US3540878A - Metallic surface treatment material - Google Patents

Metallic surface treatment material Download PDF

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US3540878A
US3540878A US693691A US3540878DA US3540878A US 3540878 A US3540878 A US 3540878A US 693691 A US693691 A US 693691A US 3540878D A US3540878D A US 3540878DA US 3540878 A US3540878 A US 3540878A
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alloy
coating
present
titanium
oxidation
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David J Levine
Moses A Levinstein
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General Electric Co
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General Electric Co
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    • 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
    • C23C12/00—Solid state diffusion of at least one non-metal element other than silicon and at least one metal element or silicon into metallic material surfaces
    • C23C12/02—Diffusion in one step
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C16/00—Alloys based on zirconium
    • 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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
    • C23C10/34—Embedding in a powder mixture, i.e. pack cementation
    • C23C10/52—Embedding in a powder mixture, i.e. pack cementation more than one element being diffused in one step

Definitions

  • METALLIC SURFACE TREATMENT MATERIAL Filed Dec. 14. 1967 mJy-w United States Patent O 3,540,878 METALLIC SURFACE TREATMENT MATERIAL David J. Levine and Moses A. Levinstein, Cincinnati,
  • a principal object of the present invention is to provide an improved superalloy surface treatment method which, while substantially maintaining the original dimensions and surface finish of an article, provides both oxidation and hot corrosion protection particularly for the articles surface based on one or more of the elements iron, cobalt and nickel.
  • Another object is to provide an improved alloy and particulate mixture including that alloy, useful in the control of the application of the elements titanium, aluminium or their combinations to such article surfaces.
  • Still another object is to provide an improved surface treatment method and material for the application of 3,540,878 Patented Nov. 17, 1970 lCC titanium, aluminum or their combinations through the judicious selection of such particulate mixture.
  • the present invention provides a particulate mixture of a powdered ternary alloy of Ti, Al and C in the range, by weight, of about 5070% titanium, 20-48% aluminum and 0.5-9% combined carbon.
  • the alloy has a dispersion of substantially acicular TiZAlC complex carbide in a matrix of Ti or Al or their alloys, preferably the binary Ti-Al with the Ti in the gamma range of the Ti-Al phase diagram.
  • the particulate mixture includes a halide salt activator which will react with the metallic elements in the ternary alloy to form a halide.
  • the activator preferably is one selected from the chlorides and uorides of NH4 and of the alkali metals in Group l-A of the Periodic Table of Elements.
  • a most practical activator is a halide salt selected from NaF, KF, NH4C1 and NH4F, and included in an amount of about 0.1-10 weight percent of the mixture.
  • One aspect of the present invention is the recognition of a significant relationship between aluminum, titanium and carbon, referred to herein as the ⁇ Deposition Factor or (D/F).
  • D/F ⁇ Deposition Factor
  • This relationship is a common denominator for control of the method of the present invention through the use of the particulate mixture especially for the codeposition of Al and Ti. It is useful in dening the aluminum concentration in the Ti-Al matrix form of the ternary alloy in relation to the stoichiometric TiAl compound composition, for use in a diffusion type coating process to which the present invention relates.
  • composition range of the ternary alloy of the present invention is particularly suitable for control of the codeposition of aluminum and titanium or, if desired, individually of aluminum or of titanium. This will be discussed in more detail in connection with the drawing. However, during the evaluation of such a ternary alloy as a powder in a pack diffusion coating process, it was recognized that a difference in coating behavior was at least partially based on the carbon content of the alloy. Powders including combined carbon below about 0.5 weight percent responded differently than those within the range of about 0.5 to about 9 weight percent combined carbon.
  • the particulate pack mixture used in the practice of the method of the present invention includes a powder of the multiphase ternary alloy of Ti, Al and C in the above defined range; an inert filler material, which will not react with other components of the mixture, to prevent powder sintering; and a halide salt activator, preferably of the above defined type, which reacts with the elements to be deposited to form a volatile compound.
  • a ller material which has been found to be satisfactory and which was used extensively in the evaluation of the present invention is the refactory oxide A1203 powder, comprising about -80 Weight percent of the total pack mixture.
  • the filler powder, the powdered ternary alloy and the activator are blended together such as in an ordinary powder blender.
  • the ternary alloy powders described here in connection with the present invention were prepared by vacuum induction melting virgin materials into an ingot of desired composition. The ingot was then pulverized to obtain a powder, for example -100 mesh, which has been found to be suitable for the practice of the method of the present invention.
  • Typical of examples of the ternary alloy of Ti, Al and C evaluated in connection with the present invention are those shown in the following Table I.
  • the amount of carbon shown is that analyzed and found to be combined as the TigAlC complex carbide.
  • the Ti2AlC complex carbide was specifically identified by chemical analysis of the acicular phase residue extracted from the matrix as well as by electron microprobe analysis. X-ray diffraction testing identified the TiZAlC complex carbide as having an hexagonal close packed lattice parameter rather than the known cubic structures usually found in the alpha Ti range.
  • Some of the alloy powders included small amounts of uncombined carbon. For instance, the alloy of Example 1 included about 3% uncombined carbon.
  • the coating box was then placed in a retort located in a yfurnace preset at 1950 F. After purging the retort and coating box with argon, a hydrogen atmosphere was introduced and the coating box was kept at 1950 F. for about 4 hoursjThen it was pulled back into the cold zone of the retort where it was allowed to cool to 300 F.1The retort was then opened and the coating box was removed.
  • l y n As can be seen from Table II, those ternary alloys having a Deposition Factor of up to about 1l resulted in a relatively uniform weight gain. However, those ternary alloys having a Deposition Factor of between about 11 and 16 showed a slowly increasing weight gain rate. Above about 16, the weight gain rate became extremely rapid.
  • the Deposition Factor associated with the present invention is a measure ofthe aluminum in excess of the sum of the amount which will lform the stoichiometric compound AlTi in the matrix and the amount necessary to form the complex carbide TigAlC, in that preferred form of the present invention in which the matrix is a binary of Ti and Al, with the nonstoichiometric Ti being in the gamma form.
  • this preferred form avoids the formation of substantial quantities of TiAl3 which can, under certain compositional lconditions, precipitate in the gamma Ti of the matrix.
  • the Deposition Factor is a dimensionless number related to the present inventions recognitionof. the unique interaction of carbon with the aluminum and titanium.
  • the Deposition Factor is a mathematical tool which physically defines this unique interaction considering the effective amount of carbon as that .inthe combined state in the form of a complex carbided TigAlC.
  • the Deposition Factor which is a ineasu'r'e of excess Yaliiminum as described above, can be derived or explained mathematically as follows:
  • the Deposition Factor can be approximated from:
  • the D/ F number representing a materials balancefor positive numbers defines the aluminum in the matrix in excess of the TiAl stoichiometric composition. Hence it represents the excess aluminum which is available for coating deposition.
  • the D/F number reaches zero, there is no excess aluminum over the amount of Ti in the matrix and the remaining phases are TizAlC and stoichiometric TiAl.
  • equal numbers of aluminum and titanium atoms will be deposited in the same manner. If the D/F number is less than zero, there is an excess of Ti and deposition of Ti will become even more pronounced.
  • the deposition of either aluminum, or titanium, or combinations of the two are possible to control, through the present invention, the deposition of either aluminum, or titanium, or combinations of the two.
  • those ternary alloys having a D/F number less than zero, and hence lying within the area AGHBA include Ti in the matrix in the alpha condition and have an excess of titanium rather than aluminum. Surfaces or coatings produced from these alloy forms can be useful in certain instances. However, the oxidation and hot corrosion resistance is less than that produced from alloys found to the right of vertical line AB, in which area gamma titanium is formed. Therefore, in its preferred form, the present invention defines the D/F number as being greater than zero. In addition, it was found that a phase change occurs in the area of a D/F number of about 18. This change is represented in the drawing by broken line CD. Above that area, the matrix can include substantial amounts of TiAl3 which tends to produce coatings of excessive thicknesses. Therefore, the specifically preferred form of the present invention defines the D/F number as being between zero and about 18.
  • the matrix in the area AIFA is predominantly aluminum and that only aluminum will be deposited at a relatively high rate from such a system.
  • the present invention has as one of its principal objects the provision of an improved surface treatment which substantially maintains the original dimensions of the article being treated, the rapid deposition of aluminum, though useful in certain instances, is not specifically preferred for jet engine components. Therefore, the specifically preferred form of the present invention contemplates the use of ternary alloy of Al, Ti and C within that area of the drawing defined by ABCDA, having a composition by weight of about 50-70% Ti, 20-48% Al and 0.5-9% C (combined) and a D/F number of between zero and about 18.
  • the range of combined carbon in such ternary alloys is limited to about 9 weight percent.
  • aluminum is preferentially deposited along with some titanium.
  • substantially equal amounts of titanium and aluminum appear to be deposited. Because larger amounts of titanium, such as would occur in this latter instance, can have deterimental effects on oxidation and hot corrosion resistance of the resulting coating, the present invention requires the presence of carbon combined as described above within a critical range.
  • Coatings produced from ternary alloys of Table I having a Deposition Factor between about 3 and 16 resulted in relatively low titanium content.
  • coatings resulting from the use of the ternary alloy powders having a D/ F number of close to or below Zero resulted in relatively high titanium concentrations in the coating.
  • Oxidation testing of the specimens coated with the ternary alloys of Table I showed a gross failure in the coated specimens with high titanium concentrations whereas the coatings having lower titanium concentrations showed no indication of oxidation attack even though the coatings were of equal thickness and were exposed to the same oxidation parameters.
  • coatings of the type to which the present invention relates and with higher titanium concentrations when applied to nickel base superalloys exhibit poor oxidation resistance as a result of the formation of a poor oxidation resistant titanium-rich Ni3(Al, Ti) phase in the outer coating layer.
  • the preferred compounds in such coating are NiAl or Al-rich NiAl which have excellent resistance to high temperature oxidation.
  • Oxidation failure of the coating which occurred at a D/F number of 2.8, is believed to be the result of the coatings higher titanium content forming the/lower oxidation resistant Ti-rich Ni3(Al, Ti) phase.
  • the oxidation characteristics of the applied coating remained substantially the same and no oxidation failure was observed.
  • the alloy powder of Example 5 of D/F number 13.6 through application was reduced to 12.0 and then to 10.4. The resultant coating showed no substantial decrease in oxidation resistance.
  • the coating formed on a cobalt base alloy using the same powders and processing parameters consists mainly of CoAl(Ti).
  • the NiAl compound has excellent oxidation resistance.
  • the Ti replaces the Al in CoAl in cobalt base alloys such as one consisting nominally, by weight, of 25% Cr, 10% Ni, 7.5% W, .5% C with the balance Co, sometimes referred to as X-40 alloy.
  • This decrease in oxidation resistance is based on the fact that cobalt-titanite (CoTi) is a relatively poor oxidation resistant compound compared with CoAl which is extremely oxidation resistant.
  • Evaluation of the present invention included application of various ternary alloy powders of Table I to X-40 Cobalt base alloy specimens in the manner described above in connection with nickel base alloys.
  • the evaluation of the powder of Example 18, having a D/F number of 5.6 and excessive concentrations of Ti in the coating in the form of CoTi resulted in coating failure during oxidation testing.
  • Other specimens coated with powders having D/F numbers of 13.6 (Example 5) and 13.7 (Example 4) showed no evidence of oxidation failures even after several reuses which would reduce the D/F number substantially.
  • the present invention when applied to surfaces based on cobalt is preferably confined to the use of a powder consisting essentially of, by weight, 59-62% Ti, S2-35% Al and 4 5-6% combined carbon.
  • the Deposition Factor number is preferred in the range of 9-16 to control the amount of titanium in the coating and to limit the precipitation of the undesirable TiAl3 to concentrations which have been found to be acceptable from the coating thickness viewpoint.
  • the Ti-Al-C ternary alloy in which this invention requires the presence of the cornplex carbide TigAlC is useful in certain applications, for example on nickel base superalloys as the above described Ren 41 alloy, when the ternary alloy combined carbon range is about 0.5-3.
  • a preferred form of the present invention for application to nickel base alloys for severe hot oxidation conditions employs the ternary alloy having a composition, by weight, of 60-63% Ti, 32-35% Al and 3.5-5% combined carbon, with the Deposition Factor maintained in the range of about 9-13.
  • uncombined carbon for example, up to 3 weight percent or more can be present without detrimental effect on the ternary alloy.
  • small amounts of such impurities as Ni, Mn, Cr and Fe can be present in the total amount of about 2 weight percent.
  • One type of hot corrision evaluation of the coating resulting from the present invention Iwas conducted in a dynamic oxidation flame tunnel provided with means to ingest a 1.6% NaCl/NazSO.,l salt solution and to produce a corrodent concentration of about p.p.m.
  • the NaCl/NA2SO4 ratio was 9:1, closely simulating the Cl/SO4 ratio in sea water.
  • One such test was conducted on the airfoil surface section of nickel base alloy jet engine turbine blades having a nominal composition, by weight, of 18% Cr, 3% Ti, 3% Al, 18% Co, 4% Mo, 0.005% B, 0.05% C, balance Ni and incidental impurities.
  • the pack mixture used in the manner described above included the ternary alloy by weight of 62.0% Ti, 34.8% A1, 4.6% carbon, total, 0.16% carbon, free with less than 0.15% Fe.
  • the alloy was mixed with powdered A1203 in an amount such that the ternary alloy consisted essentially of 40 weight percent and the A1203 powder consisted of about 60 weight percent of the pack mixture.
  • To this mixture was added 0.2 weight percent NH4F activator. Processing was conducted at 1950 F. for four hours.
  • comparison testing was made with the same article coated with two commercially available high temperature pack diffusion type coatings currently used as a coating in production on jet engine turbine blade airfoils. After tests of 25 and 50 hours at temperatures ranging between l600-l800 F.
  • halide salt activators as NaF, KF, NHrCl and NH4F in pack mixtures described above have shown that range to be applicable to the present invention as Well.
  • bromide and iodide forms of such salts were tested and found to be satisfactory, though more sluggish in action.
  • Such halide salt activators as CrF for example, in an amount of about 0.5% with the last described specific pack mixture, was shown to operate successfully as an activator in the present invention.
  • the more reactive activators as NHCl, KCl, NaCl and NH4F, when included in the pack mixture at somewhat less than 0.2 fweight percent. This amount, which is herein stated as about 0.1 weight percent, means a small but reasonably effective amount.
  • halide salt activators in the range of about 0.1-10 weight percent can be included in the particulate pack mixture and in the practice of the method of the present invention.
  • the more reactive activators of the type described above tend to perform their function of bringing about transfer of appropriate amounts of aluminum and titanium at a relatively low point in the useful range.
  • a typical simplified mechanism for the coating of a nickel base alloy with aluminum from the ternary Ti-Al-C alloy using lNI-LlF as the halide carrier first involves the reaction to produce aluminum fluoride and the ammonium ion. Then there occurs a reaction with nickel in the surface of the nickel base alloy to form a 65 nickel aluminum.
  • the use of excessive amounts of activator can result in the transfer of too much titanium, thereby reducing coating oxidation resistance.
  • the rate of conversion of such elements as aluminum in the ternary alloy to the halogen prior to the reaction with the article surface increases in rate up to about 2% activator content in the pack. Thereafter, there is a much slower, if any, increase in rate. Usually, such a small rate increase would not warrant the inclusion of greater amounts of activator from a practical and economical viewpoint. Therefore, the preferred range for the inclusion of the reactive activators as Nal-T, KF, NHQCI and NH4F is about 0.1-2 weight percent.
  • the alloy having a dispersion of TizAlC complex carbide in a matrix selected from the group consisting of Ti, Al and their alloys.
  • the alloy of claim 1 in which the matrix is a binary alloy of Ti and Al with the Ti in the gamma range of the Ti-Al phase diagram and having a Deposition Factor (D/F) number in the range of 0 and about 18 as determined by the relationship:
  • D/F Deposition Factor
  • the alloy of claim 3 in which the elements consist essentially of, by fweight, 59-62% Ti, 32-35% Al and 4.5-6% combined carbon with the Deposition Factor number in the range of about 9-16 5.
  • the alloy of claim 3 in which the elements consist essentially of, by Weight, 60-63% Ti, 32-35% Al and 3.5-5% combined carbon with the Deposition Factor number in the range of about 9-13.

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  • Engineering & Computer Science (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Powder Metallurgy (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
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Cited By (30)

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US3951642A (en) * 1974-11-07 1976-04-20 General Electric Company Metallic coating powder containing Al and Hf
US3953193A (en) * 1973-04-23 1976-04-27 General Electric Company Coating powder mixture
US4071638A (en) * 1974-11-07 1978-01-31 General Electric Company Method of applying a metallic coating with improved resistance to high temperature to environmental conditions
US4294615A (en) * 1979-07-25 1981-10-13 United Technologies Corporation Titanium alloys of the TiAl type
US5334263A (en) * 1991-12-05 1994-08-02 General Electric Company Substrate stabilization of diffusion aluminide coated nickel-based superalloys
US5900102A (en) * 1996-12-11 1999-05-04 General Electric Company Method for repairing a thermal barrier coating
US6146696A (en) * 1999-05-26 2000-11-14 General Electric Company Process for simultaneously aluminizing nickel-base and cobalt-base superalloys
EP1236810A1 (de) * 2001-02-28 2002-09-04 Vacuheat GmbH Verfahren und Vorrichtung zur partiellen thermochemischen Vakuumbehandlung von metallischen Werkstücken
US6482470B1 (en) 2000-07-18 2002-11-19 General Electric Company Diffusion aluminide coated metallic substrate including a thin diffusion portion of controlled thickness
US6559094B1 (en) 1999-09-09 2003-05-06 Engelhard Corporation Method for preparation of catalytic material for selective oxidation and catalyst members thereof
US20030165414A1 (en) * 1998-05-01 2003-09-04 Galligan Michael P. Exhaust treatment apparatus containing catalyst members having electric arc sprayed substrates and methods of using the same
US20040009106A1 (en) * 1998-05-01 2004-01-15 Galligan Michael P. Catalyst members having electric arc sprayed substrates and methods of making the same
US20040038819A1 (en) * 1998-05-01 2004-02-26 Galligan Michael P. Pliable metal catalyst carriers, conformable catalyst members made therefrom and methods of installing the same
US20050163677A1 (en) * 1998-05-01 2005-07-28 Engelhard Corporation Catalyst members having electric arc sprayed substrates and methods of making the same
US20050260346A1 (en) * 2004-03-16 2005-11-24 General Electric Company Method for aluminide coating a hollow article
US20050262965A1 (en) * 2004-05-26 2005-12-01 Honeywell International, Inc. Ternary carbide and nitride composites having tribological applications and methods of making same
US20060088435A1 (en) * 2004-05-26 2006-04-27 Honeywell International, Inc. Ternary carbide and nitride materials having tribological applications and methods of making same
US20060211241A1 (en) * 2005-03-21 2006-09-21 Christine Govern Protective layer for barrier coating for silicon-containing substrate and process for preparing same
US20060210800A1 (en) * 2005-03-21 2006-09-21 Irene Spitsberg Environmental barrier layer for silcon-containing substrate and process for preparing same
US20060222884A1 (en) * 2005-03-31 2006-10-05 Nagaraj Bangalore A Turbine component other than airfoil having ceramic corrosion resistant coating and methods for making same
US20060280954A1 (en) * 2005-06-13 2006-12-14 Irene Spitsberg Corrosion resistant sealant for outer EBL of silicon-containing substrate and processes for preparing same
US20060280952A1 (en) * 2005-06-13 2006-12-14 Hazel Brian T Bond coat for corrosion resistant EBC for silicon-containing substrate and processes for preparing same
US20060280953A1 (en) * 2005-06-13 2006-12-14 Hazel Brian T Bond coat for silicon-containing substrate for EBC and processes for preparing same
US20060280955A1 (en) * 2005-06-13 2006-12-14 Irene Spitsberg Corrosion resistant sealant for EBC of silicon-containing substrate and processes for preparing same
EP1939318A2 (en) 2006-12-27 2008-07-02 General Electric Company Carburization process for stabilizing nickel-based superalloys
US7553517B1 (en) 2005-09-15 2009-06-30 The United States Of America As Represented By The United States Department Of Energy Method of applying a cerium diffusion coating to a metallic alloy
DE102017204279A1 (de) 2017-03-15 2018-09-20 Siemens Aktiengesellschaft CMC mit MAX-Phasen und Keramikschicht
DE102017205787A1 (de) * 2017-04-05 2018-10-11 Siemens Aktiengesellschaft MAX-Phasen als Beschichtung, Bauteil und Verwendung
DE102018205183A1 (de) * 2018-04-06 2019-10-10 Siemens Aktiengesellschaft Oxidationsschutz für MAX-Phasen
US10794210B2 (en) 2014-06-09 2020-10-06 Raytheon Technologies Corporation Stiffness controlled abradeable seal system and methods of making same

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FR2486103A1 (fr) * 1980-07-02 1982-01-08 Zaets Inna Composition pour le revetement de metaux ferreux par diffusion a base de titane, d'oxyde d'aluminium et d'un halogenure d'ammonium
FR2511396A1 (fr) * 1981-08-14 1983-02-18 Electricite De France Procede de revetement de surfaces metalliques par diffusion d'aluminium pour la protection contre le soufre a haute temperature
GB2517653B (en) * 1989-01-03 2017-08-30 United Technologies Corp Fabrication of gamma titanuim (TiAl) alloy articles by powder metallurgy

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US3203794A (en) * 1957-04-15 1965-08-31 Crucible Steel Co America Titanium-high aluminum alloys
US3052538A (en) * 1960-04-21 1962-09-04 Robert W Jech Titanium base alloys

Cited By (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3953193A (en) * 1973-04-23 1976-04-27 General Electric Company Coating powder mixture
US3951642A (en) * 1974-11-07 1976-04-20 General Electric Company Metallic coating powder containing Al and Hf
US4071638A (en) * 1974-11-07 1978-01-31 General Electric Company Method of applying a metallic coating with improved resistance to high temperature to environmental conditions
US4294615A (en) * 1979-07-25 1981-10-13 United Technologies Corporation Titanium alloys of the TiAl type
US5334263A (en) * 1991-12-05 1994-08-02 General Electric Company Substrate stabilization of diffusion aluminide coated nickel-based superalloys
US5900102A (en) * 1996-12-11 1999-05-04 General Electric Company Method for repairing a thermal barrier coating
US20030165414A1 (en) * 1998-05-01 2003-09-04 Galligan Michael P. Exhaust treatment apparatus containing catalyst members having electric arc sprayed substrates and methods of using the same
US20040009106A1 (en) * 1998-05-01 2004-01-15 Galligan Michael P. Catalyst members having electric arc sprayed substrates and methods of making the same
US20040038819A1 (en) * 1998-05-01 2004-02-26 Galligan Michael P. Pliable metal catalyst carriers, conformable catalyst members made therefrom and methods of installing the same
US20050163677A1 (en) * 1998-05-01 2005-07-28 Engelhard Corporation Catalyst members having electric arc sprayed substrates and methods of making the same
US8062990B2 (en) 1998-05-01 2011-11-22 Basf Corporation Metal catalyst carriers and catalyst members made therefrom
SG84598A1 (en) * 1999-05-26 2001-11-20 Gen Electric Process for simultaneously aluminizing nickel-base and cobalt-base superalloys
US6146696A (en) * 1999-05-26 2000-11-14 General Electric Company Process for simultaneously aluminizing nickel-base and cobalt-base superalloys
US6559094B1 (en) 1999-09-09 2003-05-06 Engelhard Corporation Method for preparation of catalytic material for selective oxidation and catalyst members thereof
US6482470B1 (en) 2000-07-18 2002-11-19 General Electric Company Diffusion aluminide coated metallic substrate including a thin diffusion portion of controlled thickness
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GB1218295A (en) 1971-01-06
SE366344B (enExample) 1974-04-22
SE346126B (enExample) 1972-06-26
DE1783199B2 (de) 1980-04-03
ES362491A1 (es) 1970-12-01
IL30969A (en) 1972-03-28
DE1758987A1 (de) 1971-03-18
CH523966A (de) 1972-06-15
DE1783199C3 (de) 1981-01-29
BE720827A (enExample) 1969-03-13
FR1582301A (enExample) 1969-09-26
ES362492A1 (es) 1970-12-01
ES358033A1 (es) 1970-04-01
DE1783199A1 (de) 1977-06-23
IL30969A0 (en) 1968-12-26

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