GB2105748A - Minor element additions to single crystals for improved oxidation resistance - Google Patents

Minor element additions to single crystals for improved oxidation resistance Download PDF

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Publication number
GB2105748A
GB2105748A GB08225449A GB8225449A GB2105748A GB 2105748 A GB2105748 A GB 2105748A GB 08225449 A GB08225449 A GB 08225449A GB 8225449 A GB8225449 A GB 8225449A GB 2105748 A GB2105748 A GB 2105748A
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United Kingdom
Prior art keywords
hafnium
oxidation resistance
silicon
additions
group
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GB08225449A
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GB2105748B (en
Inventor
David Noel Duhl
Frederick Albert Schweizer
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Raytheon Technologies Corp
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United Technologies Corp
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • C22C19/05Alloys based on nickel or cobalt based on nickel with chromium
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B11/00Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10Inorganic compounds or compositions
    • C30B29/52Alloys

Abstract

The additions of minor amounts of hafnium and silicon and mixtures thereof to nickel base superalloy single crystal articles provide significantly improved oxidation resistance. The oxidation resistance is improved both for the case of uncoated articles and in the case where a protective coating such as for example, a MCrAlY coating is present. For example the addition of 0.1% hafnium is observed to improve the oxidation resistance by a factor of 4 at 1149 DEG C and a similar addition improved the coated oxidation resistance by a factor of about 2.5 at 1177 DEG C. The preferred single-crystal alloy composition lies within the range:- <IMAGE>

Description

SPECIFICATION Minor element additions to single crystals for improved oxidation resistance The present invention concerns a nickel base superalloy single crystal article provided with enhanced oxidation resistance by the addition of 0.050.2% of a material selected from a group consisting of hafnium and silicon and mixtures thereof. Additions of these elements improved the oxidation resistance of the articles in both coated and uncoated form.
Nickel base superalloys are widely used in gas turbine engines. Originally such alloys were used in conventionally cast form consisting of many randomly oriented equiaxed grains. Substantial property improvements were obtained by a casting technique known as directional solidification which was initially used to produce columnar grains articles consisting of a multiplicity of elongated oriented grains whose axis of elongation is constrained to be parallel to the axis of maximum stress. A subsequent refinement permits the production of single crystal articles and these articles represent the state-of-the-art in superalloy technology. The present invention concerns the improvement of the oxidation resistance of single crystal superalloy articles through the addition of small amounts of hafnium and/or silicon.
Silicon is known as a constituent of superalloys and is shown for example in U.S. patents 2 621 122,2 2 994 605, 3 005 704, 3 411 898 and 3 524 744. Such minor additions have, to our knowledge, been made only to alloys intended for use in equiaxed form. The applicants are unaware that silicon has even been intentionally added to single crystal nickel base superalloy articles Hafnium has also been used in nickel base superalloy articles although to a lesser extent. U.S.
patent 3 005 705 suggests the use of 0.11.0% hafnium in a equiaxed alloy article. The benefit attributed to hafnium in this patent is improved high temperature mechanical properties and it does not appear that any improvement in oxidation resistance was recognized. Hafnium has also been widely used in directional solidification columnar grained alloys where it provides improved transverse grain boundary ductility. This is described for example in U.S. patent 3 677 747. Again, in this patent there is no discussion of enhanced oxidation resistance. Applicant is unaware that small hafnium additions have ever been made to single crystals for any purpose and in fact it was previously thought that hafnium should be avoided in single crystal articles as discussed in U.S. patent 4 11 6 723.
The present invention concerns the additions of from 0.05 to 0.2% of a material selected from a group consisting of hafnium, silicon and mixtures thereof to nickel base superalloy articles. The addition of hafnium and silicon in these levels can provide from 2--4x improvement in oxidation resistance. Improvement in oxidation resistance are observed in both coated and uncoated form. Other features and advantages will be apparent from the specification and claims and from the accompanying drawings.
Figure 1 shows the coated oxidation resistance of the single crystal article as a function of hafnium and silicon additions.
Figure 2a and 2b show the effect of hafnium and silicon additions on gamma prime solvus temperature and incipent melting temperature.
Figure 3a and 3b show the effect of hafnium and silicon additions on rupture life and 1% creep life.
This invention concerns a method for substantially improving the oxidation resistance of nickel base single crystal superalloy articles in both uncoated and coated forms. The invention results from the discovery that small additions of silicon and hafnium to the substrate alloy can significantly increase the oxidation resistance of the article. This result is somewhat surprising and not predictable from the prior art since it was not formerly appreciated that the degree of protection provided by coatings employed on superalloy articles was so sensitive to the substrate alloy composition.
The essence of the present invention is the addition of from about 0.05 to about 0.2 weight percent of silicon or hafnium or mixtures thereof to nickel superalloy single crystal articles. Such single crystal articles will in general contain from 5 to 18% chromium, at least 5% of the material selected from the group consisting of aluminum and titanium with the provision that aluminum be present from a minimum of 2% to a maximum of 8% and the titanium be present in from a minimum of 1% to a maximum of 5%. Further, the alloy must contain at least 5% of an element selected from the group consisting of up to 10% molybdenum, up to 15% tungsten, up to 12% tantalum, up to 3% niobium, up to 7% rhenium and mixtures thereof with the balance being essentially nickel.This composition is presented in U.S. patent 4 11 6 723. This patent also suggests that up to 3.5% hafnium might be present The present invention calls for the addition of from about 0.05 to 0.2% hafnium and the range suggested in the present invention is critical as will subsequently be demonstrated. The present invention was evaluated using a particular alloy denoted as Alloy 454 having a nominal composition of 10 weight percent chromium, 5% cobalt, 5% aluminum, 1.5% titanium, 12% tantalum, 4% tungsten balance nickel. This single crystal alloy formulation is described in and claimed in U.S. patent 4 209 348 which is incorporated herein by reference.This single crystal composition has an outstanding combination of properties but is generally representative of a wide range of such compositions. Additions of 0.1%, 0.4% and 0.6% weight percent hafnium as well as additions of 0.1 and 0.3 weight percent silicon were made to this nominal alloy composition.
The resultant samples were tested under a variety of test conditions with the following results.
Figure 1 shows the effect of minor additions of silicon and hafnium on coated oxidation resistance of Alloy 454. In this instance the coating was a coating known as an overlay coating with a nominal composition of 22% cobalt, 20% chromium, 120Jo aluminum, and 0.8% yttrium. This is a NiCoCrAIY overlay coating and is described in some detail in U.S. patent 3 928 026. Overlay coatings typically contain 1035% Cr, 8-25% Al, O, 1 --1 Y Y balance selected from the group consisting of nickel and cobalt. Small additions of other elements including silicon, hafnium and tantalum may also be present.
Overlay coatings are generally applied by vacuum vapor deposition process to produce a thin uniform adherent layer of the overlay coating alloy on the substrate surface. The data presented in Figure 1 is the test time to penetration of the coating divided by the coating thickness. This type of measurement gives a relatively accurate indication of coating performance and eliminates coating thickness as a variable. From the figure it can be seen that the additions of small amounts of hafnium and silicon to the substrate compositions have a marked effect on coated article life. The data in Figure 1 are the result of testing at 11 770C using a burner rig test. In this type of test, hot gases are generated by the combustion of jet fuel and these gases are impinged on the sample in test.The particular cycle employed included 29 minutes of exposure at 11 770C followed by a 1 minute forced air cooling period. The purpose of the forced air cooling is to simulate the thermal fiuctuations which occur during the operation of a gas turbine engine.From Figure 1 it can be seen that the addition of about 0.1% silicon improves the coated oxidation life by about 90 or 100% while the addition of an equivalent amount of hafnium increases the coated oxidation life by about 150%. Hafnium is seen to be somewhat more effective than silicon in improving coated oxidation life and it is significant that with additions of both hafnium and silicon that no significant increase in oxidation resistance is provided by additions of more than about 0.2 weight percent of the element. From Figure 1 the broad range of element additions can be set at from about 0.05 to about 0.2%.
The effects of small additions of hafnium and silicon on the uncoated oxidation resistance of single crystal articles are described in Table I. Alloy 454 is the previous single crystal material. The table shows the effect of small additions of hafnium and silicon on the various parameters which are evaluated in oxidation testing. Both weight loss and maximum depth of penetration are substantially reduced by minor element additions. The column labeled oxidation resistance is determined by dividing the hours of testing into the maximum depth of penetration and the column labeled relative oxidation resistance compares the oxidation resistance of the various alloys to unmodified Alloy 454 material.
From this latter column, it can be seen that additions of both hafnium and silicon significantly increase the uncoated oxidation resistance of the material. Hafnium appears to be more effective than silicon at the same level and additions of hafnium in the amount of 0.4 weight percent are substantially more effective than 0.1% hafnium additions. As has been seen, this latter effect is not observed in testing of coated oxidation resistance.
Table 1 1093 C Uncoatad Oxidation Results Maximum Depth Reiative Oxidation Hours Weight of penetration Oxidation Resistance Resistance Alloy in Test Loss (Grams) (micronsiside) (hours/microns) (X Alloy 454) Alloy 454 503 -1.42 432 1.16 1.0 Alloy 454 +0.1 wt% Hf 503 -0.12 109 4.60 4.0 Alloy 454 +0.4 wt% Hf 503 -0.10 18 28.29 24.3 Alloy 454 +0.1 wt% Si 503 -0.52 162.5 3.09 2.7 From the preceding discussion it appears that hafnium is more effective than silicon in improving the oxidation resistance of single crystal articles in both coated and uncoated form. It is also obvious that hafnium has less deleterious effects on mechanical properties (as shown in Figure 3) and on incipent melting temperature (as shown in Figure 2). For this reason hafnium is preferred over silicon.
Figures 2a and 2b illustrate the effect of hafnium and silicon additions on the gamma prime solvus temperature and the incipient melting temperature of the substrate alloy. The gamma prime so!vus temperature of the alloy is that temperature which must be exceeded if the gamma prime strengthening phase is to be dissolved into solid solution. The gamma prime solvus temperature must be approached and preferably exceeded for effective heat treatment of nickel base superalloys. The incipient melting temperature is that temperature above which localized melting of the superalloy will occur. For optimum heat treating results the gamma prime solvus temperature must be exceeded while the incipient melting temperature should not be exceeded.Further, as a consequence of the limitations of practical heat treating equipment, it is desirable that a temperature span of at least 50C, and preferably a greater span, exists between the gamma prime solvus and the incipient melting point.
In the case of single crystals it is not catastrophic if minor incipient melting occurs, but it is preferable to avoid incipient melting if possible. Turning now to Figure 2a the effect of hafnium additions on the gamma prime solvus and incipient melting temperatures of Alloy 454 are shown and it can be seen that for hafnium additions in excess of about 0.25 weight percent the incipient temperature lies below the gamma prime solvus leading to an undesirable heat treating situation. A similar situation can be seen to exist in Figure 2b with respect to silicon additions. The information presented in Figures 2a and 2b leads to the conclusion that additions of silicon and/or hafnium in excess of about 0.25% are deleterious from the standpoint of heat treatment capability.
In metallurgy as in most highly developed art areas, it is unusual that a modification which improves one property will not have deleterious effect on other properties. This is the case in the present invention. Figures 3a and 3b show the effect of hafnium and silicon additions on the creep properties of Alloy 454. Figure 3a shows that additions of small amounts of hafnium lead to the steady decrease in both the rupture life and the time to 1% creep for specimens tested at 8700C with an applied load of 482.65 MPa. Figure 3b shows a similar effect on the creep properties of Alloy 454 as a consequence of additions of small amounts of silicon. However, it appears that small silicon additions have more of a deleterious effect on the creep properties than similar amounts of hafnium.The data presented in Figures 3a and 3b demonstrates another reason for limiting the silicon/hafnium additions to the lowest possible level consistent with the achievement of improved oxidation resistance.
While it has been suggested in the prior art that additions of various elements including hafnium and silicon to the overlay coating composition itself produces improvements in oxidation resistance, such prior art suggestions have to our knowledge been limited to the suggestion that the elements be added to the coating itself and further have generally suggested that elemental additions substantially in excess of those contemplated in the present invention be made. It appears that by making the addition of hafnium or silicon to the substrate alloy that the substrate thereby acts as a large reservoir of silicon and/or hafnium and that these elements diffuse into and through the coating and affect the oxidation process at the free surface of the coating.Because of the relatively large amounts of hafnium and silicon which are present in the total substrate, the diffusion through the coating can occur for long periods of time without significantly decreasing the effective amount of silicon and hafnium which is available. It is somewhat surprising, and unexpected, that these protective overlay coatings are so sensitive to the presence of silicon and hafnium in the substrate in such small amounts.
The overlay coatings derive their effectiveness from the development of a thin adherent scale of aluminum oxide on the free surface. It appears that the improvement in coated oxidation life results from some modification of this aluminum oxide layer by the silicon and hafnium in the substrate. The other significant type of protective coating employed on superalloys is that referred to as aluminide coatings. Such coatings are produced by the diffusion of aluminum into the superalloy surface to produce a modified surface layer relatively rich in aluminum. This aluminum rich surface layer develops an oxide on its free surface which protects the coated part in a manner similar to that of the protection derived by the overlay coatings.In view of this it is fully expected that additions of silicon and hafnium to the substrate will produce a similar improvement in coated oxidation resistance of parts of superalloy single crystals which have been given a protective aluminide coating.
Finally, although the invention has been extensively investigated with regard to an alloy known as Alloy 454, this alloy is representative of many other single crystal alloys and it is anticipated that similar results will be obtained on other alloys. Another alloy containing lesser amounts of tantalum and greater amounts of tungsten was also tested with and without the addition of 0.1% hafnium and an improvement of oxidation life of about 70% was obtained. This tends to confirm the belief that the effect of silicon and hafnium will be generally observed in nickel base superalloys of the type previously described.
It should be understood that the invention is not limited to the particular embodiments shown and described herein, but that various changes and modifications may be made without departing from the scope of this novel concept as defined by the following claims.

Claims (4)

Claims
1. In a nickel superalloy single crystal article, characterized by the improvement which comprises adding from about 0.05 to about 0.2% of a material selected from the group consisting of hafnium, silicon and mixtures thereof to the article whereby the coated and uncoated oxidation resistance of the article will be improved.
2. An article according to claim 1 characterized in that the additional element is hafnium.
3. A single crystal article containing 5-1 8% chromium, at least 5% of the material selected from the group consisting of aluminum and titanium with the aluminum contents ranging from 2% to 8% and titanium contents ranging from 15%, at least 5% of the material selected from the group consisting of up to 10% Mo, up to 15% W, up to 12% Ta, up to 3% Nb, up to 7% Re, characterized by comprising from 0.05 to 0.2% of a material selected from the group consisting of hafnium and silicon and mixtures thereof balance essentially nickel.
4. A coated single crystal article having enhanced oxidation resistance consisting of a nickel superalloy substrate consisting of 5-1 8% chromium, at least 5% of the material selected from the group consisting of aluminum and titanium with the aluminum contents ranging from 2% to 8% and titanium content ranging from 1-5% at least 5% of the material selected from the group consisting of up to 10% Mo, up to 1 5% W, up to 12% Ta, up to 3% Nb, up to 7% Re, characterized in that it further contains from 0.05 to 0.2% of a material selected from a group consisting of hafnium and silicon and mixtures thereof, balance nickel, said substrate having a coating thereon consisting of 10-36% chromium, 8-25% aluminum, 0.1-1% yttrium balance selected from the group consisting of nickel, cobalt and mixtures thereof.
GB08225449A 1981-09-14 1982-09-07 Minor element additions to single crystals for improved oxidation resistance Expired GB2105748B (en)

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US20110142712A1 (en) * 2008-03-03 2011-06-16 Magnus Hasselqvist Nickel base gamma prime strengthened superalloy
US20120014832A1 (en) * 2009-01-15 2012-01-19 Hiroshi Harada Ni-BASED SINGLE CRYSTAL SUPERALLOY
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US5154884A (en) * 1981-10-02 1992-10-13 General Electric Company Single crystal nickel-base superalloy article and method for making
US5399313A (en) * 1981-10-02 1995-03-21 General Electric Company Nickel-based superalloys for producing single crystal articles having improved tolerance to low angle grain boundaries
US5100484A (en) * 1985-10-15 1992-03-31 General Electric Company Heat treatment for nickel-base superalloys
US6074602A (en) * 1985-10-15 2000-06-13 General Electric Company Property-balanced nickel-base superalloys for producing single crystal articles
US5122206A (en) * 1989-05-16 1992-06-16 Mitsubishi Metal Corporation Precipitation hardening nickel base single crystal cast alloy
EP1184473A3 (en) * 2000-08-30 2002-05-22 Kabushiki Kaisha Toshiba Nickel-base single-crystal superalloys, method of manufacturing same and gas turbine high temperature parts made thereof
EP1184473A2 (en) * 2000-08-30 2002-03-06 Kabushiki Kaisha Toshiba Nickel-base single-crystal superalloys, method of manufacturing same and gas turbine high temperature parts made thereof
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US8926897B2 (en) * 2005-09-27 2015-01-06 National Institute For Materials Science Nickel-base superalloy excellent in the oxidation resistance
US20090196760A1 (en) * 2005-09-27 2009-08-06 Hiroshi Harada Nickel-Base Superalloy Excellent in the Oxidation Resistance
US20090041615A1 (en) * 2007-08-10 2009-02-12 Siemens Power Generation, Inc. Corrosion Resistant Alloy Compositions with Enhanced Castability and Mechanical Properties
US20100310411A1 (en) * 2008-02-13 2010-12-09 The Japan Steel Works, Ltd. Ni-BASED SUPERALLOY WITH EXCELLENT UNSUSCEPTIBILITY TO SEGREGATION
US10221473B2 (en) 2008-02-13 2019-03-05 The Japan Steel Works, Ltd. Ni-based superalloy with excellent unsusceptibility to segregation
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FR2512838B1 (en) 1985-04-19
GB2105748B (en) 1984-12-12
IT8223257A0 (en) 1982-09-14
DE3234090C2 (en) 1988-12-15
JPS5861244A (en) 1983-04-12
IL66721A (en) 1986-02-28
DE3234090A1 (en) 1983-04-28
IL66721A0 (en) 1982-12-31
IT1152573B (en) 1987-01-07
CA1212020A (en) 1986-09-30
FR2512838A1 (en) 1983-03-18

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