US 3918139 A
There is described nickel, cobalt and nickel-cobalt alloy coating compositions having improved hot corrosion resistance. In particular, an improved MCrAlY type alloy coating composition consists essentially of, by weight, approximately 8-30 percent chromium, 5-15 percent aluminum, up to 1 percent reactive metal selected from the group consisting of yttrium, scandium, thorium and the other rare earth elements and 3-12 percent of a noble metal selected from the group consisting of platinum or rhodium, the balance being selected from the group consisting of nickel, cobalt and nickel-cobalt.
Description (OCR text may contain errors)
United States Patent 1191 Goward et al. 75/l7l Felten Nov. 11, 1975 541 MCrAlY TYPE COATINGALLOY,  Inventor: Edward J. Felten, Cheshire, Conn. 'm i' Rutledge Assistant Eta,mmer-E. L. WeIse [7.3] Ass1gnee: United Technologies Corporation, Attorney, Agent, or Firm-John D. De] Ponti Hartford, Conn. 22] Filed: July 10, 1974 I I I I  Appl 48,7074 There is described nickel, cobalt and nickel-cobalt alloy coating compositions having improved hot corro- [52 US. Cl 29/194; 75/171 Sion resistance In Particular, n improved MCrAlY  Int. Cl. B32B 15/04; C22C 19/00 yp alloy coating composition consists essentially  Field of Search 29/194; 75/171, 170, 134 F by weight, appr ximately 8-30 per nt m um, 5 -l5 percent aluminum, up to 1 percent reactive  References Cit d metal selected from the group consisting of yttrium, UNITED STATE P T TS scandlum, thorium and the other rare earth elements 3 399 68 s A EN and 3-12 percent of a noble metal selected from the 3 589 232 ROUSh g p consisting of platinum or rhodium, the balance 3 649 225 3/1972 Simmons .1: I: 29/194 being selected from the group cmsistitg of nickel 3,676,085 7/1972 Evans et a1. 29/194 F mckel'cobah- Boone et al 75/l7l 7 Claims 5 Drawing Figures US. Patent Nov. 11, 1975 SheetlofS 3,918,139
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-SxW w J s; a W ,2 x W Qfi z MCrAIY TYPE COATING ALLOY BACKGROUND OF THE INVENTION The present invention relates to alloys and more particularly to nickel, cobalt or nickel-cobalt coating alloys having improved hot corrosion resistance.
It is known that the modern day jet engine superalloys are susceptible to oxidation-erosion and hot corrosion at very high temperatures and that it is the usual practice to coat the superalloys with a composition different from and more oxidation-erosion and corrosion resistant than the substrate alloy.
In general, there are two primary types of coatings: (1) aluminide coatings, such as those described in the patent to Joseph U.S. Pat. No. 3,102,044 or the patents to Bungardt et al. U.S. Pat. No. 3,677,789 and U.S. Pat.
No. 3,692,554 wherein aluminides are formed by a re- MCrAlY type, e.g., NiCrAlY described in the patent to Goward et al. U.S. Pat. No. 3,754,903, CoCrAlY described'in the patent to Evans et al. U.S. Pat. No. 3,676,085, NiCoCrAlY described in the patent application to I-Iecht et al. Ser. No. 469,186 filed May 13, 1974 and FeCrAlY described in the patent to Talboom, Jr. et al. U.S. Pat. No. 3,542,530. Particularly useful overlay MCrAlY coatings are those consisting essentially of, by weight, approximately 8-30 percent chromium, 5-15 percent aluminum, up to 1 percent reactive metal selected from the group'consisting of yttrium, scandium, thorium and lanthanum and the other rare earth elements, balance selected from the group consisting of nickel, cobalt and nickel-cobalt, preferably applied to a thickness of approximately 0.005-0.006 inch.
In contrast to the overlay coatings, the diffusion aluminide coatings are typically provided by reacting aluminum with the deoxidized surface of the article to be protected the aluminide layer being formed as a barrier zone of varying component concentration with consumption of the substrate components. This aluminide layer in turn oxidizes to form the inert barrier oxide. In the Bungardt et alpatents, a separate layer of metal from the platinum group is applied before the aluminum diffusion treatment. However, because of the complex nature of most of the contemporary alloys, and because the coating composition thereon is derived in part from the components of the substrate alloys, it
is difficult to control the coating composition so as to cause the formation of a suitable barrier oxide. In addition, it is inherent in the diffusion technique that the coating formed. is nonhomogeneous and, with respect to platinum group metal content for example, there approvements, particularly for example, in hot-corrosion .resistance, has remained. 1
SUMMARY OF THE INVENTION The present invention contemplates alloy compositions and more particularly nickel, cobalt and nickelcobalt coating alloy compositions having improved hot corrosion resistance. In particular, the present invention contemplates an improved MCrAlY type alloy coating composition consisting essentially of, by weight, approximately 8-30 percent chromium, 5-15 percent aluminum, up to 1 percent reactive metal selected from the group consisting of yttrium, scandium, thorium and the other rare earth elements, and 3-12 percent of a noble metal selected from the group consisting of platinum or rhodium, the balance being se- 0 lected from the group consisting of nickel, cobalt and nickel-cobalt. As will be appreciated, the inclusion of the noble metal as an alloying ingredient results in a substantially uniform dispersion thereof throughout the composition and thus retains the homogeneity which is characteristic of MCrAlY type overlay coatings.
In a preferred embodiment, the reactive metal is yttrium and the noble metal is 5-10 percent platinum. In another embodiment, the reactive metal is yttrium and the noble metal is 5 percent rhodium.
BRIEF DESCRIPTION OF THE DRAWINGS An understanding of the invention will become more apparent to those skilled in the art by reference to the havior of various NiCrAl alloys at l, l 00C and 1,200C
respectively, in air;
FIG. 4 is a graph showing the hot corrosion behavior of various CoCrAlY and NiCrAlY alloys at 1,750F 2.0 mg cm Na,SO and FIG. 5 is a graph showing the hot corrosion behavior of NiCrAlY alloys at 1,750F 0.5 mg cm" Na,SO
DESCRIPTION OF THE PREFERRED EMBODIMENTS The alloys of the present invention exhibit markedly improved hot corrosion resistance and are considered particularly useful as coatings on the contemporary superalloys. The inventive alloys are in themselves corrosion resistant and do not depend for their protective effect upon a reaction with the substrate material. Inaddition, these alloys are uniform throughout their thickness and thus will exhibit their protective properties more continuously and consistently than do the aluminide coatings.
The desired results are obtained with a basic alloy containing approximately, by weight, 8-30 percent chromium, 5-15 percent aluminum, 5-10 percent platinum "or rhodium, up to 1 percent reactive metal selected from the group consisting of yttrium, scandium, thorium and lanthanum and the other'rare earth elements, balance nickel and/or cobalt. A preferred alloy composition utilizes 0.5 percent yttrium and 5-10 percent platinum.
It was surprising to find that the addition, as alloying I ingredients, of specified amounts of platinum or rhodiumto the MCrAlY type coatings would not only greatly enhance sulfidation resistance but also, even without the presence of the reactive'metals (Y, Sc, -Th,
La and the other rare earths) which normally provide oxide adherence to the underlying substrate, would promote additional oxide adherence.
With respect to the processes whereby the alloy may I be applied as a coating to the surface to be protected, the presence of platinum or rhodium to'the coating alof platinum or rhodium. As an alternative, the coatings may be accomplished by plasma spraying techniques.
A better understanding of the invention will result when viewed in light of the following examples:
EXAMPLE 1 Alloys of Ni-AlCr-6A with alloying additions of platinum and rhodium were made by the conventional arc melt-drop cast technique. Specimens of the compositions depicted in the graph of FIG. 1 had dimensions of 1 cm X 1 cm X -0.2 cm and were subjected to hot corrosion tests as follows. Specimens of the alloys were spray coated with an aqueous solution of Na SO4, dried and weighed. Afterachieving a coating of 0.5 mg cm- Nag. S04, they were oxidized for 20 hours at 1,000C in one atmosphere O in a thermal balance. The specimen Weight was recorded continuously as a function of time with the weight changes converted to weight gain per unit surface area and shown in FIG. 1.
As can be seen, the. addition of 2.5 weight percent Pt did not significantly improve the performance of the Ni-8Cr-6Al alloy in this test. However a significant improvement in performance was obtained when 5 or 10 weight percent Pt was added. Specimens of the Ni- 8Cr-6Al-5Rh alloy were approximately equivalent to that of the 10 Pt alloy.
EXAMPLE 2 Specimens were formed as in Example 1 to the compositions as shown inFIGS. 2 and 3. The specimens were subjected to high temperature cyclic oxidation tests and surprisingly, those containing platinum or rhodium, were found to have improved oxide adherence of the A1 formed on the alloys. It can be seen that the alloys with or weight percent Pt are supe-, rior to the 2.5 weight percent Pt alloy which, in turn, is significantly better than the unmodified alloy. Oxide adherence on a Ni-8Cr-6Al-5Rh alloy at l,200C was,
found to be equivalent to that of the Ni-8Cr-6Al-10Pt alloy at the same temperature.
EXAMPLE 3 Alloy specimens having dimensions of 1 cm X 0.8 cm X 0.l-0.2 cm and compositions of Ni-l 7Cr-l2Al-0.5Y, Ni-17Cr-12Al-5Rh-O.5Y, Ni-l7Cr'l2Al-1OPt-O5Y, Co-l7Cr-l lAl-0.5Y, Co-l7Cr-1lAl-5Rh-O.5Y and Col7Cr-llAl-l0Pt-0.5Y were prepared, measured and.
R11 to either CoCrAlY, or NiCrAlY dramatically im-.
prove their hot corrosion resistance.
EXAMPLE 4 Erosion bars of Ni-l'iCr-IZAl-QSY, Ni-l7Cr-l2Al 10pt-O.5Y were evaluated in a cyclic hot corrosion Y burner rig at 1,7530%" using 35 ppm of sea salt ingested in the fuel prior to combustion'Sevcre attack of the tip of both the NiCrAli base composition and the rho. dium modified composition occurredafter hours.
Hot zone failures were observed between300 and 400 hours for both these bars, the rhodium modified specimen surviving for a slightly longer time than the base composition. Although the rhodium modified composition showed little improvement over the base alloy in i this test, the nature of its failure was unusual and ren dered these results somewhat dubious and inconclusive. in contrast, the platinum modified compositions were found to be dramatically more resistant to hot corrosion than the base composition. For these compositions no sign of failure was observed up to 675 hours, when testing was terminated.
What has been set forth above is intended primarily as exemplary to enable those skilled in the art in the practice of 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.
Whatis claimed is:
ll. in a coating composition of the MCrAlY type. wherein the coating composition consists essentially of,
by weight, approximately 830 percent chromium, 5-l5 percent aluminum, up to 1 percent reactive metal selected from the groupconsisting of yttrium, scandium, thorium and the other rare earth elements, balance selected from the group consisting of nickel, cobalt and nickel-cobalt, the improvement for increasing hot corrosion resistance which comprises 3-12 percent of a noble metal selected from the group consisting of 1 platinum and rhodium as an alloying ingredient.
2. The. invention of claim ll wherein said reactive metal is yttrium.
3. The invention of claim 2 wherein said noble metal is 5-10 percent platinum.
4. The invention of claim is 5 percent rhodium.
2; wherein said noble metal 5. A coated article comprising a nickel-base or co-' halt-base superalloy, and an overlay coating thereon of the MCrAlY type wherein the coating composition consists essentially of, by weight, approximately 830 percent chromium, 5-15 percent aluminum, up to 1 percent reactive metal selected from the group consisting of yttrium, scandiurn, thorium and the other rare earth elements, 3-l2 percent of a noble metal selected from the group consisting of platinum or rhodium, balance selected from the group consisting of nickel, .cobalt and nickel-cobalt, said platinum or rhodium being:
6 wherein said noble metal UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,918,139
DATED November ll, 1975 INVENTOR(S) EDWARD J. FELTEN It is certified that error appears in the above-identified patent and that said Letters Patent a are hereby corrected as shown below:
Column 3, line 14 "Ni-AlCr-6A" should read --Ni-8Cr-6Al-- u n a Column 3, lane 22. Na SO should read Na SO Column 4, lines 6-7: "Ni-l7Cr-l2Al-l0pt0.5Y" should read -Ni-l7Cr-l2Al-lOPt-O.5Y--
Engncd and Scaled thus ninth Day of Marc h1976 [SEAL] Attest:
RUTH C. MASON C. MARSHALL DANN Aff s ing Offic Commissioner uj'Parems and Trademarks