US3399058A - Sulfidation and oxidation resistant cobalt-base alloy - Google Patents

Sulfidation and oxidation resistant cobalt-base alloy Download PDF

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Publication number
US3399058A
US3399058A US617755A US61775567A US3399058A US 3399058 A US3399058 A US 3399058A US 617755 A US617755 A US 617755A US 61775567 A US61775567 A US 61775567A US 3399058 A US3399058 A US 3399058A
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cobalt
sulfidation
alloy
yttrium
alloys
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US617755A
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Milton S Roush
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Garrett Corp
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Garrett Corp
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Priority to US617755A priority Critical patent/US3399058A/en
Priority to GB0673/68A priority patent/GB1210561A/en
Priority to DE19681608156 priority patent/DE1608156A1/de
Priority to FR137412A priority patent/FR93750E/fr
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    • 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

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  • ABSTRACT OF THE DISCLOSURE A sulfidation and oxidation resistant cobalt-base alloy comprised of a major amount of cobalt, between about 0.05% and 3.0% by weight yttrium, between about 1.0% and 6.0% by weight aluminum and preferably also containing chromium, tungsten and/ or molybdenum, columbium and/ or tantalum and carbon.
  • This invention relates generally to metal alloys and more particularly to alloys provided for use in the manufacture of machine parts, such as gas turbine wheels and/or blades, and nozzle vanes, which are exposed to high-temperature combustion gases containing oxygen, sulfur, lead, and/ or other chemicals that cause oxidation, sulfidation, corrosion and other deleterious effects.
  • Sulfidation is a metal deterioration which takes place particularly in the heated sections of gas turbines which are exposed to gaseous combustion products of sulfur and/ or lead containing fuels such as fuel oil, diesel fuel, aviation gasoline and the like.
  • the problem is especially serious under desert or salt water atmosphere conditions where the presence of alkali or alkaline-earth metal salts such as sodium chloride, even in concentrations as low as 0.1 part per million, are found to catalyze the sulfidation reaction.
  • high-temperature metallurgy for use in oxygen containing environments has been limited to: (1) nickel-base alloys which, although oxidation resistant to 2000 F. are not satisfactory in sulfur containing atmospheres over 1650 especially when alkali and alkalineearth metal salts are present, or over 1750 F. when lead deposits are present; and (2) cobalt-base alloys which are resistant to sulfidation and lead attack up to 1850 F. but are not resistant to oxidation above 1750 F.
  • One aim of this invention is to provide an alloy having an equal or better oxidation resisting quality than the high strength nickel-base alloys, such as the alloy known as Inconel 713C, and an equal or better sulfidation resisting quality than the cobalt-base alloys, such as that identified by the trademark WI52.
  • An object of this invention is to provide an alloy having high resistance to oxidation, sulfidation and lead corrosion when exposed, in oxygen containing environments, to gaseous products of combustion at about 2000 F. temperatures, such as are produced by burning JP4 or other gas turbine fuels.
  • Still another object of the invention is to provide a cobalt-base alloy having a maximum of about 6.0 weight percent aluminum and a maximum of about 3.0 weight percent yttrium to further increase the resistance of the alloy to oxidation, sulfidation and lead corrosion when exposed to an atmosphere containing combustion products of fuels of the type employed to operate gas turbine engines.
  • the superior alloys of this invention are cobalt-base alloys containing a small amount of yttrium and aluminum and preferably a number of other metals which will improve the strength properties of the material.
  • cobalt-base alloy as used herein and as understood in the art, is meant a metallic composition wherein the major element present in cobalt and preferably wherein the cobalt is present in a major amount. More specifically it has been found according to the invention cobalt-base alloys containing from about 0.05 to about 3.0% by weight yttrium and from about 1.0 to about 6.0% by weight aluminum possess outstanding sulfidation and oxidation deterioration resistance.
  • the cobalt-base alloys of the invention contain between about 50% and 65% cobalt.
  • the composition is also necessary for the composition to contain tungsten and/or tantalum wherein the total amount of this group of metals is between about 3% and 20% by weight of the alloy composition.
  • the preferred amounts of these metals individually are between 0% and 15% and more preferably between about 4% and 10% individually for tungsten and tantalum with the total amount of this group of metals being no more than about 20% by weight of the alloy composition.
  • molybdenum may be present to replace all or part of the tungsten and columbium may be present to replace a part or all of the tantalum.
  • Molybdenum preferably may be present up to about 10% and columbium up to about 2.0% by weight of the alloy composition. It is also desirable to have chromium present in order to provide a higher strength alloy for many uses. Thus, amounts of chromium up to about 25% and preferably between about 10% and about 25% may be used. The presence of a small amount of carbon also increases the strength of the alloy. However, where the carbon content gets above about 0.5% by Weight oxidation corrosion resistance may be sacrificed somewhat. Thus, suitable carbon concentrations are between about 0.05% and about 0.5% by Weight.
  • a convenient way to express the concentrations of the preferred cobalt-base alloys of this invention is by mole ratios based on cobalt.
  • the preferred alloy composi- Patented Aug. 27, 1968 .tions corresponding to the concentrations as set forth above are as follows:
  • the yttrium used in the alloys of the invention may be pure or may be added as a yttrium composition referred to as a misch metal containing at least about 70% yttrium and a small amount of other elements such as lanthanum, cerium, neodymium, Samarium, gadolinium, dysprosium, erbium, ytterbium, etc., as Well as copper, calcium, magnesium, silicon and the like.
  • a yttrium composition referred to as a misch metal containing at least about 70% yttrium and a small amount of other elements such as lanthanum, cerium, neodymium, Samarium, gadolinium, dysprosium, erbium, ytterbium, etc., as Well as copper, calcium, magnesium, silicon and the like.
  • Example I In carrying out the present invention, one of the presently available cobalt alloys, identified as WI-52 and having the following analysis:
  • a graph is shown in FIG. 1 having curves to indicate the results of the tests. As shown in the upper left-hand corner of FIG. 1, the following symbols are used to identify the alloys and the curves plotted to illustrate the effect of the test thereon. It will be apparent from the graph that the cobalt alloy WI-SZ, modified to include small portions of both yttrium and aluminum, gained less weight and was therefore more oxidation resistant than the unmodified cobalt-base alloy or the alloy modified by the addition of either of the elements alone. The graph also shows that the alloy WI52 modified by the addition of 1% yttrium and 3% aluminum (designated X) 'has oxidation resisting qualities equal to the nickel-base alloy.
  • Example II Test samples of the modified cobalt-base alloy X were subjected to sulfidation resistance tests which. were run in an environment consisting of the combustion products of JP4 fuel (CO N 0 H O, S0 at elevated temperatures. After completion of the test the samples are cleaned by boiling in concentrated HNO and wire brushed. The cleaned samples are then weighed to determined any weight change. The results of such tests were compared with the results of similar tests made on the alloy WI-52 without modification and with the addition of a small part of yttrium alone.
  • a chart, identified as FIG. 2 in the drawings, shows the increased resistance to sulfidation secured by the addition of similar small percentages of aluminum and yttrium to the selected cobalt alloy.
  • the chart also shows the results of similar tests applied to samples of the nickel-base alloy Inconel 713C. It is obvious from the chart that the modified cobalt-base alloy X is far superior from a sulfidation resisting standpoint than the nickel-base alloy tested and it is far better than the unmodified cobalt-base alloy.
  • Example III An accelerated oxidation-sulfidation test procedure was worked out and applied to the cobalt-base alloy WI-52, other cobalt-base alloys available on the market, and certain modified cobalt-base alloys including the one (alloy X) forming the subject matter of the present invention.
  • the nominal chemical compositions of the alloys tested are shown in the chart illustrated in FIG. 3.
  • the furnace in which the test was to be conducted was purged for thirty minutes with 2.0 c.f.h. N 0.072 c.f.h. C0 and 0.013 c.f.h. H 8.
  • the test specimens were then placed in a silica retort which was in turn placed in the furnace and supplied with a gaseous mixture of 2.0 c.f.h. N 0.072 c.f.h. CO and 0.013 c.f.h. H 8 for two hours.
  • the retort was supplied with a mixture of 2.0 c.f.h. air, 0.072 c.f.h. CO and 0.013 c.f.h.
  • Example IV The sulfidation test procedure set forth in Example III was repeated with the exception that about 1 p.p.m. NaCl was introduced into the gas stream which contacted the alloy. This was accomplished by bubbling the synthetic gas combustion mixtures through a 10% salt solution. The comparative weight losses for the different alloys tested are set forth and graphically illustrated in FIG. 6.
  • Example IV The sulfidation test procedure set forth in Example IV was repeated. Various alloys were tested with the results total amount of metals of the group is between about 3% and about 20% by weight of the total composition.
  • composition of claim 5 wherein the respective individual amounts of tungsten and tantalum are between and compositions set forth in the following table: 5 about 4% and 10%, the amount of molybdenum is up to Composition, percent Sulfidation, Alloy wt. loss,
  • cobalt-base alloys containing aluminum and yttrium possess vastly superior sulfidation resistance over other alloys including nickel-base alloys containing both aluminum and yttrium.
  • the alloys of the invention may :also contain small amounts of phosphorus and sulfur and preferably in amounts not over 0.04%, silicon in an amount not over about 0.5%.
  • Nickel may be present in amounts up to about 10% as well as iron and manganese in amounts up to about 2.5% in addition to small amounts of zirconium and boron.
  • the absence or presence of these elements is not critical or necessary to the alloys of the invention.
  • the superior sulfidation resistant cobalt-base alloys as disclosed herein may be used for a number of varied purposes.
  • the alloy may be cast, rolled into sheets or prepared as bars or tubing for any uses where superior resistance to sulfur attack as well as oxidation is necessary.
  • a sulfi'dation and oxidation resistant cobalt-base alloy comprising a major amount of cobalt and a small effective amount of the metals aluminum and yttrium in combination, the amount of aluminum and yttrium being effective to increase the sulfidation and oxidation resistance of the cobalt-base alloy.
  • composition of claim 1 wherein the amount of aluminum is up to about 6.0% by weight and the amount of yttrium is up to about 3.0% by weight.
  • composition of claim 1 wherein the amount of aluminum is at least about 1.0% by 'weight and the amount of yttrium is at least about 0.05% by weight.
  • composition of claim 1 wherein the amount of aluminum is between about 1.0% and 6.0% by weight andthe amount of yttrium is between about 0.05 and 3.0% by weight.
  • composition of claim 1 which contains one or more metals selected from the group consisting of tungsten, tantalum, molybdenum and columbium wherein the about 10% and the amount of columbium is up to about 2%.
  • composition of claim 1 which contains up to about 25% chromium and between about 0.05% and about 0.5% by weight, carbon.
  • a sulfidation and oxidation resistant cobalt-base alloy comprising cobalt, between about 1.0% and 6.0% aluminum, between about 0.05% and 3.0% yttrium, a total amount of between about 8% and 20% of one or more of the metals selected from the group consisting of tungsten, tantalum, molybdenum and columbium, between about 10% and 25% chromium and between about 0.05% and 0.5% carbon, with cobalt being the major metal present and wherein the percents specified are by weight of the total composition.
  • composition of claim 8 wherein the amount of cobalt is between about 50% and about and wherein the mole ratios of aluminum and yttrium combined to cobalt is between 1:50 and 1:7, chromium to cobalt is between 1:5 and 2:5 and tungsten, tantalum and molybdenum and columbium combined to cobalt is between 1:6 and 1:3.
  • composition of claim 9 which contains up to the following specified amounts of the following elements: 0.04% phosphorus, 0.04% sulfur, 0.5% silicon, 2.5% iron, 2.5% manganese, 10% nickel, 0.5% boron and 1.0% zirconium.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
US617755A 1963-11-07 1967-01-25 Sulfidation and oxidation resistant cobalt-base alloy Expired - Lifetime US3399058A (en)

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US617755A US3399058A (en) 1963-11-07 1967-01-25 Sulfidation and oxidation resistant cobalt-base alloy
GB0673/68A GB1210561A (en) 1963-11-07 1968-01-11 Oxidation, sulphidation and lead corrosion resistant alloy
DE19681608156 DE1608156A1 (de) 1963-11-07 1968-01-19 Metallegierung auf Kobaltbasis
FR137412A FR93750E (fr) 1963-11-07 1968-01-25 Alliage résistant a la corrosion par oxydation, sulfuration et action du plomb.

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US32209663A 1963-11-07 1963-11-07
US617755A US3399058A (en) 1963-11-07 1967-01-25 Sulfidation and oxidation resistant cobalt-base alloy

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3549354A (en) * 1968-05-29 1970-12-22 Garrett Corp Sulfidation resistant cobalt-base alloys
US3907552A (en) * 1971-10-12 1975-09-23 Teledyne Inc Nickel base alloys of improved properties
US3918139A (en) * 1974-07-10 1975-11-11 United Technologies Corp MCrAlY type coating alloy
DE2655617A1 (de) * 1975-12-08 1977-06-23 United Technologies Corp Oxydationsbestaendige legierung auf kobaltbasis
US4088606A (en) * 1974-05-06 1978-05-09 Gould Inc. Cobalt base nox reducing catalytic structure
US4459263A (en) * 1982-09-08 1984-07-10 Jeneric Industries, Inc. Cobalt-chromium dental alloys containing ruthenium and aluminum
US4530664A (en) * 1980-09-29 1985-07-23 Jeneric Industries, Inc. Cobalt-chromium alloys
US4606887A (en) * 1983-05-28 1986-08-19 Degussa Aktiengesellschaft Cobalt alloys for the production of dental prothesis
US4837389A (en) * 1984-06-04 1989-06-06 Turbine Components Corporation Composite alloy structures
US6756012B2 (en) 2000-08-10 2004-06-29 Jeneric/Pentron, Inc. High expansion dental alloys
EP1925683A1 (fr) * 2005-09-15 2008-05-28 Japan Science and Technology Agency Alliage à base de cobalt ayant une résistance à la chaleur élevée et une résistance élevée et procédé servant à produire celui-ci

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2304353A (en) * 1935-05-09 1942-12-08 Int Nickel Co Heat resistant alloy
US2513471A (en) * 1946-05-09 1950-07-04 Union Carbide & Carbon Corp Alloy articles for high-temperature service
US2513472A (en) * 1946-05-09 1950-07-04 Union Carbide & Carbon Corp Alloy articles for use at high temperatures
US2703355A (en) * 1950-10-23 1955-03-01 Kanthal Corp Electric heater
US2920956A (en) * 1956-10-08 1960-01-12 Universal Cyclops Steel Corp Method of preparing high temperature alloys
US2977223A (en) * 1957-12-10 1961-03-28 Westinghouse Electric Corp Stabilized and precipitation-hardened nickel-base alloys
US2983602A (en) * 1957-09-24 1961-05-09 Armour Res Found Cobalt alloys
US3202506A (en) * 1963-01-23 1965-08-24 David E Deutsch High-temperature oxidation-resistant cobalt base alloys

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2304353A (en) * 1935-05-09 1942-12-08 Int Nickel Co Heat resistant alloy
US2513471A (en) * 1946-05-09 1950-07-04 Union Carbide & Carbon Corp Alloy articles for high-temperature service
US2513472A (en) * 1946-05-09 1950-07-04 Union Carbide & Carbon Corp Alloy articles for use at high temperatures
US2703355A (en) * 1950-10-23 1955-03-01 Kanthal Corp Electric heater
US2920956A (en) * 1956-10-08 1960-01-12 Universal Cyclops Steel Corp Method of preparing high temperature alloys
US2983602A (en) * 1957-09-24 1961-05-09 Armour Res Found Cobalt alloys
US2977223A (en) * 1957-12-10 1961-03-28 Westinghouse Electric Corp Stabilized and precipitation-hardened nickel-base alloys
US3202506A (en) * 1963-01-23 1965-08-24 David E Deutsch High-temperature oxidation-resistant cobalt base alloys

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3549354A (en) * 1968-05-29 1970-12-22 Garrett Corp Sulfidation resistant cobalt-base alloys
US3907552A (en) * 1971-10-12 1975-09-23 Teledyne Inc Nickel base alloys of improved properties
US4088606A (en) * 1974-05-06 1978-05-09 Gould Inc. Cobalt base nox reducing catalytic structure
US3918139A (en) * 1974-07-10 1975-11-11 United Technologies Corp MCrAlY type coating alloy
DE2655617A1 (de) * 1975-12-08 1977-06-23 United Technologies Corp Oxydationsbestaendige legierung auf kobaltbasis
US4078922A (en) * 1975-12-08 1978-03-14 United Technologies Corporation Oxidation resistant cobalt base alloy
US4530664A (en) * 1980-09-29 1985-07-23 Jeneric Industries, Inc. Cobalt-chromium alloys
US4459263A (en) * 1982-09-08 1984-07-10 Jeneric Industries, Inc. Cobalt-chromium dental alloys containing ruthenium and aluminum
US4606887A (en) * 1983-05-28 1986-08-19 Degussa Aktiengesellschaft Cobalt alloys for the production of dental prothesis
US4837389A (en) * 1984-06-04 1989-06-06 Turbine Components Corporation Composite alloy structures
US6756012B2 (en) 2000-08-10 2004-06-29 Jeneric/Pentron, Inc. High expansion dental alloys
EP1925683A1 (fr) * 2005-09-15 2008-05-28 Japan Science and Technology Agency Alliage à base de cobalt ayant une résistance à la chaleur élevée et une résistance élevée et procédé servant à produire celui-ci
EP1925683A4 (fr) * 2005-09-15 2012-08-22 Japan Science & Tech Agency Alliage à base de cobalt ayant une résistance à la chaleur élevée et une résistance élevée et procédé servant à produire celui-ci

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GB1210561A (en) 1970-10-28
DE1608156A1 (de) 1970-12-03
FR93750E (fr) 1969-05-09

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