni, the nickel content being at least about 15%, will be effective in this regard.
- a generally, higher range of cobalt is preferred, a preferred coating consisting essentially of 25-40% Co, l4-22% Cr, l3-15% Al, 0.0l-l.0% Y, balance essentially Ni.
- Curve B a generally lower range of cobalt is preferred, a preferred coating consisting essentially of 15-35% Co, l422% Cr, l0-l3% Al, 0.0l-0.1% Y.
- ductility curves for selected coatings show ductility as a function of temperature and indicate the markedly superior tensile cracking resistance of the NiCoCrAlY coatings.
- thermomechanical fatigue tests a directionally solidified specimen substrate of MAR- M200 (with hafnium) was coated with Ni-24Co-l6- Cr12.5Al-40.3Y and run on a thermomechanical fatigue machine which pushes and pulls the specimen in severe fatigue and temperature cycles which simulate the strain-temperature cycle of a cooled turbine blade.
- a number of identical substrates were coated with Co-20Cr12Al-0.5Y and another number with a diffusion aluminide coating. Both the CoCrAlY and the diffusion aluminide coated specimens failed after approximately 1,000 cycles or less on the thermomechanical fatigue machine whereas the NiCoCrAlY coated specimen did not fail until after 1,925 cycles.
- FIGS. 3-5 a comparison of the interdiffusional, oxidation resistance and corrosion resistance properties of various NiCoCrAlY alloy coatings is shown.
- 3-5 mil coatings of NiCoCr- AlY alloy consisting essentially of the indicated amounts of cobalt, 18-21% Cr, 13-14% Al and 0.05-0.8% Y were vapor deposited onto B-l900 substrates as well as onto directionally solidified MAR- M200 (plus Hf) substrates (erosion bars).
- the coated samples were aged 100 hours in air at the indicated temperature.
- FIG. 3 the coated samples were aged 100 hours in air at the indicated temperature.
- coated components were subjected to 2000F cyclic burner-rig oxidation tests (2000F, 29 minutes forced air cool, 1 minute, JP fuel used) for up to 2,100 hours (2,030 hours hot time).
- coated components were treated under cyclic conditions (1 ,750F, 3 minutes 2000F, 2 minutes cool, 2 minutes) in a high velocity hot gas stream derived from the combustion of JP 5 jet fuel, with 35 ppm salt/air added.
- the claimed NiCoCrAlY coatings while giving unexpectedly increased ductility also simultaneously give adjustable and satisfactory degrees of interdiffusion and oxidation and hot corrosii n resistance.
- B-l900 Ni-base alloy erosion bars were coated with a 3-5 mil thick alloy having a composition, consisting essentially of, by weight, Co-20Ni-24Cr-1- 5Al0.75Y generally in accordance with the procedures outlined above.
- the coated erosion bars were subjected to 62.5 hours of vane cyclic sulfidation testing (1750F, 3 minutes 2050F, 2 minutes cool, 2 minutes with 35 ppm artificial sea salt: air ingested after combustion and using JP 5 fuel).
- the coatings exhibited a specific life of from 21.1-24.4 hours/mil and were comparable to Fe-27Cr-13Al-.75Y coatings which exhibited specific lifetimes of 22.2-27.9 hours/- mil.
- EXAMPLE 6 A 3.6 mil coating of Co20Ni-24Cr-15Al-0.75Y was vapor deposited onto a MAR-M302 Co-base alloy erosion bar and subjected to a modified vane cyclic sulfidation test (1750F, 3 minutes 2150F, 2 minutes cool, 2 minutes with 35 ppm artificial sea salt: air ingested after combustion using JP 5 fuel) in order to evaluate diffusional stability combined with the very high temperature sulfidation. The coating had a failure time of 162 hours and a specific life of 45 hours/mil.
- Coatings consisting essentiallyof Co-20Ni-20Cr-l- 2Al-0.5Y, Co20Ni16Cr-l6Al-0.5Y, Ni32.5Co-20- Cr-12Al-O.5Y and Co-20Cr-12Al-O.5Y were vapor deposited to thicknesses of 4.5-5.5 mil on Co-20Ni- -l 8Cr-2ThO alloy airfoil specimens. All coatings were essentially a two phase mixture of beta CoAl or (CoNi- )Al and gamma solid solution. The Co20Ni-16Cr-l- 6A1-0.5Y coatings were predominantly beta with a small volume percent solid solution gamma phase.
- the beta phase was continuous and represented an undesirable structure because of its potential low strain-tocrack characteristics.
- the Co-20Ni-20Cr-12Al-0.5Y and the Co-20Cr-12Al-0.5Y coatings also exhibited a continuous beta type structure but contained substantially more gamma.
- the Ni-32.5Co20Cr-12Al-0.5Y had a desired two phase plus gamma structure with the gamma phase being the continuous matrix phase.
- Additional airfoil shaped specimens of Co20Ni-l 8- Cr-2ThO were vapor deposition coated with Co20- Crl2Al-0.5Y, Co20Ni-20Cr-l2Al-0.5Y and Ni- -32.5Co-20Cr-12Al-0.5Y to a thickness of 4.5-5.5 mil using the same techniques and subjected to 1800F, 2000F, 2200F and 2400F isothermal oxidation testing, to 2200F cyclic oxidation testing (1750F, 3 minutes 2200F, 2 minutes cool, 2 minutes) and to 2200F cyclic hot corrosion testing (1750F, 3 minutes 2200F, 2 minutes cool, 2 minutes).
- the 1800F and 2000F isothermal oxidation tests were discontinued at 214 and 222 hours, respectively. All specimens shows no visual signs of degradation. Based on metallographic examination of specimens from the 1800F tests, coating degradation was least for the Ni32.5Co-20Cr-12Al-0.5Y. Also in the 2000F test, the NiCoCrAlY coating exhibited the least degradation. The extent of degradation of the CoNiCrAlY and CoCrAlY coatings was approximately equal.
- the 2400F isothermal oxidation test was run to coating failure.
- the NiCoCrAlY composition exhibited the longest life, 226 hours.
- the cyclic oxidation and-cyclic hot corrosion tests were discontinued at 207 (59 hours hot time) and 204 (58 hours hot time) hours, respectively. Coating failure had not occurred. Essentially no difference was observed in the structure between the three samples in the hot corrosion test. However, in the cyclic oxidation test, the Ni-32.5Co20Cr-l 2Al-0.5Y coating exhibited a far greater amount of retained beta than either of the other two.
- EXAMPLES 15-16 In a series of especially severe engine tests, first stage turbine blades of the alloys indicated were coated as indicated in Table l and run for 297 hours including 2,000 cycles (acceleration to full takeoff power followed by holding for a period of time, rapid deceleration to idle power and holding for a period of time). Over 100 cycles were with water injection (for thrust augmentation) which imposed the severest possible thermal shock to the coatings.
- nickel aluminum, 0.01-1.0% yttrium, balance essentially nickel, the nickel content being at least about 15%.
- a coating composition for the nickel-base and cobalt-base alloys which consists essentially of, by weight, -40% cobalt, 14-22% chromium, 13-15% aluminum, 0.01-l.0% yttrium, balance essentially nickel.
- a coating composition for the nickel-base and cobalt-base alloys which consists essentially of, by weight, 1535% cobalt, 14-22% chromium, 10-13% aluminum, 0.01-1.0% yttrium, balance essentially nickel.
- a coating composition for the nickel-base and cobalt-base alloys which consists essentially of, by weight, 32.5% cobalt, 20% chromium, 12% aluminum, 0.5% yttrium, balance essentially nickel.
- a coating composition for the nickel-base and cobalt-base alloys which consists essentially of, by weight, 20% nickel, 20% chromium, 12% aluminum, 0.5% yttrium, balance essentially cobalt.
- inventive alloy coatings are effective not only in providing long term oxidation resistance, corrosion resistance and stability but dramatically improved ductility.
- a coating composition for the nickel-base and cobalt-base alloys which consists essentially of, by weight, 1 1-48% cobalt, 10-40% chromium, 9-l5% aluminum, 0.01-1 .O% of a reactive metal selected from the group consisting of yttrium, scandium, thorium, lanthanum and other rare earth elements balance essentially nickel, the nickel content being at least about 15%.
- a coating composition for the nickel-base and cobalt-base alloys which consist essentially of, by weight, 15-40% cobalt, 12-30% chromium, lO-l5% 7.
- a gas turbine engine component comprising a nickel-base or cobalt-base superalloy coated to a thickness of at least about 0.003 inch with a coating consisting essentially of, by weight, 11-48% cobalt, l0-40% chromium, 9-l5% aluminum, 0.0l-l.0% of a reactive metal selected from the group consisting of yttrium, scandium, thorium and other rare earth elements, balance essentially nickel, the nickel content being at least about 15%.
- a gas turbine engine component comprising a nickel-base or cobalt-base superalloy coated to a thickness of at least about 0.003 inch with a coating consisting essentially of, by weight, 1540% cobalt, l2-30% chromium, l0-15% aluminum, 0.01-1 0% yttrium, balance essentially nickel, the nickel content being at least about 15%.
- a gas turbine engine component comprising a nickel-base or cobalt-base superalloy coated to a thickness of at least about 0.003 inch with a coating consisting essentially of, by weight 25-40% cobalt, 14-22% chromium, l3-l5% aluminum, 0.0l-l.0% yttrium, balance essentially nickel.
- a gas turbine engine component comprising a nickel-base or cobalt-base superalloy coated to a thick ness of at least about 0.003 inch with a coating consisting essentially of, by weight, l5-35% cobalt, 14-22% chromium, 10-l3% aluminum, 0.0l1.0 yttrium, balance essentially nickel.
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Abstract
A highly ductile coating for the nickel- and cobalt-base superalloys having long term elevated temperature oxidationerosion and sulfidation resistance and diffusional stability consists essentially of, by weight, 11-48% Co, 10-40% Cr, 9-15% Al, 0.1-1.0% reactive metal selected from the group consisting of yttrium, scandium, thorium, lanthanum and the other rare earth elements, balance essentially Ni, the nickel content being at least about 15%.
Description
United States Patent [191 [111 3, Iecht et a1. 5] Dec. 23, 1975 4] HIGH TEMPERATURE NICOCRALY 3,676,085 7/1972 Evans et a1. 29/194 COATINGS 3,754,902 8/1973 Boone er al 75/171 3,754,903 3/1973 Goward a a1. 75/171 Inventors: Ralph J. Hecht, West Palm Beach,
Fla; George W. Goward, North Haven; Richard C. Elam, Manchester, both of Conn.
Assignee: United Technologies Corporation,
Hartford, Conn.
Filed: May 13, 1974 Appl. No.: 469,186
US. Cl. 75/134 F; 75/171; 29/194 Int. Cl. C22C 30/00 Field of Search 29/194; 75/134 F, 171
References Cited UNITED STATES PATENTS 3/1972 Simmons 29/194 Primary Examiner-L, Dewayne Rutledge Assistant ExaminerE. L. Weise Attorney, Agent, or Firm-John D. Del Ponti [57] ABSTRACT A highly ductile coating for the nickeland cobalt- 10 Claims, 5 Drawing Figures NQ Q & Q
US. Patent Dec. 23, 1975 Sheet 2 of4 3,928,026
US. Patent Dec. 23, 1975 Sheet 3 of 4 I I I l I (P7/M y/z/az 0212274727 7%? away HIGH TEMPERATURE NICOCRALY COATINGS BACKGROUND OF THE INVENTION The invention described in claims 5 and 6 was made in the course of or under a contract or subcontract thereunder with the Department of the Air Force.
The present invention relates to coatings and coated articles and more particularly to coatings for the nickeland cobalt-base superalloys having high ductility while retaining desirable stability and elevated temperature oxidation and hot corrosion resistance.
Design trends for advanced gas turbine engines are toward ever increasing turbine inlet temperatures, and the demands on turbine materials have increased to the extent where contemporary aluminide coating systems can be the life limiting component of alloy-coating composites Coatings are prone to failure by a variety of mechanisms. Aluminide coatings can be, for example, a source of fracture initiation in fatigue. Coating ductility has been found to be an important determinant in fatigue life since at relatively low temperatures aluminide coatings tend to crack in a brittle manner at low strains in the tensile portions of the fatigue cycle. Although various coatings, such as the CoCrAlY type coatings described in the patent to Evans and Elam U.S. Pat. No. 3,676,085, the NiCrAlY type coatings described in the patent to Goward, Boone and Pettit U.S. Pat. No. 3,754,903 and the FeCrAlY type coatings described in the patent to Talboom and Grafwallner U.S. Pat. No. 3,542,530 have in the past provided significant improvements in the lifetimes of the superal- Ioys, further improvements are, of course, desirable. In particular, an improved coating having properties comparable to the conventional coating alloys together with significantly improved ductility would be desirable and useful. Such an improved coating is found in the nickeI-cobalt-chromium-aluminum-yttrium system as described herein.
SUMMARY OF THE INVENTION In brief, the present invention relates to a nickelcobalt-chromium-aluminum-yttrium coating alloy having greatly improved ductility as well as other properties which together render it eminently suitable for use in gas turbine engine hardware and other rigorous environments. The invention more particularly relates to a high ductility coating alloy which possesses both oxidation-erosion and sulfidation resistance and which consists of a particular combination of nickel, cobalt, chromium, aluminum and a reactive metal selected from the group consisting of yttrium, scandium, thorium, lanthanum and the other rare earth elements. The invention contemplates a coating composition consisting essentially of, by weight, 1 1-48% cobalt, 1()-40% chromium, 9-15% aluminum, 0.01-1.0% of a reactive metal selected from the group consisting of yttrium, scandium, thorium, lanthanum and other rare earth elements, balance essentially nickel, the nickel content being at least about 15%. Advantageously, the coating composition consists essentially of, by weight, about 15-40% cobalt, 12-30% chromium, -15% aluminum, 001-1 .0% yttrium, balance essentially nickel, the nickel content being at least about 15%.
In one preferred embodiment, the coating composition consists essentially of, by weight, about 25-40% cobalt, 14-22% chromium, 13-15% aluminum, 0.01-1.0% yttrium, balance essentially nickel.
In another preferred embodiment, the coating composition consists essentially of, by weight, about 1535% cobalt, 1422% chromium, 10l3% aluminum, 0.0ll'.0% yttrium, balance essentially nickel.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph which dramatically illustrates the ductility behavior of various nickel-cobalt-chromiumaluminum-yttrium coating alloys as compared to representative CoCrAlY and NiCrAlY coating alloys.
FIG. 2 is a graph showing ductility as a function of temperature of some NiCoCrAlY coating alloys as compared to representative CoCrAlY and NiCrAlY coating alloys.
FIG. 3 is a graph illustrating the diffusional stability of various nickel-cobalt-chromium-aluminum-yttrium coating alloys as compared to representative CoCrAlY and NiCrAlY coating alloys.
FIG. 4 is a graph illustrating the oxidation characteristics of various nickel-cobaIt-chromium-aluminumyttrium coating alloys as compared to representative CoCrAlY and NiCrAlY coating alloys.
FIG. 5 is a graph illustrating the sulfidation characteristics of various nickel-cobaIt-chromium-aluminumyttrium coating alloys as compared to representative CoCrAlY and NiCrAlY coating alloys.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS In the description which follows, reference will be made to various of the conventional or contemporary nickel-base and cobalt-base superalloys. Representative of alloys of this nature are those identified in the industry as follows:
NOMINAL COMPOSITION ALLOY DESIGNATION (Percent by weight) 8-1900 8 Cr, 10 Co. 1 Ti, 6 Al.
6 Mo, .11 C. 4.3 Ta,
.15 B, .07 Zr, balance Ni 21.5 Cr, 10 W. 9 Ta.
.85 C, .25 Zr, 1 Fe. balance Co 20 Ni, 18 Cr, 2 ThO balance Co 20 Ni. 30 Cr, 3 ThO balance Co 10 Cr. 15 Co. 4.5 Ti.
55 Al, 3 Mo. .17 C.
.75 V, .075 Zr, .015 B. balance Ni 9 Cr, 10 Co. 2 Ti, 5 A1. 12.5 W, .15 C, 1 Nb.
.05 Zr, .015 B, balance Ni 21 Cr. 1.75 Fe, 11 W. 2(Nb Ta), .45 C. balance Co 15 Cr. 18.5 Co, 3.3 Ti. 4.3 A1. 5 Mo, .07 C. .03 B. balance Ni MARM302 TD Cobalt Alloy TD Cobalt Alloy MAR-M200 Udimet 700 It will be appreciated that while the superalloys including those which are directionally solidified, taken as a class, are generally oxidation resistant, it is a necessary and usual practice to coat certain of the components formed therefrom in order to improve their oxidation, sulfidation, erosion and thermal shock resistance and thus extend their operating lives in advanced gas turbine engines.
As noted hereinbefore, the CoCrAlY and NiCrAlY coatings have provided significant improvements in the lifetimes 'of the superalloys. However, it was found that NiCrAlY coatings, while providing extremely high oxidation resistance and diffusional stability required improvement in sulfidation resistance and that CoCrAlY coatings, while providing extremely-high sulfidation resistance required improvement in oxidation resistance and diffusional stability. In an effort to develop a better combination of properties, a variety of overlay coatings was evaluated. It was found that coating alloys of a composition, by weight, of 11-48% cobalt, 10-40% chromium, 9-1 aluminum, 0.01-1 .0% reactive metal selected from the group consisting of yttrium, scandium, thorium, lanthanum and the other rare earth elements, balance essentially nickel, the nickel content being at least about 15%, preferably 15-40% cobalt, l2-30% chromium, -l5% aluminum, 0.01-1 .0% yttrium, balance essentially nickel, the nickel content being at least about and most preferably (1) -40% Co, 14-22% Cr, 13-15% Al, 0.0l-l.0% Y, balance essentially Ni and (2) 15-35% Co, 14-22% Cr, 10l3% Al, 0.0l-l.0% Y, balance essentially Ni dramatically and unexpectedly gave an increase in ductility while providing a satisfactory and adjustable balance of oxidation and hot corr'osion resis tance as well as acceptably low interdiffusional characteristics. While it had been known that certain of the useful NiCrAlY coatings exhibited a ductility higher than certain of the useful CoCrAlY coatings and it had been surmised therefore that a substitution of some nickel for the cobalt in the CoCrAlY composition might improve ductility, it was surprising and unexpected that the nickel-cobalt-chromium-aluminumyttrium system as defined above would provide a ductility improvement which was markedly superior to either the NiCrAlY or CoCrAlY.
While not completely understood at the present time, it appears that there is a correlation between coating ductility and the phases present. More specifically, chemistry changes which increase the amount and continuity of the (Ni, Co) solid solution phase, 7, tend to increase coating ductility while chemistry changes which increase the amount and continuity of the (Ni, Co) Al, ,8, Ni Al, y, and Cr, (1, tend to decrease ductility. Correlation of coating microstructure with coating chemistry indicates that, in the nickel-cobalt-chromium-aluminum-yttrium system herein described, desirable y B microstructures are obtained at a higher aluminum content, the increased stability of the y B microstructure caused by cobalt additions to NiCrAlY being the result ofa significant reduction of the amount of y (Ni Al) and a(chromium) phases which are pre cipitated at lower temperatures.
Those skilled in the art will recognize that certain other elements are known to be compatible with the basic chemistry of the present alloys. Accordingly, other elements such as tantalum or hafnium may be advantageously added to the alloy as required in certain applications for modification of the mechanical, diffusional or hot corrosion characteristics of the coatln coating the nickel-base and cobalt-base turbine blades and vanes the surfaces to be coated are first thoroughly cleaned free of all dirt, grease and other objectional foreign matter followed by conditioning by abrasive blasting. The coating is achieved by vapor deposition from a suitably heated molten pool of the coating material held in a vacuum chamber at 10 torr or better. The ingot melted and evaporated by electron beam heating has essentially the same chemistry as that v of the desired finished coating.
Parts are preferably preheated to 1750F i 50 for 5 to 6, minutes before deposition is initiated and this temperature is maintained throughout the coating operation. Deposition time varies'somewhat but is controlled to obtain the preferred coating thickness of 0003-0005 inch. Subsequent cooling to below 1000F is accomplished in a nonoxidizing atmosphere. Following the coating step, the parts may be heat treated for 1 hour at 1900F i 25 in vacuum to more fully bond the coating to the substrate and provide for easier peening.
The coated articles may be dry glass bead peened using 0007-001 1 inch diameter beads with an intensity equivalent to 19 N. In general, the peening is conducted in accordance with the provisions of the processing specification AMS 2430. The parts may then be heated to 1975F i 25 in dry argon, dry hydrogen or vacuum; held at heat for 4 hours;.and cooled in the protective atmosphere at a rate equivalent to air cooling. Blades and vanes so processed exhibit a coating thickness, excluding the diffused zone of 0003-0005 inch.
Of course, it will be recognized that other methods for applying the coatings may be practiced, such as sputtering, ion plating or plasma spraying, without departing from the intent of the present invention.
Referring to FIG. 1, a graph is shown of the unexpected ductility behavior of various nickel-cobaltchromium-aluminum-yttrium coating alloys as compared to representative CoCrAlY and NiCrAlY coating alloys. The results shown therein were obtained by measuring strain to fracture of coatings deposited on tensile specimens of appropriate superalloys. 1n particular, Curve A is a plot showing the effects of substituting various amounts of cobalt for nickel in a NiCrAlY alloy having a nominal composition of, by weight, Ni- -19Cr-l4Al-O.5Y while Curve B is a plot showing the effects of substituting various amounts of cobalt for nickel in a NiCrAlY alloy having a nominal composition of, by weight, Ni-l 9Cr-l 2.5Al-0.5Y. As is evident from the drawing, dramatic increases in ductility are obtained and it has been found, in general, that Ni- CoCrAlY, or CoNiCrAlY as the case may be, coating alloys have compositional ranges consisting essentially of, by weight, 11-48% Co, l040% Cr, 9l5% Al, 0.1-1.0% reactive metal selected from the group consisting of yttrium, scandium, thorium, lanthanum and the other rare earth elements, balance essentially nickel (at least about 15%), preferably l5-40% Co, 12-30% Cr, 10l5% Al, O.ll.0% Y, balance essentially Ni, the nickel content being at least about 15%, will be effective in this regard. As will be appreciated, with the higher Al content, as shown by Curve A, a generally, higher range of cobalt is preferred, a preferred coating consisting essentially of 25-40% Co, l4-22% Cr, l3-15% Al, 0.0l-l.0% Y, balance essentially Ni. With lower Al content, as shown by Curve B, a generally lower range of cobalt is preferred, a preferred coating consisting essentially of 15-35% Co, l422% Cr, l0-l3% Al, 0.0l-0.1% Y. In FIG. 2, ductility curves for selected coatings show ductility as a function of temperature and indicate the markedly superior tensile cracking resistance of the NiCoCrAlY coatings.
In one series of thermomechanical fatigue tests, a directionally solidified specimen substrate of MAR- M200 (with hafnium) was coated with Ni-24Co-l6- Cr12.5Al-40.3Y and run on a thermomechanical fatigue machine which pushes and pulls the specimen in severe fatigue and temperature cycles which simulate the strain-temperature cycle of a cooled turbine blade. A number of identical substrates were coated with Co-20Cr12Al-0.5Y and another number with a diffusion aluminide coating. Both the CoCrAlY and the diffusion aluminide coated specimens failed after approximately 1,000 cycles or less on the thermomechanical fatigue machine whereas the NiCoCrAlY coated specimen did not fail until after 1,925 cycles.
Referring to FIGS. 3-5, a comparison of the interdiffusional, oxidation resistance and corrosion resistance properties of various NiCoCrAlY alloy coatings is shown. In the drawings, 3-5 mil coatings of NiCoCr- AlY alloy consisting essentially of the indicated amounts of cobalt, 18-21% Cr, 13-14% Al and 0.05-0.8% Y were vapor deposited onto B-l900 substrates as well as onto directionally solidified MAR- M200 (plus Hf) substrates (erosion bars). In FIG. 3, the coated samples were aged 100 hours in air at the indicated temperature. In FIG. 4, coated components were subjected to 2000F cyclic burner-rig oxidation tests (2000F, 29 minutes forced air cool, 1 minute, JP fuel used) for up to 2,100 hours (2,030 hours hot time). In FIG. 5, coated components were treated under cyclic conditions (1 ,750F, 3 minutes 2000F, 2 minutes cool, 2 minutes) in a high velocity hot gas stream derived from the combustion of JP 5 jet fuel, with 35 ppm salt/air added. As will be appreciated, the claimed NiCoCrAlY coatings, while giving unexpectedly increased ductility also simultaneously give adjustable and satisfactory degrees of interdiffusion and oxidation and hot corrosii n resistance.
For a clearer unders ancing of the invention and, in addition to the data gi 1611 in the drawings, other specific examples are set forth below.
EXAMPLES 1-5 Five B-l900 Ni-base alloy erosion bars were coated with a 3-5 mil thick alloy having a composition, consisting essentially of, by weight, Co-20Ni-24Cr-1- 5Al0.75Y generally in accordance with the procedures outlined above. The coated erosion bars were subjected to 62.5 hours of vane cyclic sulfidation testing (1750F, 3 minutes 2050F, 2 minutes cool, 2 minutes with 35 ppm artificial sea salt: air ingested after combustion and using JP 5 fuel). The coatings exhibited a specific life of from 21.1-24.4 hours/mil and were comparable to Fe-27Cr-13Al-.75Y coatings which exhibited specific lifetimes of 22.2-27.9 hours/- mil.
EXAMPLE 6 A 3.6 mil coating of Co20Ni-24Cr-15Al-0.75Y was vapor deposited onto a MAR-M302 Co-base alloy erosion bar and subjected to a modified vane cyclic sulfidation test (1750F, 3 minutes 2150F, 2 minutes cool, 2 minutes with 35 ppm artificial sea salt: air ingested after combustion using JP 5 fuel) in order to evaluate diffusional stability combined with the very high temperature sulfidation. The coating had a failure time of 162 hours and a specific life of 45 hours/mil.
EXAMPLES 7-10 Two B-l900 Ni-base alloy erosion bars and two MAR-M302 Co-base alloy erosion bars were coated with nominally three mil thick coatings of Co-20Ni- -24Cr-l5Al-0.75Y as above and were subjected to oxidation-erosion testing at 2000F until failure. The 8-1900 coatings failed at 263.2 and 153.7 hours while the MAR-M302 coatings both failed at 309.2 hours.
' EXAMPLES 11-14 I Coatings consisting essentiallyof Co-20Ni-20Cr-l- 2Al-0.5Y, Co20Ni16Cr-l6Al-0.5Y, Ni32.5Co-20- Cr-12Al-O.5Y and Co-20Cr-12Al-O.5Y were vapor deposited to thicknesses of 4.5-5.5 mil on Co-20Ni- -l 8Cr-2ThO alloy airfoil specimens. All coatings were essentially a two phase mixture of beta CoAl or (CoNi- )Al and gamma solid solution. The Co20Ni-16Cr-l- 6A1-0.5Y coatings were predominantly beta with a small volume percent solid solution gamma phase. The beta phase was continuous and represented an undesirable structure because of its potential low strain-tocrack characteristics. The Co-20Ni-20Cr-12Al-0.5Y and the Co-20Cr-12Al-0.5Y coatings also exhibited a continuous beta type structure but contained substantially more gamma. The Ni-32.5Co20Cr-12Al-0.5Y had a desired two phase plus gamma structure with the gamma phase being the continuous matrix phase.
These systems were exposed in a static air environment for hours at 2000F, 2100F, 2200F and 2400F to evaluate stability and elemental interactions. The resultant coating hardness after exposure, showed no detrimental change in hardness or brittle layer formation. The Co20Nil6Cr-16A1-0.5Y composition retained its continuous beta structure during exposure and, due to its high crack susceptibility was not tested further. The other coating systems retained or transformed to a two phase mixture of beta in a continuous gamma matrix. The best stability was obtainedwith the Ni-32.5Co-2OCr12Al-0.5Y coating.
Additional airfoil shaped specimens of Co20Ni-l 8- Cr-2ThO were vapor deposition coated with Co20- Crl2Al-0.5Y, Co20Ni-20Cr-l2Al-0.5Y and Ni- -32.5Co-20Cr-12Al-0.5Y to a thickness of 4.5-5.5 mil using the same techniques and subjected to 1800F, 2000F, 2200F and 2400F isothermal oxidation testing, to 2200F cyclic oxidation testing (1750F, 3 minutes 2200F, 2 minutes cool, 2 minutes) and to 2200F cyclic hot corrosion testing (1750F, 3 minutes 2200F, 2 minutes cool, 2 minutes). In all testing the airfoil samples were rotated at 1,750 rpm in a 400-500 feet/second gas stream of combusted JP 5 fuel. For cyclic hot corrosion testing, the fuel was doped with 0.3% butyl disulfide and synthetic sea salt solution was injected into the combusted flame to yield a 3.5 ppm salt concentration in the burner flame.
The 1800F and 2000F isothermal oxidation tests were discontinued at 214 and 222 hours, respectively. All specimens shows no visual signs of degradation. Based on metallographic examination of specimens from the 1800F tests, coating degradation was least for the Ni32.5Co-20Cr-12Al-0.5Y. Also in the 2000F test, the NiCoCrAlY coating exhibited the least degradation. The extent of degradation of the CoNiCrAlY and CoCrAlY coatings was approximately equal.
The 2200F isothermal oxidation test was discontinued at 305 hours. Again the NiCoCrAlY coating showed the least degradation while the CoCrAlY coating showed the most. 1
The 2400F isothermal oxidation test was run to coating failure. Of the three coatings systems evaluated, the NiCoCrAlY composition exhibited the longest life, 226 hours.
The cyclic oxidation and-cyclic hot corrosion tests were discontinued at 207 (59 hours hot time) and 204 (58 hours hot time) hours, respectively. Coating failure had not occurred. Essentially no difference was observed in the structure between the three samples in the hot corrosion test. However, in the cyclic oxidation test, the Ni-32.5Co20Cr-l 2Al-0.5Y coating exhibited a far greater amount of retained beta than either of the other two.
EXAMPLES 15-16 In a series of especially severe engine tests, first stage turbine blades of the alloys indicated were coated as indicated in Table l and run for 297 hours including 2,000 cycles (acceleration to full takeoff power followed by holding for a period of time, rapid deceleration to idle power and holding for a period of time). Over 100 cycles were with water injection (for thrust augmentation) which imposed the severest possible thermal shock to the coatings.
aluminum, 0.01-1.0% yttrium, balance essentially nickel, the nickel content being at least about 15%.
3. A coating composition for the nickel-base and cobalt-base alloys which consists essentially of, by weight, -40% cobalt, 14-22% chromium, 13-15% aluminum, 0.01-l.0% yttrium, balance essentially nickel.
4. A coating composition for the nickel-base and cobalt-base alloys which consists essentially of, by weight, 1535% cobalt, 14-22% chromium, 10-13% aluminum, 0.01-1.0% yttrium, balance essentially nickel.
5. A coating composition for the nickel-base and cobalt-base alloys which consists essentially of, by weight, 32.5% cobalt, 20% chromium, 12% aluminum, 0.5% yttrium, balance essentially nickel.
6. A coating composition for the nickel-base and cobalt-base alloys which consists essentially of, by weight, 20% nickel, 20% chromium, 12% aluminum, 0.5% yttrium, balance essentially cobalt.
Table 1 Number Number with Percent with Alloy Coating Tested Cracked Coatings Cracked Coatings & Hf platinum aluminide 8 8 100 rhodium aluminide 7 7 100 high temperature pack aluminide 14 13 93 low temperature pack aluminide 56 5b 100 "Ni-l8Cr-l4Al- 4 4 100 Ni-l2Cr-l4Al-0.5Y 2 2 100 Ni-l8Cr-l0Al-0.5Y 2 2 100 "Ni-l2Cr-l2Al- 3 3 100 Ni-18Cr-l2Al-05Y 3 3 100 Directionally solidified MAR-M200 & Hf Ni-lXCr-IZAl-OjY .7 5 71 & Hf Ni-l lCo-ZZCr-l 1Al-0.06Y 5 0 0 Ni-20Co-l6Cr-1 1.5Al-0.05Y 5 0 0 While NiCrAlY had not previously cracked in other engine tests and is therefore considered acceptable for most engine conditions, this test was particularly severe and, as shown, only the NiCoCrAlY coated blades were completely free of coating cracks. In similar tests, CoCrAlY coatings consistently cracked.
It has been clearly established that the inventive alloy coatings are effective not only in providing long term oxidation resistance, corrosion resistance and stability but dramatically improved ductility.
What has been set forth above is intended primarily as exemplary to-enable those skilled in the art to practice the invention and it should therefore be understood that, within the scope of the appended claims, the invention may be practiced in other ways than as specifically described.
What is claimed is:
l. A coating composition for the nickel-base and cobalt-base alloys which consists essentially of, by weight, 1 1-48% cobalt, 10-40% chromium, 9-l5% aluminum, 0.01-1 .O% of a reactive metal selected from the group consisting of yttrium, scandium, thorium, lanthanum and other rare earth elements balance essentially nickel, the nickel content being at least about 15%.
2. A coating composition for the nickel-base and cobalt-base alloys which consist essentially of, by weight, 15-40% cobalt, 12-30% chromium, lO-l5% 7. A gas turbine engine component comprising a nickel-base or cobalt-base superalloy coated to a thickness of at least about 0.003 inch with a coating consisting essentially of, by weight, 11-48% cobalt, l0-40% chromium, 9-l5% aluminum, 0.0l-l.0% of a reactive metal selected from the group consisting of yttrium, scandium, thorium and other rare earth elements, balance essentially nickel, the nickel content being at least about 15%.
8. A gas turbine engine component comprising a nickel-base or cobalt-base superalloy coated to a thickness of at least about 0.003 inch with a coating consisting essentially of, by weight, 1540% cobalt, l2-30% chromium, l0-15% aluminum, 0.01-1 0% yttrium, balance essentially nickel, the nickel content being at least about 15%.
9. A gas turbine engine component comprising a nickel-base or cobalt-base superalloy coated to a thickness of at least about 0.003 inch with a coating consisting essentially of, by weight 25-40% cobalt, 14-22% chromium, l3-l5% aluminum, 0.0l-l.0% yttrium, balance essentially nickel.
10. A gas turbine engine component comprising a nickel-base or cobalt-base superalloy coated to a thick ness of at least about 0.003 inch with a coating consisting essentially of, by weight, l5-35% cobalt, 14-22% chromium, 10-l3% aluminum, 0.0l1.0 yttrium, balance essentially nickel.
Claims (10)
1. A COATING COMPOSITION FOR THE NICKEL-BASE AND COBALTBASE ALLOYS WHICH CONSISTS ESSENTIALLY OF, BY WEIGHT, 11-48% COBALT, 10-40% CHROMIUM, 9-15% ALUMINUM, 0.01-10% OF A REACTIVE METAL SELECTED FROM THE GROUP CONSISTING OF YTTRIUM, SCANDIUM, THORIUM, LANTHANUM AND OTHER RARE EARTH ELEMENTS BALANCE ESSENTIALLY NICKEL, THE NICKEL CONTENT BEING AT LEAST ABOUT 15%.
2. A coating composition for the nickel-base and cobalt-base alloys which consist essentially of, by weight, 15-40% cobalt, 12-30% chromium, 10-15% aluminum, 0.01-1.0% yttrium, balance essentially nickel, the nickel content being at least about 15%.
3. A coating composition for the nickel-base and cobalt-base alloys which consists essentially of, by weight, 25-40% cobalt, 14-22% chromium, 13-15% aluminum, 0.01-1.0% yttrium, balance essentially nickel.
4. A coating composition for the nickel-base and cobalt-base alloys which consists essentially of, by weight, 15-35% cobalt, 14-22% chromium, 10-13% aluminum, 0.01-1.0% yttrium, balance essentially nickel.
5. A coating composition for the nickel-base and cobalt-base alloys which consists essentially of, by weight, 32.5% cobalt, 20% chromium, 12% aluminum, 0.5% yttrium, balance essentially nickel.
6. A coating coMposition for the nickel-base and cobalt-base alloys which consists essentially of, by weight, 20% nickel, 20% chromium, 12% aluminum, 0.5% yttrium, balance essentially cobalt.
7. A gas turbine engine component comprising a nickel-base or cobalt-base superalloy coated to a thickness of at least about 0.003 inch with a coating consisting essentially of, by weight, 11-48% cobalt, 10-40% chromium, 9-15% aluminum, 0.01-1.0% of a reactive metal selected from the group consisting of yttrium, scandium, thorium and other rare earth elements, balance essentially nickel, the nickel content being at least about 15%.
8. A gas turbine engine component comprising a nickel-base or cobalt-base superalloy coated to a thickness of at least about 0.003 inch with a coating consisting essentially of, by weight, 15-40% cobalt, 12-30% chromium, 10-15% aluminum, 0.01-1.0% yttrium, balance essentially nickel, the nickel content being at least about 15%.
9. A gas turbine engine component comprising a nickel-base or cobalt-base superalloy coated to a thickness of at least about 0.003 inch with a coating consisting essentially of, by weight 25-40% cobalt, 14-22% chromium, 13-15% aluminum, 0.01-1.0% yttrium, balance essentially nickel.
10. A gas turbine engine component comprising a nickel-base or cobalt-base superalloy coated to a thickness of at least about 0.003 inch with a coating consisting essentially of, by weight, 15-35% cobalt, 14-22% chromium, 10-13% aluminum, 0.01-1.0 yttrium, balance essentially nickel.
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US469186A US3928026A (en) | 1974-05-13 | 1974-05-13 | High temperature nicocraly coatings |
CA220,942A CA1045421A (en) | 1974-05-13 | 1975-02-24 | High temperature nicocraly coatings |
CH498775A CH606454A5 (en) | 1974-05-13 | 1975-04-19 | |
IL47181A IL47181A (en) | 1974-05-13 | 1975-04-28 | High temperature nicocraiy coatings |
DE2520192A DE2520192C2 (en) | 1974-05-13 | 1975-05-06 | Use of Nicocraly alloys as materials for coating superalloy articles |
FR7514277A FR2271299B1 (en) | 1974-05-13 | 1975-05-07 | |
JP50055366A JPS5919977B2 (en) | 1974-05-13 | 1975-05-07 | High temperature Ni Co Cr Al Y coating composition |
SE7505339A SE410476B (en) | 1974-05-13 | 1975-05-07 | COATING COMPOSITION FOR ALLICATIONS BASED ON NICKEL OR COBOL AND GASTURBINE ENGINE COMPONENT COATED WITH THE COMPOSITION |
GB20193/75A GB1489796A (en) | 1974-05-13 | 1975-05-13 | High temperature nicocraly coatings |
IT23242/75A IT1038126B (en) | 1974-05-13 | 1975-05-13 | COMPOSITION OF COVERING FOR SUPERLAKES RESISTANT TO HIGH TEMPERATURES |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US469186A US3928026A (en) | 1974-05-13 | 1974-05-13 | High temperature nicocraly coatings |
Publications (1)
Publication Number | Publication Date |
---|---|
US3928026A true US3928026A (en) | 1975-12-23 |
Family
ID=23862796
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US469186A Expired - Lifetime US3928026A (en) | 1974-05-13 | 1974-05-13 | High temperature nicocraly coatings |
Country Status (10)
Country | Link |
---|---|
US (1) | US3928026A (en) |
JP (1) | JPS5919977B2 (en) |
CA (1) | CA1045421A (en) |
CH (1) | CH606454A5 (en) |
DE (1) | DE2520192C2 (en) |
FR (1) | FR2271299B1 (en) |
GB (1) | GB1489796A (en) |
IL (1) | IL47181A (en) |
IT (1) | IT1038126B (en) |
SE (1) | SE410476B (en) |
Cited By (81)
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US3993454A (en) * | 1975-06-23 | 1976-11-23 | United Technologies Corporation | Alumina forming coatings containing hafnium for high temperature applications |
US4029477A (en) * | 1975-10-29 | 1977-06-14 | General Electric Company | Coated Ni-Cr base dispersion-modified alloy article |
FR2406000A1 (en) * | 1977-10-17 | 1979-05-11 | United Technologies Corp | ARTICLES IN NICKEL, COBALT AND / OR IRON SUPERALLY COATED, RESISTANT TO OXIDATION AND WEAR |
US4198442A (en) * | 1977-10-31 | 1980-04-15 | Howmet Turbine Components Corporation | Method for producing elevated temperature corrosion resistant articles |
DE3010608A1 (en) * | 1979-05-29 | 1980-12-11 | Howmet Turbine Components | COATING COMPOSITION FOR NICKEL, COBALT AND IRON CONTAINING SUPER ALLOY AND SUPER ALLOY COMPONENT |
US4275124A (en) * | 1978-10-10 | 1981-06-23 | United Technologies Corporation | Carbon bearing MCrAlY coating |
US4275090A (en) * | 1978-10-10 | 1981-06-23 | United Technologies Corporation | Process for carbon bearing MCrAlY coating |
US4339509A (en) * | 1979-05-29 | 1982-07-13 | Howmet Turbine Components Corporation | Superalloy coating composition with oxidation and/or sulfidation resistance |
USRE30995E (en) * | 1977-06-09 | 1982-07-13 | General Electric Company | High integrity CoCrAl(Y) coated nickel-base superalloys |
US4346137A (en) * | 1979-12-19 | 1982-08-24 | United Technologies Corporation | High temperature fatigue oxidation resistant coating on superalloy substrate |
US4372377A (en) * | 1981-03-16 | 1983-02-08 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Heat pipes containing alkali metal working fluid |
DE3229293A1 (en) * | 1981-08-05 | 1983-03-24 | United Technologies Corp., 06101 Hartford, Conn. | COVERINGS FOR SUPER ALLOYS |
DE3229285A1 (en) * | 1981-08-05 | 1983-03-24 | United Technologies Corp., 06101 Hartford, Conn. | COATING COMPOSITION FOR PRODUCING A PROTECTIVE COATING ON SUBSTRATES FROM A SUPER ALLOY |
DE3234090A1 (en) * | 1981-09-14 | 1983-04-28 | United Technologies Corp., 06101 Hartford, Conn. | SINGLE CRYSTAL ITEM FROM A NICKEL-BASED SUPER ALLOY |
USRE31339E (en) * | 1977-08-03 | 1983-08-09 | Howmet Turbine Components Corporation | Process for producing elevated temperature corrosion resistant metal articles |
US4451299A (en) * | 1982-09-22 | 1984-05-29 | United Technologies Corporation | High temperature coatings by surface melting |
US4514469A (en) * | 1981-09-10 | 1985-04-30 | United Technologies Corporation | Peened overlay coatings |
GB2152082A (en) * | 1983-12-27 | 1985-07-31 | United Technologies Corp | Enhancement of superalloy resistance to environmental degradation |
US4615865A (en) * | 1981-08-05 | 1986-10-07 | United Technologies Corporation | Overlay coatings with high yttrium contents |
US4711665A (en) * | 1985-07-26 | 1987-12-08 | Pennsylvania Research Corporation | Oxidation resistant alloy |
US4729799A (en) * | 1986-06-30 | 1988-03-08 | United Technologies Corporation | Stress relief of single crystal superalloy articles |
US4758480A (en) * | 1987-12-22 | 1988-07-19 | United Technologies Corporation | Substrate tailored coatings |
US4842953A (en) * | 1986-11-28 | 1989-06-27 | General Electric Company | Abradable article, and powder and method for making |
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US5015502A (en) * | 1988-11-03 | 1991-05-14 | Allied-Signal Inc. | Ceramic thermal barrier coating with alumina interlayer |
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- 1975-04-19 CH CH498775A patent/CH606454A5/xx not_active IP Right Cessation
- 1975-04-28 IL IL47181A patent/IL47181A/en unknown
- 1975-05-06 DE DE2520192A patent/DE2520192C2/en not_active Expired
- 1975-05-07 SE SE7505339A patent/SE410476B/en not_active IP Right Cessation
- 1975-05-07 FR FR7514277A patent/FR2271299B1/fr not_active Expired
- 1975-05-07 JP JP50055366A patent/JPS5919977B2/en not_active Expired
- 1975-05-13 IT IT23242/75A patent/IT1038126B/en active
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Cited By (110)
Publication number | Priority date | Publication date | Assignee | Title |
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US3993454A (en) * | 1975-06-23 | 1976-11-23 | United Technologies Corporation | Alumina forming coatings containing hafnium for high temperature applications |
USRE33876E (en) * | 1975-09-11 | 1992-04-07 | United Technologies Corporation | Thermal barrier coating for nickel and cobalt base super alloys |
US4029477A (en) * | 1975-10-29 | 1977-06-14 | General Electric Company | Coated Ni-Cr base dispersion-modified alloy article |
USRE30995E (en) * | 1977-06-09 | 1982-07-13 | General Electric Company | High integrity CoCrAl(Y) coated nickel-base superalloys |
USRE31339E (en) * | 1977-08-03 | 1983-08-09 | Howmet Turbine Components Corporation | Process for producing elevated temperature corrosion resistant metal articles |
FR2406000A1 (en) * | 1977-10-17 | 1979-05-11 | United Technologies Corp | ARTICLES IN NICKEL, COBALT AND / OR IRON SUPERALLY COATED, RESISTANT TO OXIDATION AND WEAR |
US4198442A (en) * | 1977-10-31 | 1980-04-15 | Howmet Turbine Components Corporation | Method for producing elevated temperature corrosion resistant articles |
US4275124A (en) * | 1978-10-10 | 1981-06-23 | United Technologies Corporation | Carbon bearing MCrAlY coating |
US4275090A (en) * | 1978-10-10 | 1981-06-23 | United Technologies Corporation | Process for carbon bearing MCrAlY coating |
US4339509A (en) * | 1979-05-29 | 1982-07-13 | Howmet Turbine Components Corporation | Superalloy coating composition with oxidation and/or sulfidation resistance |
US4313760A (en) * | 1979-05-29 | 1982-02-02 | Howmet Turbine Components Corporation | Superalloy coating composition |
DE3010608A1 (en) * | 1979-05-29 | 1980-12-11 | Howmet Turbine Components | COATING COMPOSITION FOR NICKEL, COBALT AND IRON CONTAINING SUPER ALLOY AND SUPER ALLOY COMPONENT |
US4346137A (en) * | 1979-12-19 | 1982-08-24 | United Technologies Corporation | High temperature fatigue oxidation resistant coating on superalloy substrate |
US4372377A (en) * | 1981-03-16 | 1983-02-08 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Heat pipes containing alkali metal working fluid |
DE3229293A1 (en) * | 1981-08-05 | 1983-03-24 | United Technologies Corp., 06101 Hartford, Conn. | COVERINGS FOR SUPER ALLOYS |
DE3229285A1 (en) * | 1981-08-05 | 1983-03-24 | United Technologies Corp., 06101 Hartford, Conn. | COATING COMPOSITION FOR PRODUCING A PROTECTIVE COATING ON SUBSTRATES FROM A SUPER ALLOY |
US4615865A (en) * | 1981-08-05 | 1986-10-07 | United Technologies Corporation | Overlay coatings with high yttrium contents |
US4514469A (en) * | 1981-09-10 | 1985-04-30 | United Technologies Corporation | Peened overlay coatings |
DE3234090A1 (en) * | 1981-09-14 | 1983-04-28 | United Technologies Corp., 06101 Hartford, Conn. | SINGLE CRYSTAL ITEM FROM A NICKEL-BASED SUPER ALLOY |
US4451299A (en) * | 1982-09-22 | 1984-05-29 | United Technologies Corporation | High temperature coatings by surface melting |
GB2152082A (en) * | 1983-12-27 | 1985-07-31 | United Technologies Corp | Enhancement of superalloy resistance to environmental degradation |
US5043138A (en) * | 1983-12-27 | 1991-08-27 | General Electric Company | Yttrium and yttrium-silicon bearing nickel-base superalloys especially useful as compatible coatings for advanced superalloys |
US5035958A (en) * | 1983-12-27 | 1991-07-30 | General Electric Company | Nickel-base superalloys especially useful as compatible protective environmental coatings for advanced superaloys |
US4711665A (en) * | 1985-07-26 | 1987-12-08 | Pennsylvania Research Corporation | Oxidation resistant alloy |
US4889589A (en) * | 1986-06-26 | 1989-12-26 | United Technologies Corporation | Gaseous removal of ceramic coatings |
US4729799A (en) * | 1986-06-30 | 1988-03-08 | United Technologies Corporation | Stress relief of single crystal superalloy articles |
US4842953A (en) * | 1986-11-28 | 1989-06-27 | General Electric Company | Abradable article, and powder and method for making |
US4937042A (en) * | 1986-11-28 | 1990-06-26 | General Electric Company | Method for making an abradable article |
US5277936A (en) * | 1987-11-19 | 1994-01-11 | United Technologies Corporation | Oxide containing MCrAlY-type overlay coatings |
US4758480A (en) * | 1987-12-22 | 1988-07-19 | United Technologies Corporation | Substrate tailored coatings |
US4851300A (en) * | 1988-05-09 | 1989-07-25 | United Technologies Corporation | Precoat for improving platinum thin film adhesion |
US5015502A (en) * | 1988-11-03 | 1991-05-14 | Allied-Signal Inc. | Ceramic thermal barrier coating with alumina interlayer |
US4916022A (en) * | 1988-11-03 | 1990-04-10 | Allied-Signal Inc. | Titania doped ceramic thermal barrier coatings |
US4944858A (en) * | 1988-12-08 | 1990-07-31 | United Technologies Corporation | Method for applying diffusion aluminide coating |
US5039477A (en) * | 1989-06-02 | 1991-08-13 | Sugitani Kinzoku Kogyo Kabushiki Kaisha | Powdered metal spray coating material |
US5154885A (en) * | 1989-08-10 | 1992-10-13 | Siemens Aktiengesellschaft | Highly corrosion and/or oxidation-resistant protective coating containing rhenium |
US5273712A (en) * | 1989-08-10 | 1993-12-28 | Siemens Aktiengesellschaft | Highly corrosion and/or oxidation-resistant protective coating containing rhenium |
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 |
US5409748A (en) * | 1990-12-31 | 1995-04-25 | Pohang Iron & Steel Co., Ltd. | Heat radiating tube for annealing furnace, with ceramic coated on the inside thereof |
US5384200A (en) * | 1991-12-24 | 1995-01-24 | Detroit Diesel Corporation | Thermal barrier coating and method of depositing the same on combustion chamber component surfaces |
US5538796A (en) * | 1992-10-13 | 1996-07-23 | General Electric Company | Thermal barrier coating system having no bond coat |
US20050121116A1 (en) * | 1992-10-13 | 2005-06-09 | General Electric Company | Low-sulfur article having a platinum aluminide protective layer and its preparation |
US7510779B2 (en) | 1992-10-13 | 2009-03-31 | General Electric Company | Low-sulfur article having a platinum aluminide protective layer and its preparation |
US6969558B2 (en) | 1992-10-13 | 2005-11-29 | General Electric Company | Low sulfur article having a platinum-aluminide protective layer, and its preparation |
US20040123923A1 (en) * | 1992-10-13 | 2004-07-01 | Walston William S. | Low sulfur article having a platinum-aluminide protective layer, and its preparation |
US5455119A (en) * | 1993-11-08 | 1995-10-03 | Praxair S.T. Technology, Inc. | Coating composition having good corrosion and oxidation resistance |
US5783318A (en) * | 1994-06-22 | 1998-07-21 | United Technologies Corporation | Repaired nickel based superalloy |
US5741556A (en) * | 1994-06-24 | 1998-04-21 | Praxair S.T. Technology, Inc. | Process for producing an oxide dispersed MCrAlY-based coating |
US5716720A (en) * | 1995-03-21 | 1998-02-10 | Howmet Corporation | Thermal barrier coating system with intermediate phase bondcoat |
US5856027A (en) * | 1995-03-21 | 1999-01-05 | Howmet Research Corporation | Thermal barrier coating system with intermediate phase bondcoat |
EP0780484A1 (en) | 1995-12-22 | 1997-06-25 | General Electric Company | Thermal barrier coated articles and method for coating |
US5824423A (en) * | 1996-02-07 | 1998-10-20 | N.V. Interturbine | Thermal barrier coating system and methods |
US5987882A (en) * | 1996-04-19 | 1999-11-23 | Engelhard Corporation | System for reduction of harmful exhaust emissions from diesel engines |
US6006516A (en) * | 1996-04-19 | 1999-12-28 | Engelhard Corporation | System for reduction of harmful exhaust emissions from diesel engines |
US6422008B2 (en) | 1996-04-19 | 2002-07-23 | Engelhard Corporation | System for reduction of harmful exhaust emissions from diesel engines |
WO1999049100A1 (en) * | 1998-03-23 | 1999-09-30 | United Technology Corporation Pratt & Whitney | Method for electron beam applying leader free coating |
US6306515B1 (en) * | 1998-08-12 | 2001-10-23 | Siemens Westinghouse Power Corporation | Thermal barrier and overlay coating systems comprising composite metal/metal oxide bond coating layers |
US6565931B1 (en) | 1999-10-23 | 2003-05-20 | Rolls-Royce Plc | Corrosion protective coating for a metallic article and a method of applying a corrosion protective coating to a metallic article |
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Also Published As
Publication number | Publication date |
---|---|
FR2271299B1 (en) | 1978-06-09 |
CH606454A5 (en) | 1978-10-31 |
GB1489796A (en) | 1977-10-26 |
DE2520192A1 (en) | 1975-11-27 |
SE410476B (en) | 1979-10-15 |
JPS5919977B2 (en) | 1984-05-10 |
JPS50158531A (en) | 1975-12-22 |
IL47181A0 (en) | 1975-08-31 |
IT1038126B (en) | 1979-11-20 |
SE7505339L (en) | 1975-11-14 |
IL47181A (en) | 1977-07-31 |
CA1045421A (en) | 1979-01-02 |
DE2520192C2 (en) | 1986-02-06 |
FR2271299A1 (en) | 1975-12-12 |
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