EP0348858B1 - Metallische Schutzschicht für Bauelemente aus hochtemperaturbeständigen Legierungen für Düsentriebwerke - Google Patents

Metallische Schutzschicht für Bauelemente aus hochtemperaturbeständigen Legierungen für Düsentriebwerke Download PDF

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Publication number
EP0348858B1
EP0348858B1 EP19890111586 EP89111586A EP0348858B1 EP 0348858 B1 EP0348858 B1 EP 0348858B1 EP 19890111586 EP19890111586 EP 19890111586 EP 89111586 A EP89111586 A EP 89111586A EP 0348858 B1 EP0348858 B1 EP 0348858B1
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Prior art keywords
ruthenium
atom percent
iron
alloy
chromium
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Expired - Lifetime
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EP19890111586
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English (en)
French (fr)
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EP0348858A1 (de
Inventor
Melvin Robert Jackson
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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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/08—Metallic material containing only metal elements
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/06—Alloys based on chromium

Definitions

  • the present invention relates generally to improving the resistance of components of jet engines to oxidation and other environmental attacks. More specifically, it relates to a method by which the environmental attack of refractory metal parts in a jet engine is inhibited by coating of the parts and it relates as well to the parts which are formed by the method.
  • jet engines operate at higher efficiency if they operate at higher temperatures. If the operating temperature of a jet engine can be increased by 100° the efficiency of operation of the engine can be significantly improved. Jet engines last more than 10 years in service. If the fuel consumed by a jet engine is reduced by a significant degree over the 10 of more years of expected life of a jet engine, then there is a cost saving in the operation of engine which is very substantial and which permits the engine to be formed at higher costs. The higher engine cost is more than offset by the lower costs of operation of the engine.
  • jet engines at higher temperatures also results in a greater thrust-to-weight ratio.
  • the materials which are employed in a jet engine which is operated at higher temperature must have greater temperature capability.
  • materials can be found which operate at the same or higher temperature but which have lower density then a higher thrust-to weight ratio may be achieved.
  • the portions of a jet engine are operated at the same temperature.
  • the portions of the engine which operate at the highest temperature presently operate below 1204°C (2200°F).
  • the present invention contemplates the modification of the components in the hottest sections of the engines, and particularly of the coatings on the component elements of the hottest sections, so that the component temperature in these sections will operate at temperatures above 1315°C (2400°F). These temperatures are far greater than encountered in present components.
  • Most materials, such as nickel base alloys, which are presently employed in jet engines are molten at temperatures above 1343-1371°C (2450-2500°F).
  • the nickel base alloys are protected by an alumina-forming metallic coating.
  • alumina-forming metallic coating has a sufficient Al reservoir in the coating to re-form the protective scale when spallation of the oxide from the outer surface occurs.
  • iron, cobalt, and nickel base alloys and their alumina-forming metallic coatings are intended for use at lower temperatures below their melting points.
  • the nickel base alloys are not the most reactive metals and in cases where the protective coating is lost the nickel alloy can withstand the engine environment in its uncoated condition for relatively short periods so that loss of the coating for such short periods is not catastrophic to engine performance.
  • the substrate metal may be degraded very rapidly either by oxidation loss of metal cross-section or by environmental embrittlement.
  • the large surface area between the matrix and the reinforcement may serve as a rapid diffusion path for such oxidation and/or embrittlement.
  • the demands on a coating and the requirements for a coating on a component to protect the component from the engine environment is much more severe than is the case for the components formed of the nickel base alloys which operate at lower temperatures.
  • One such requirement is that a coating have the capability of rapidly healing of any breach of the protective oxide due to spallation or similar cause so that a "fail-safe" performance of the base metal and coating system may be achieved.
  • Another object is to provide a coating system for a metal base which permits growth of the protective oxide scale under jet engine environmental conditions and particularly high temperature oxidation conditions.
  • Another object is to provide a coating system which is self-healing at operating temperatures in the range of greater than 1204°C (2200°F).
  • objects of the invention are achieved by applying a coating having a composition corresponding to one of those enclosed within the envelope A of the accompanying Figure 5 and containing eventually yttrium in an amount less than 1.0 atom percent as a substituent for ruthenium to a refractory metal substrate.
  • the invention may be achieved by applying a coating having a composition corresponding to one of those enclosed within the smaller envelope B of the accompanying Figure 5, and containing eventually yttrium in an amount less than 1.0 atom percent as a substituent for ruthenium.
  • certain modifications may be made to the above composition by substituting other metals for at least part of the ruthenium and/or chromium.
  • Metals which can be substituted for ruthenium in the above composition include iron, nickel and cobalt.
  • the elements iron, nickel and cobalt all have very large solubilities in the hexagonal close packed ruthenium crystal structure, especially at high temperatures.
  • the three elements iron, nickel and cobalt form aluminides of the B2 ordered body centered cubic structure. This is the same structure as the RuAl of the above composition and the solubility of these three substituent metals, iron, nickel and cobalt, in the RuAl aluminide is deemed to be substantial.
  • the substituent metals iron, nickel and cobalt are substituted in the above compositions in the place of ruthenium.
  • the iron can, be substituted to a limited degree for chromium.
  • iron, nickel and cobalt can be substituted into the CrRuAl up to 15 atomic percent for nickel and cobalt and up to 20% for iron.
  • compositions of the present invention may be represented as follows: (Ru (19-x)to(34-x) ( ⁇ Fe+Ni+Co) x Al 19to34 ) ⁇ Cr (62-y)to(32-y) Fe y wherein ⁇ is a symbol indicating that the sum of the concentrations of the iron, nickel and cobalt present add up to the concentration x in atom percent, and wherein the value of x is between 0 and 15, and wherein the value of y is between 0 and 5 atom percent, and wherein the total value of the expression in atom percent is 100, and contain eventually yttrium in an amount less than 1.0 atom percent as a substituent for ruthenium.
  • compositions of the present invention may be expressed as follows: (Ru (22-x)to(28-x) ( ⁇ Fe+Ni+Co) x Al 22to28 ) ⁇ Cr (56-y)to(44-y) Fe y wherein ⁇ has the meaning stated above, and wherein x has a value between 0 and 10, and wherein y has a value between 0 and 5, and wherein the total value of the expression in atom percent is 100, and contain eventually yttrium in an amount less than 1.0 atom percent as a substituent for ruthenium.
  • What is sought is to form a protective layer on a substrate structural material as a coating which has a relatively low oxidation rate.
  • the material sought is a composition readily adapted to forming a layer which also has relatively high resistance to oxidation.
  • the layer is formed of a chromium base and has a ruthenium aluminum additive.
  • the material of the substrate on which the layer of the composition of the present invention is to be formed is one which has suitable high temperature properties such as the needed high strength at high temperature, but which does not have sufficiently high resistance to oxidation or similar deteriorating change.
  • compositions is the group of refractory metals such as tungsten, molybdenum, niobium and alloys having a refractory metal base.
  • refractory metals such as tungsten, molybdenum, niobium and alloys having a refractory metal base.
  • Such metals have good strength at high temperatures but are subject to oxidation attack at a high rate at the high temperatures at which they have good strength.
  • compositions having high strength at high temperature are the intermetallic compounds such as titanium aluminide, TiAl, and niobium aluminide, Al3Nb. Such intermetallic compounds are also subject to oxidation at the high temperatures at which these compounds exhibit good strength.
  • the compositions of the present invention have good resistance to oxidation at such high temperatures and can be used as protective coatings on these and other intermetallic compounds.
  • the substrate metal to be protected have aluminum as one of the ingredients thereof.
  • the aluminides as for example the aluminides of titanium or niobium, have aluminum as one of their ingredients and are suitable for protection by a layer of the alloy of the present invention as described above.
  • the protective coating of this invention may be applied directly to the substrate material.
  • the substrate does not contain aluminum as an ingredient or where the coated substrate is to be used at temperatures above 1260°C (2300°F) then it is advisable to employ a barrier coating layer under the protective coating layer as provided pursuant to this invention.
  • RuAl alloy was made up to have the composition RuAl + 0.2 at.% yttrium.
  • the ruthenium and aluminum components of the composition were in equal atomic percentages. Oxidation resistance studies on this alloy were made by heating the alloy in air for one hour at temperatures of 1400, 1500 and 1600°C. Weight change measurements were made and the results are listed in Table I below.
  • the RuAl composition was spalling oxide at all three temperatures, with spallation at 1600°C being the worst.
  • the numbers listed under the respective temperatures represent the milligrams per square centimeter of surface area of the sample which was lost during cooling after the heating for one hour.
  • All four elements form aluminides of the B2 ordered body centered cubic structure, and solubility of each of iron, nickel and cobalt in the ruthenium aluminide (RuAl) is deemed to be substantial. These elements are lower atomic weight than ruthenium, so that alloyed aluminides will be lower in density than is RuAl. The high cost of ruthenium is another reason to consider partial replacement of ruthenium with iron, cobalt or nickel. Again, oxidation resistance studies were made of the (Ru,Fe)Al alloy and the procedure used in Example 1 was repeated so that exposures of the alloy for one hour in air were made for the material at 1400°C, 1500°C and 1600°C. The weight change measurements and results of these tests are listed in Table II below.
  • compositions were made up as set forth in Table III below. Additions of chromium were made to a level where a separate ⁇ Cr phase was expected. The two alloys can be considered as being similar, with 15% iron replacing 10% ruthenium and 5% chromium. The high solubility of iron in ⁇ Cr suggested that alloy balance would be maintained by iron substitution for both ruthenium and chromium. In the table the compositions are listed and also the weight changes which are found after one hour exposure at 1400°C, 1500°C and 1600°C are listed.
  • the metal of the test sample is an ⁇ Ru solid solution, the remnant of Al2O3, aluminum oxide, formation depleting the ⁇ structure of aluminum.
  • the oxide was adjacent to a metallic zone devoid of any RuAl as is evident from Figure 3. This metallic zone was an ⁇ Cr solid solution.
  • Lattice parameters measured from oxide scraped from each sample after removal from test are shown in Figure 4.
  • these oxides were those present at failure, and represent exposures of 100 or less hours.
  • the scale was essentially identical in parameters to corundum-Al2O3.
  • the oxide tended to be very similar to that expected from solid solutions of Al2O3 and chromium oxide, Cr2O3.
  • Figure 4 plots lattice parameter measurements, a o and c o , against the atomic percent chromium in the alloy.
  • a o is the lattice parameter measurement along the "a" axis
  • c o is the lattice parameter measurement along the "c" axis of a unit crystal of the alloys.
  • the 40 and 50 atomic percent chromium materials of Examples 11 and 12 indicated a relatively pure corundum-Al2O3 existed on the surface after 105 hours. At 60 atomic percent chromium, although the sample survived the 105 hour test, the oxide on the surface was clearly heavily alloyed.
  • Al2O3 forms on low chromium CrRuAl alloys, a fine two phase scale forms, containing ⁇ Ru as well.
  • the interfaces between Al2O3 and the metal may act as high diffusivity paths for rapid oxidation of aluminum in the substrate.
  • the ⁇ Cr layer under the scale may be so extensive that spallation consumes aluminum in solution before more aluminum can be supplied by the underlying substrate.
  • compositions of the Cr-Ru-Al base system with very good high temperature oxidation resistance are represented by the compositions in Figure 5 which reside in the large oval, A.
  • Compositions which retain a relatively greater oxidation resistance for a longer exposure time are those which reside in the smaller oval, B.
  • composition ingredient ranges can be made by substituting iron, cobalt and/or nickel in amounts adding up to as much as 15 a/o of any one of the substituents. These substitutions are made in place of ruthenium, resulting in decreased system density and decreased cost, but at the expense of decreased melting point. The substitutions of iron, nickel or cobalt for ruthenium decreases maximum use temperature.
  • the present invention makes possible the protection of high strength at high temperature materials which are normally subject to oxidative deterioration at the high temperatures at which the materials display their high strength. Materials such as the refractory metals and intermetallic compounds may be protected in this way.
  • the base alloy is for example a CrRuAlY having the following composition: 60Cr 19.8Ru 20Al 0.2Y
  • composition may be formulated as follows: 60Cr 16.8Ru 20Al 0.2Y 3.0Co
  • compositions By replacing part of the chromium with iron and part of the ruthenium with iron the following compositions can be formulated: 57Cr 16.8Ru 20Al 0.2Y 6.0Fe 55Cr 13.8Ru 20Al 0.2Y 11.0Fe 55Cr 7.8Ru 20Al 0.2Y 17.0Fe
  • compositions of the present invention can be formulated within the scope of the present invention by substituting nickel, cobalt or iron or any combination of these substituents for ruthenium in the compositions. As indicated above the iron substitutes both for ruthenium and for chromium in the compositions of the present invention.
  • compositions of the present invention are deemed primarily useful as protective and oxidation resistant coatings when used in heavier gauge they may also serve useful structural functions. For coatings or structures greater than 0.254mm (0.01") in thickness, these compositions may contribute to the load carrying capability of the structure, particularly for structures of total thickness of 0.508mm (0.02") to 1.27mm (0.05").

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Claims (6)

  1. Eine Legierung, bestehend aus den Bestandteilen in den Anteilen, wie sie sich aus dem folgenden Ausdruck ergeben:



            (Ru(19-x) - (34-x)(ΣFe+Ni+Co)xAl19 - 34).Cr(62-y) - (32-y)Fey



    worin das Symbol Σ die Summe der Konzentrationen von Eisen, Nickel und Kobalt, die zur Konzentration x in Atomprozent aufaddiert sind, angibt, und worin der Wert von x zwischen 0 und 15 Atomprozent liegt und der Wert von y zwischen 0 und 5 Atomprozent liegt und der Gesamtwert des Ausdruckes in Atomprozent 100 beträgt und schließlich Yttrium in einer Menge von weniger als 1,0 Atomprozent als Ersatz für Ruthenium.
  2. Eine Legierung nach Anspruch 1, bestehend aus den Bestandteilen in den Anteilen, wie sie sich aus dem folgenden Ausdruck ergeben:



            (Ru(22-x) - (28-x)(ΣFe+Ni+Co)xAl22 - 28).Cr(56-y) - (44-y)Fey



    worin das Symbol Σ die Summe der Konzentrationen von Eisen, Nickel und Cobalt zur Konzentration x in Atomprozent aufaddiert anzeigt und der Wert von x zwischen 0 und 10 Atomprozent und der Wert von y zwischen 0 und 5 Atomprozent liegt, der Gesamtwert des Ausdruckes in Atomprozent 100 beträgt und schließlich Yttrium in einer Menge von weniger als 1,0 Atomprozent als einen Ersatz für Ruthenium.
  3. Eine Legierung nach Anspruch 1, bestehend aus der folgenden Zusammensetzung in Atomprozent:
    55 Cr 20 Al 14 Ru 11 Fe und schließlich Yttrium in einer Menge von weniger als 1,0 Atomprozent als einen Ersatz für Ruthenium.
  4. Die Legierung nach irgendeinem der Ansprüche 1 bis 3, die 0,2 Atomprozent oder weniger an Yttrium anstelle von Ruthenium enthält.
  5. Einen auf einer Grundlage ausgebildeten Überzug, der hochschmelzende Metalle und Legierungen nach irgendeinem der Ansprüche 1 bis 4 umfaßt.
  6. Einen hochschmelzenden bzw. feuerbeständigen Metallgegenstand, der durch eine Schicht aus einer Legierung nach irgendeinem der Ansprüche 1 bis 5 gegen oxidative Beeinträchtigung geschützt ist.
EP19890111586 1988-07-01 1989-06-26 Metallische Schutzschicht für Bauelemente aus hochtemperaturbeständigen Legierungen für Düsentriebwerke Expired - Lifetime EP0348858B1 (de)

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US21407888A 1988-07-01 1988-07-01
US214078 1988-07-01

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EP0348858B1 true EP0348858B1 (de) 1993-08-25

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WO1993007302A1 (en) * 1991-10-10 1993-04-15 Battelle Memorial Institute Oxidation-resistant refractory metal alloys
US6746782B2 (en) * 2001-06-11 2004-06-08 General Electric Company Diffusion barrier coatings, and related articles and processes
JP4847814B2 (ja) * 2006-07-25 2011-12-28 田中貴金属工業株式会社 スパークプラグ用の貴金属合金チップ及びその製造方法

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US3063835A (en) * 1959-06-18 1962-11-13 Union Carbide Corp Corrosion-resistant alloys
FR1351321A (fr) * 1963-03-22 1964-01-31 Gen Electric Alliages de chrome avec additions d'aluminium, tungstène ou rhénium

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DE68908629D1 (de) 1993-09-30
EP0348858A1 (de) 1990-01-03
DE68908629T2 (de) 1994-03-24
JPH02182857A (ja) 1990-07-17

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