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June 27, 1972 N, BREDZS ETAL 3,672,849 CERMET-TYPE ALLOY COATING 0N METAL BASE 'Original Filed Feb

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June 27, 1972 N, BREDZS ETAL 3,672,849 CERMET-TYPE ALLOY COATING 0N METAL BASE 'Original Filed Feb June 27, 1972 N, BREDZS ETAL 3,672,849 CERMET-TYPE ALLOY COATING 0N METAL BASE 'Original Filed Feb. 19, 1969 2 Sheets-Sheet 1 Juné 27, 1972 N, BREDzs ETAL 3572,84’ CERMET-TYPE ALLOY COATING ON METAL BASE 'QriginaZL Filed Feb. 19. 1969 2 Skits-SHOW! 3,672,849 United States Patent O?ice Patented June 27, 1972 1 2 proved thermal fatigue and oxidation resistance enabling 3,672,849 such alloys to be employed directly in high temperature CERMET-TYPE ALLOY COATING ON situations without the need of applying various protective METAL BASE coatings to the surfaces thereof. In accordance with an Nikolajs Bredzs, Detroit, and Forbes M. Miller, Dear born, Mich., assignors to Wall Colmonoy Corporation other aspect of the present invention, an improved cermet Application Feb. 19, 1969, Ser. No. 800,540, now Patent type alloy and method for making the alloy is provided No. 3,547,673, dated Dec. 15, 1970, which is a continu which can be employed in the fabrication of components ation-in-part of application Ser. No. 646,654, June 16, subject to high temperatures and stresses such as for com 1967. Divided and this application July 7, 1969, Ser. ponents of gas turbines and the like, providing increased No. 871,121 10 thermal fatigue and oxidation resistance and thereby en The portion of the term of the patent subsequent to :abling engine operation at higher temperatures, providing Dec. 15, 1987, has been disclaimed for a substantial improvement in operating e?‘iciency. Int. Cl. B32b 15/00 U.S. Cl. 29-195 3 Claims ‘SUMMARY ‘OF THE INVENTION 15 In its composition aspects, the present invention is di rected to an improved cermet-type alloy either in the form ABSTRACT OF THE DISCLOSURE of an ingot or in the form of a protective coating on a sub An improved cermet-type alloy and method of making strate in which the cermet-type alloy is characterized as same which is particularly adaptable for forming protec comprising a substantially continuous phase or matrix of tive surface coatings on heat-resistant alloys. A particu 20 a nickel and/or cobalt base alloy containing from about lated mixture is formed containing titanium and/or zir 10% to about 40% chromium, and preferably 15% to conium reactive metal constituents that undergo an exo 25% chromium, along with other conventional impurities thermic reaction upon fusion at an elevated temperature and alloying agents in amounts which do not appreciably in a substantially inert atmosphere with silicon and/or reduce the heat-resistant properties of the continuous alloy boron present in the mixture forming the corresponding 25 matrix and a discontinuous phase of precipitated borides silicides or borides of the reacted metals in situ which are and/or silicides of titanium and/or zirconium which are subsequently precipitated as a uniformly dispersed dis present in the form of compressed crystals and are dis continuous phase in a continuous phase of a nickel and/ or tributed substantially uniformly throughout the continuous cobalt :base matrix. The invention also encompasses novel matrix and are present in an amount ranging from about powder compositions for exothermically forming the 30 2% to about 40%, and preferably from about 4% up to cermet-type alloys and coatings. about 30% of the alloy. In its method aspects, the present invention encom passes the formation of the improved cermet-type alloy CROSS-REFERENCE TO RELATED :by exothermically reacting a particulated mixture con APPLICATIONS 35 taining the cobalt and/ or nickel-base matrix metals and a reactive metal selected from the group consisting of This application is a divisional application of copend titanium and zirconium and a nonmetallic element select ing application Ser. No. 800,540, ?led Feb. 19, 1969', Pat. ed from the group consisting of silicon and boron which 3,547,673, dated Dec. 15, 1970, which comprises a con are present in controlled amounts so as to effect the for tinuation-impart application of application Ser. No. mation of the corresponding titanium or zirconium bor 646,654, ?led June 16, ‘1967, for “Metallic Surface Coat ide or silicide in situ through an exothermic reaction re ing and Method of Making Same,” now abandoned. sulting from the heating of the particulated mixture at a BACKGROUND OF THE INVENTION temperature at which at least 1a partial fusion thereof occurs. Various coating compositions andcoating techniques 45 'In the method of forming an ingot of the improved have heretofore been used or proposed for use for pro alloy, the particulated mixture is heated in a suitable re viding a protective coating on metal alloys which them— fractory crucible or mold in a substantially inert atmos selves are characterized as heat and oxidation resistant phere to an elevated temperature which varies depending alloys so as to elfect a further improvement in the ther upon the speci?c composition of the mixture but generally mal fatigue and oxidation resistance thereof. Heat-resist 50 ranges from about 1900° F. up to about 2100“ F. for a ant metals and alloys of the general types to which the period of time sui?cient to complete the interaction be coating composition comprising one aspect of the present tween the reactive metals and the nonmetallic elements invention is applicable include stainless steels, nickel-base forming a fused ingot of the cermet-type alloy. alloys, and the so-called superalloys, such as Hastelloy-X, In the method of forming protective coatings on metal Inconel 600 and the like. Such heat-resistant alloys are in 55 substrates, the particulated mixture is applied to the sur widespread use in the manufacture of components for gas face of the metal substrate to be protected in an amount turbine engines or the like, in which they are concurrently so as to provide a resultant protective layer having an subjected to high stresses at elevated temperatures in the average thickness of from about 0.001 to about 0.010 presence of an oxidizing atmosphere which effects a pro inch, and preferably of an average thickness of about gressive deterioriation in the physical strength properties 60 0.002 to about 0.005 inch. It is usually preferred to em thereof, as well as a progressive oxidation thereof. Pro ploy a suitable organic binder for preliminarily adhering tective coatings of the types heretofore known have either the particulated mixture to the surface of the substrate, not been particularly effective in providing a substantial which subsequently decomposes without residue upon a improvement in the corrosion resistance and thermal heating of the coated substrate in a substantially inert fatigue characteristics of such heat-resistant alloys, have 65 atmosphere such as, for example, an argon atmosphere been exceedingly di?icult to apply, and/or have been or in vacuum at elevated temperatures within the range de?cient in their adherence to the substrate in order to hereinabove set forth, effecting at least partial fusion of form a continuous impervious barrier layer which is not the coating and an inter-reaction between the metal re brittle and susceptible to fracture or separation due to actants and nonmetallic elements, effecting the formation shock loading and stresses applied thereto. 70 of the cermet-type alloy coating. The heating of the coat There has also been a continuing need for improved ing is preferably continued so as to effect a partial dif high-strength heat-resistant metal alloys which possess im fusion of the continuous metal alloy matrix with a sub 3,672,849 3 4 strate metal, forming therewith a tenacious bond. The additional hardening and/or strengthening agents to pro protective coatings thus formed, upon subsequent cool vide the desired physical properties of the resultant alloy ing, possess a substantially higher remelt temperature formed consistent with the ultimate intended use there which conventionally is in the order of about 21000 F. of. In this regard, it is contemplated that iron can be up to about 2350” F. and above, which further enhances 5 included in the matrix metal mixture in amounts up to the effectiveness of the protective coating and provides about 5%, manganese in amounts usually up to about for an improved coated article possessing increased re 1%, as well as other conventional impurities such as alu sistance against thermal fatigue and oxidation at ele minum, carbon, etc. vated temperatures. The balance of the metallic powder consists essentially A further composition aspect of the present invention IO of at least one reactive metal selected from the group con is directed to a novel particulated composition contain sisting of titanium and zirconium, and at least one non ing controlled proportions of the matrix metals and re metallic element selected from the group consisting of active constituents which preferably are pre-alloyed, facil— silicon and boron, which are effective during the fusion itating their handling and increasing their resistance of the powder mixture at an elevated temperature to to oxidation attack during shipment and storage, as well undergo an exothermic reaction forming the correspond as providing for lower melting eutectics which reduces ing titanium or zirconium silicide or boride. In accordance the temperature to which the particulated mixtures must with the preferred practice, the reactive metal and non be heated to effect a partial fusion thereof and the ini metallic element or mixtures thereof are present in tiation of the exothermic reaction. The particulated com stoichiometric proportions so that no residual unreacted positions, when intended for use in forming protective reaction metal and nonmetallic element is present in the coatings on metal substrates, are of controlled particle resultant cermet-type alloy. It is, however, possible to sizes to facilitate their application in the form of uniform incorporate quantities of titanium, zirconium and silicon coatings whereas greater latitude is provided in particle in excess of the stoichiometric proportions such that the size when such particulated mixtures are employed for reaction metal or silicon will be present in an unreacted making ingots of the improved cermet-type alloy.
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