EP0006951A1 - Ameliorations aux alliages a base de nickel, cobalt et fer, ou s'y rapportant. - Google Patents

Ameliorations aux alliages a base de nickel, cobalt et fer, ou s'y rapportant.

Info

Publication number
EP0006951A1
EP0006951A1 EP19780900280 EP78900280A EP0006951A1 EP 0006951 A1 EP0006951 A1 EP 0006951A1 EP 19780900280 EP19780900280 EP 19780900280 EP 78900280 A EP78900280 A EP 78900280A EP 0006951 A1 EP0006951 A1 EP 0006951A1
Authority
EP
European Patent Office
Prior art keywords
alloy
platinum
weight
component
nickel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP19780900280
Other languages
German (de)
English (en)
Other versions
EP0006951B1 (fr
Inventor
Alan Sydney Darling
Malcolm Mclean
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
UK Secretary of State for Defence
Original Assignee
UK Secretary of State for Defence
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by UK Secretary of State for Defence filed Critical UK Secretary of State for Defence
Publication of EP0006951A1 publication Critical patent/EP0006951A1/fr
Application granted granted Critical
Publication of EP0006951B1 publication Critical patent/EP0006951B1/fr
Expired legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur

Definitions

  • Nickel-, Cobalt- and Iron-based Alloys This invention relates to nickel-, cobalt- and iron-based alloys comprising those suitable for use at high temperatures under oxidising conditions or corrosive conditions, and more particularly, but not exclusively, is concerned with directionslly solidified nickel-based alloys for use in these conditions.
  • This invention seeks to provide high temperature nickel, cobalt and iron-based alloys having oxidation and corrosion resistance made good by controlled alloying additions which do not have any substantial adverse effect on the high temperature mechanical strength of the alleys in which they are incorporated and which, at least in some cases, lead to enhanced oxide scale adhesion.
  • alloy consisting of at least 5 wt % of chromium, from 0 to 3 wt % of carbon, a component X, a component Z, and a balance of one or more of nickel, cobalt and iron together with incidental elements and impurities if any, wherein component X is one or more of;
  • component Z comprises m p wt % of one or more platinum group metals (as herein defined) together with m c wt % of one or more platinum-complementing metals (as herein defined) with
  • a method of modifying the oxidation resistance and corrosion resistance of a nickel based, cobalt based or iron based alloy which comprises including in the alloy composition an amount m p wt % of a platinum group metal (as herein defined) together with an amount m c wt % of one or more platinum complementing elements (as herein defined), and wherein
  • platinum group metal should be taken to mean one of osmium, iridium, platinum, ruthenium, rhodium and palladium
  • platinum-complementing element should be taken to mean one of the following:- titanium, scandium, yttrium, lanthanum, hafnium, tantalum, zirconium, niobium, and any of the lanthanide elements (Ce to Lu).
  • “Incidental elements and impurities” can comprise elements such as silicon, manganese and boron or, to a lesser extent vanadium, which elements are usually found in commercial iron-based alloys, and will also generally comprise small amounts of oxygen, nitrogen, hydrogen, phosphorus and sulphur.
  • Nickel-, cobalt- and iron-based gas turbine alloys depend for their high temperature strength on carefully controlled micro-structures which generally contain, among several other phases, carbides based on Ti(Mo)C, Ti(Eb)C or other transition element compounds. Otherwise, the micro-structures may contain less stable components, such as Cr 3 C 2 . (It has been proposed to provide Cr 3 C 2 in a directionally solidified alloy in the form of slender reinforcing fibres).
  • the matrix of the alloy must have a low affinity either for carbon or for the metal from which the carbide is formed.
  • Certain metals known for their solution strengthening capabilities have a high affinity for one or the other of the components of these strengthening carbides. Their addition has been shown to render the reinforcing carbides less stable.
  • zirconium, for example which strengthens solid solutions very effectively in other alloy systems, cannot, in general, be added safely to superalloys because of its very high affinity for carbon, which tends to decompose any titanium or niobium carbides in its vicinity.
  • rare earth metals such as yttrium
  • yttrium when present in excess in the alloy, tend to decompose these reinforcing fibres, thus limiting the high temperature mechanical properties of this material, although its oxidation resistance is improved.
  • Relatively small additions of one of the six platinum group metals are known by the present Applicants to enhance the oxidation and corrosion/of specific nickel-, iron- and cobalt-based alloys, particularly when the alloy to which additions are made is one of those which form a protective layer of aluminium oxide.
  • platinum group metals can rarely be made to such materials, however, because these metals have a tendency to decompose any carbides upon which the superalloy depends for mechanical reinforcement. This decomposition is caused, not because of the affinity of the platinum metals for carbon, which is very small, but because of their exceedingly high affinity for the metals which form stable carbides. Itis known, for example, that platinum and iridium are capable of decomposing lanthanum carbide at temperatures as low as 1000oC. When platinum additions are made, therefore, to the directionally solidified
  • the above-mentioned carbide-forming and carbide-decomposing groups of metals can in certain circumstances be jointly added to superalloys in quantities up to a total of 5% by weight without any deleterious effect upon structure or mechanical properties, and with some improvement in their resistance to oxidation and corrosion at high temperatures. It is thought that this is possible because the platinum group (carbide-decomposing) metals have an affinity for the carbide-forming elements which is comparable to and in most instances higher than the affinity of these carbide-forming elements for carbon.
  • the strengthening carbides can thus remain stable, and the platinum group metals can therefore be safely added without detriment to the high temperature properties of nickel, cobalt- or iron-based alloys, provided that they are suitably associated with one or more of the platinum complementing elements titanium, scandium, yttrium, lanthanum, hafnium, tantalum, zirconium, niobium and any of the lanthanide elements (Ce to Lu).
  • component Z contains between 50 and about 93% by weight of the platinum group metals. In any case, there must be more than about 0.025 wt % of a platinum group metal present in component Z (corresponding to a lower limit of 0.3 in the quantity m p /m c , given a lower limit of 0.1 in the quantity(m p + m c ).
  • EXAMPLE 1 Tb an alloy having a nominal composition (expressed in wt %) as set out below (incidental elements and impurities amounting to 1 wt %)
  • alloys A, B, C and D as shown in Table 2.
  • Alloys C and D are according to the invention.
  • the basic alloy and alloys A and B are for comparison.
  • the observations set out below were made on the five alloy compositions given in Table 2. Microstructure.
  • the basic alloy to which no addition had been made had a relatively poor resistance to oxidation when exposed to air at high temperatures either cyclically or under isothermal conditions
  • the initially formed scale of Al 2 O 3 spalled readily and oxidation continued with the formation of Cr 3 O 3 , nickel-chromium spinels, and with internal oxidation.
  • yttrium alone alloy A
  • alloy C The alloy to which the ⁇ toichiometrically adjusted Pt 5 Y addition has been made (alloy C) developed on oxidation testing in air a protective skin of alumina which was resistant to spalling when cycled in temperature and also when handled at room temperature. After exposure to air at atmospheric pressure for 1000 hours at 1000°C no measurable oxide skin was observed and the carbide fibres retained their integrity to the specimen surface.
  • Table 2 above shows the results of creep tests performed in air on the various alloys at 1000°C under a direct tensile stress of 100mPa. ⁇ he alloy C retained the mechanical properties of the yttrium doped alloy (alloy A) and both were substantially stronger at high temperatures than those/either Pt or Y (alloys B and D respectively) above the level required to form stoichiometric Pt 5 Y.
  • EXAMPLE 2 The nominal compositions of the alloys studied are shown in Table 3. Alloy K is according to the invention and the remaining alloys are for comparison.
  • alloy J No microstructual differences between alloys J and L were observed.
  • alloy J neither electron probe micro-analysis or optical examination were able to detect any intennetallics containing platinum.
  • Alloy K (containing 0.3 Hf - 0.9 Pt) had a grain size smaller than alloy L and similar to that in Hf-containing alloys with no platinum (alloys M and N). Again, no platinum-containing intermetallics could be detected in alloy K and it would appear that the hafnium and platinum additions were both completely soluble in the alloy, at least at the concentrations used here.
  • the hafnium On oxidation of the samples of alloy K, the hafnium usually oxidised internally, but there was no apparent segregation of the platinum.
  • Figures 1 and 2 of the accompanying drawings show the effect of Pt and Pt + Hf additions on the rate of weight gain of the basic Co-10Cr-11Al alloy L under isothermal oxidising conditions at 1100°C.
  • Figure 1 shows that the addition of 1%Pt (alloy J) results in a slight decrease in the isothermal oxidation rate.
  • Figure 2 is a plot of wt gain versus time each on a logarithmic scale. When measured over the period 10 to 100 h to avoid the initial transient stages of oxidation, the slope of the curve for alloy L has a value of 0.5, corresponding almost exactly to a parabolic rate law. The slope is reduced to 0.4 for the Co-10Cr-11Al-1Pt alloy J.
  • Table 4 compares the weight gains of the four alloys after this period (1 h) and after 120 h exposure. Also included for comparison are the data for an alloy R known to the Applicants to have a particularly low overall weight gain under these conditions. This alloy R is Co-10Cr-11Al-0.3Hf internally oxiddzed for 300 h at 1200°C. TABLE 4
  • alloy J after 265 h oxidation at 1200°C was not adherent and spalled from the alloy on cooling, The oxide was multi-layered in many locations, particularly at the corners of the sample, and the outer layer of oxide at the gas/scale interface was heavily wrinkled. Similar features were observed with the ternary Co-Cr-Al alloy (alloy L) oxidized tinder similar conditions. Surface examinations of the alloy Co-10Cr-11Al-0.3Hf-0.9pt(alloy K) after oxidation at 1200°C revealed features similar to those of the alloy Co-10Cr-11Al-0.3Hf (alloy N).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)

Abstract

La resistance a l'oxydation et la resistance a la corrosion d'un alliage a base de nickel, de cobalt ou de fer peuvent etre ameliorees en incluant dans la composition de l'alliage un metal du groupe platine, tel que l'osmium, l'iridium, le platine, le ruthenium, le rhodium ou le palladium, et un ou plusieurs elements complementaires du platine, tel que le titane, le scandium, l'yttrium, le lanthane, l'hafnium, le tantale, le zirconium, le niobium et des lanthanides en proportions equilibrees. La composition de l'alliage resultant consiste en au moins 5 pour cent en poids de chrome, de 0 a 3 pour cent en poids de carbone, un composant x, un composant z, et en une balance d'un ou plusieurs composants de nickel, cobalt et fer avec des elements et des impuretes eventuels, ou le composant x est forme par une ou plusieurs des compositions suivantes: i) au moins 2 pour cent en poids au total d'un ou plusieurs des elements suivants: aluminium, titane, tantale et niobium; ii) au moins 5 pour cent en poids au total d'un ou des deux elements suivants: tungstene, molybdene, et iii) au moins 60 pour cent en poids de nickel, le composant z comprend mp pour cent en poids d'un ou plusieurs metaux du groupe platine melanges a mc pour cent en poids d'un ou plusieurs metaux complementaires du platine avec 0,1 <= mp + mc <= 5 et 0,3 <= mp/mc <= 20. La quantite mp du metal du groupe platine se situe, de preference, entre 50% et 95% en poids du total (mp + mc), et plus particulierement les quantites de metal du groupe platine et de metal complementaire du platine sont choisies en proportions stochiometriques par rapport aux composes intermetalliques pouvant se former entre eux. Les alliages ameliores sont d'un usage particulierement approprie aux composants d'une turbine a gaz.
EP78900280A 1977-12-05 1979-06-18 Ameliorations aux alliages a base de nickel, cobalt et fer, ou s'y rapportant Expired EP0006951B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB5059777 1977-12-05
GB5059777 1977-12-05

Publications (2)

Publication Number Publication Date
EP0006951A1 true EP0006951A1 (fr) 1980-01-23
EP0006951B1 EP0006951B1 (fr) 1983-01-12

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP78900280A Expired EP0006951B1 (fr) 1977-12-05 1979-06-18 Ameliorations aux alliages a base de nickel, cobalt et fer, ou s'y rapportant

Country Status (3)

Country Link
EP (1) EP0006951B1 (fr)
DE (1) DE2862157D1 (fr)
WO (1) WO1979000343A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5482789A (en) * 1994-01-03 1996-01-09 General Electric Company Nickel base superalloy and article
US6494971B1 (en) * 1996-10-28 2002-12-17 National Research Institute For Metals Iridium-containing nickel-base superalloy
DE19652562C2 (de) * 1996-12-17 1999-07-22 Heidenhain Gmbh Dr Johannes Positionsmeßeinrichtung
ES2288002T3 (es) * 1998-10-19 2007-12-16 Sulzer Metco Ag Sistema y procedimiento de revestimiento de barrera termica.

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1758010A1 (de) * 1968-03-20 1970-12-10 Dr Dietrich Merz Hochwarmfeste Legierungen mit Anteilen an Rhenium und Hafnium
US3589894A (en) * 1968-05-31 1971-06-29 Garrett Corp Sulfidation resistant cobalt-base alloy
SU322396A1 (ru) * 1969-09-25 1971-11-30 вители Центральный научно исследовательский институт черной металлургии И. П. Бардина , Ленинградский ордена Трудового Красного Знамени сталепрокатный завод Сплав для пружин
US3762918A (en) * 1972-01-26 1973-10-02 Nasa Cobalt base alloy
US3887363A (en) * 1973-12-18 1975-06-03 Gen Electric Nickel-base superalloy cast article
US3918139A (en) * 1974-07-10 1975-11-11 United Technologies Corp MCrAlY type coating alloy

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO7900343A1 *

Also Published As

Publication number Publication date
DE2862157D1 (en) 1983-02-17
WO1979000343A1 (fr) 1979-06-14
EP0006951B1 (fr) 1983-01-12

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