EP0194683B1 - Alliages nickel-chrome à phase dispersée - Google Patents

Alliages nickel-chrome à phase dispersée Download PDF

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Publication number
EP0194683B1
EP0194683B1 EP86103366A EP86103366A EP0194683B1 EP 0194683 B1 EP0194683 B1 EP 0194683B1 EP 86103366 A EP86103366 A EP 86103366A EP 86103366 A EP86103366 A EP 86103366A EP 0194683 B1 EP0194683 B1 EP 0194683B1
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EP
European Patent Office
Prior art keywords
alloy
alloy body
aluminum
nickel
chromium
Prior art date
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Expired
Application number
EP86103366A
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German (de)
English (en)
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EP0194683A1 (fr
Inventor
Raymond Christopher Benn
Jeffrey Max Davidson
Kenneth Robert Andryszak
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.)
Huntington Alloys Corp
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Inco Alloys International Inc
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Application filed by Inco Alloys International Inc filed Critical Inco Alloys International Inc
Priority to AT86103366T priority Critical patent/ATE36351T1/de
Publication of EP0194683A1 publication Critical patent/EP0194683A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0026—Matrix based on Ni, Co, Cr or alloys thereof

Definitions

  • the present invention is directed to metallic alloy bodies especially suitable for use as structures in hot sections of an industrial gas turbine (IGT) and more particularly to nickel-base alloy bodies suitable for such usage.
  • IIGT industrial gas turbine
  • a modern, advanced design industrial gas turbine has hot stage blades and vanes which are required to perform for lives of 2 to 5 x 10 4 up to 10 5 hours, e.g. at least about 30,000 hours in a corroding environment resulting from the combustion of relatively low grade fuels and, in the case of blades,,under high stress.
  • IGT industrial gas turbine
  • Even at steady-state operation a turbine blade will experience a variety of temperatures along its length from root to tip and across its width from leading to trailing edge.
  • IGT aircraft gas turbine
  • an IGT alloy structure used in the hot stage of an IGT must have the best oxidation and corrosion resistance obtainable commensurate with other required properties and characteristics.
  • the first possibility i.e., increasing the chromium and/or the aluminum content of a know y' and dispersion strengthened alloy, has two difficulties. Increasing either chromium or aluminum can tend to make a nickel-base alloy sigma prone. Increase of chromium directly dilutes the nickel content of the alloy matrix remaining after y' phase precipitation. Increasing the aluminum content increases the amount of y' phase (Ni 3 Al-Ti) which can form in the nickel-base alloy again diluting the matrix with respect to nickel. Detrimental acicular sigma phase tends to form in nickel-base alloys having low nickel matrix contents after intermediate temperature (e.g., 800°C) exposure resulting in low alloy ductility.
  • intermediate temperature e.g. 800°C
  • This coarse, elongated grain structure is developed by directional, secondary recrystallization at a temperature above the y' solvus temperature and below the incipient melting temperature of the alloy (see Column 6, line 58 et seq. of the U.S. Patent No. 4 386 976) or some temperature close to the incipient melting temperature. If y' phase is not solutioned, the secondary crystallization will not proceed. If the incipient melting temperature of the alloy is exceeded the oxide dispersion will be detrimentally affected. For practical production, the interval between the y' solvus temperature and the temperature of incipient melting must be at least about 10° and, more advantageously, at least about 20° in celsius units. Because of the complexity of modern y' strengthened alloy compositions and the complex interactions among the alloying elements, there is no way of predicting the secondary recrystallization interval which is a sine qua non for obtaining the high temperature strength in ODS alloys.
  • alloy components suitable for hot stage advanced design IGT usage is a problem that requires critical metallurgical balancing to at least provide an adequate window for thermal treatment necessary for practical production of such components.
  • alloy composition must be capable of undergoing the practical mechanical and thermomechanical processing required to reach the stage of directional recrystallization.
  • the present invention provides alloy bodies suitable for use in advance design IGTs which can be produced in a practical manner.
  • the figure is a photograph showing the grain structure of an alloy body of the invention.
  • the present invention contemplates an alloy body especially useful as a component in hot stages of industrial gas turbines having improved resistance to long term stress at temperatures in the range 800° to 1100°C combined with enhanced oxidation and corrosion resistance.
  • the alloy body comprises at least in part, an aggregation of elongated, essentially parallel metallic crystals having grain boundaries therebetween wherein the average grain aspect ratio of said metallic crystals is at least about 7.
  • These metallic crystals (I) have a y' phase dispersed therein at a temperature lower than about 1180°C and (2) have dispersed therethrough particles in the size range of about 5 to 500 nanometers in major dimension of an oxidic phase stable at temperatures below at least 1100°C.
  • the metallic crystal inclusive of dispersed material and grain boundary material consists in weight percent of about 18 to 25 % chromium, about 5.5 to 9 % aluminum, up to, i.e. 0 to about 1 % titanium with the proviso that the sum of the percentages of aluminum and titanium is no greater than 9, up to about 4.5 % molybdenum, about 3 to 8 % tungsten, up to about 0.05 %, e.g.
  • boron up to about 0.5 % zirconium, about 0.4 to 1 % yttrium, about 0.4 to about 1 % oxygen, up to about 0.2% carbon, up to about 1 % or 2 % iron, up to about 0.3 or 0.5 % nitrogen, up to about 4 % tantalum, up to about 2 % niobium (with the proviso that tantalum, if any, and niobium, if any, are present in the alloy only when the aluminum content is below about 7 %), up to about 10 % cobalt, up to about 2 % hafnium, up to about 4 % rhenium (in replacement of all or part of molybdenum and/or tungsten) the balance except for impurities being nickel.
  • the dispersed oxidic phase can comprise yttria and alumina or alumina - yttria mixed oxides such as A1 2 0 3 - 2Y 2 0 3 , A1 2 0 3 - Y 2 0 3 or 5AI 2 0 3 . 3Y 2 0 3 and comprises about 2.5 to about 4 volume percent of the metallic crystals.
  • the alloy body of the present invention is produced by mechanically alloying powdered elemental or master alloy constituents along with oxidic yttrium in an attritor or a horizontal ball mill until substantial saturation hardness is obtained along with thorough interworking of the attrited metals one within another and effective inclusion of the oxide containing yttrium within attrited alloy particles to provide homogeneity.
  • the milling charge should include powder of an omnibus master alloy, i.e. an alloy containing all non-oxide alloying ingredients in proper proportion except being poor in nickel or nickel and cobalt.
  • This omnibus master alloy powder is produced by melting and atomization, e.g. gas atomization.
  • the mill charge consists of the omnibus master alloy, yttria or oxidic yttrium and appropriate amounts of nickel, nickel and cobalt or nickel-cobalt alloy powder.
  • the milled powder is then screened, blended and packed into mild steel extrusion cans which are sealed and may be evacuated.
  • the sealed cans are then heated to about 1000°C to 1200°C and hot extruded at an extrusion ratio of at least about 5 using a relatively high strain rate.
  • the thus processed mechanically alloyed material can be hot worked, especially directionally hot worked by rolling or the like. This hot working should be carried out rapidly in order to preserve in the metal a significant fraction of the strain energy induced by the initial extrusion or other hot compaction.
  • the alloy body of the invention is processed by any suitable means, e.g., zone annealing, to provide coarse elongated grains in the body having an average grain aspect ratio (GAR) of at least 7.
  • GAR average grain aspect ratio
  • the thus produced alloy body can be given a solution treatment and a subsequent aging heat treatment to precipitate y' phase in addition to that amount of y' phase forming on cooling from grain coarsening temperatures.
  • the overall grain coarsening interval i.e., T ic (Temperature of incipient melting) - Ty 's (y' solvus temperature) is at least about 20° in Celsius units thereby providing an adequate processing window for commercial production of alloy bodies having coarse elongated grains of high GAR.
  • solution treatment can be for 1 to 20 hours at 1050 to 1300°C. Satisfactory aging treatments involve holding the alloy body at a temperature in the range of 600 to 950°C for 1 to 24 hours. An intermediate aging comprising holding the alloy body for 1 to 16 hours in the range of 800 to 1150°C interposed between the solution treatment and the final aging treatment can be advantageous.
  • Alloy bodies of the present invention advantageously contain, in combination or singly, the following preferred amounts of alloying ingredients:
  • compositions, in weight percent, of ingredients analyzed (assuming all yttrium to be present as yttria), of specific examples of alloys making up alloy bodies of the present invention are set forth in Table I.
  • each of the alloy compositions was prepared by mechanical alloying of batches in an attritor using as raw material nickel powder Type 123, elemental chromium, tungsten, molybdenum, tantalum and niobium, nickel 47.5 % AI master alloy, nickel-28 % zirconium master alloy, nickel-16.9 % boron master alloy and yttria.
  • the powder was processed to homogeneity.
  • Each powder batch was screened to remove particles exceeding 12 mesh, cone blended two hours and packed into mild steel extrusion cane which were evacuated and sealed. Up to four extrusion cane were prepared for each composition. The cans were heated in the range (1000° C to 1200° C) and extruded into bar at an extrusion ratio of about 7.
  • Extrusion was performed on 750 ton press at about 35 % throttle setting.
  • the extruded bar material was subjected to hot rolling at temperatures from about 1200°C to about 1300°C and at total reductions up to about 60 % (pass reductions of about 20 %) with no difficulties being encountered.
  • Heat treating experiments determined that the extruded bar material would grow a coarse elongated grain and that zone annealing at an elevated temperature, in the range of about 1200°C to about 1315°C was an effective grain coarsening procedure.
  • Alloy body No. 1 was tested for hot corrosion under test conditions (1) at 926° C and 843° C - JP-5 fuel + 0.3 Wt. % S, 5 ppm sea salt, 30 : 1 air-to-fuel ratio, 1 cycle/hour (58 min. in flame, 2 min. out in air) 500h test duration and (2) at 704° C - Diesel #2 fuel + 3.0 Wt. % S, 10 ppm sea salt, 30 : 1 air-to-fuel ratio, 1 cycle/day (1425 minutes in flame, 15 minutes out in air) 500 hour test duration.
  • 926°C metal loss was 0.0051 mm with a maximum attack of 0.086 mm.
  • At 843°C metal metal loss and maximum attack were both 0.0051 mm.
  • At 704°C metal loss and maximum attack were both 0.084 mm.
  • alloy bodies of the invention were subjected to cyclic oxidation tests in which alloy body specimens were held at the temperatures specified in Table VI in air containing 5 % water for 24 hour cycles and then cooled in air for the remainder of the cycle.
  • Table VI reports results in terms of descaled weight change (mg/cm 2 ) of these tests.
  • alloy bodies of the invention were exposed, unstressed, to an air atmosphere at 816°C for various times and then examined, either microscopically or by means of a room temperature tensile test. Microscopic examination of alloy bodies 1 and 3 showed no evidence of formation of sigma phase after 6272 hours of exposure. Room temperature tensile test results of alloy bodies of the present invention after specified times of unstressed exposure at 816°C in an air atmosphere are set forth in Table VII.
  • Tables III through VII together in comparison to data in U.S. Patent Nos. 4 386 976 and 4 039 330 mentioned hereinbefore show that alloy bodies of the present invention are suitable for use as IGT hot stage blades and other components.
  • Tables III to V show that in strength characteristics, the alloy bodies of the present invention parallel the strength characteristics of INCONEL TM MA6000 (U.S. Patent No. 3 926 568) whereas Tables VI and VII show that in corrosion and oxidation resistance, the alloy bodies of the present invention exhibit characteristics akin to or better than IN-939 (U.S. Patent No. 4 039 330).
  • the drawing depicts the coarse elongated grain structure of the alloy bodies of the invention which is instrumental in providing their advantageous strength characteristics. Referring now thereto, the optical photograph of the Figure shows the etched outline of coarse metallic grains bound together by grain boundary material.
  • alloy bodies of the present invention can include volumes in which the grain structure can deviate from the coarse elongated structure depicted in the drawing provided that such volumes are not required to possess extreme mechanical characteristics at very high temperatures.
  • part or all of the root portion can have a grain structure differing from the coarse, elongated, longitudinally oriented grain structure of the blade portion.
  • alloy bodies of the invention will constitute compatible substrates for both diffused aluminide coatings and for various high aluminum, high chromium deposited coatings, e.g. M-Cr-AI-Y coatings where M is a metallic element such as nickel or cobalt.
  • M-Cr-AI-Y coatings where M is a metallic element such as nickel or cobalt.

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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)
  • Powder Metallurgy (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Chemically Coating (AREA)

Claims (6)

1. Un corps en alliage particulièrement utile pour les étages chauds des turbines à gaz industrielles ayant une résistance accrue sous contrainte de longue durée à des températures comprises entre 800° et 1100°C ainsi qu'une résistance accrue à l'oxydation et à la corrosion et comprenant, au moins en partie, une agrégation de cristaux métalliques allongés essentiellement parallèles ayant des joints de grains entre eux où le rapport de forme moyen de grain desdits cristaux métalliques est d'au moins environ 7, lesdits cristaux métalliques (1) ayant une phase y' dispersée en leur sein à une température inférieure à environ 1180°C et (2) ayant des particules dispersées au travers, de tailles comprises entre environ 5 et 500 nanomètres dans la grande dimension, d'une phase oxyde stable contenant de l'yttrium, et lesdits cristaux métalliques et matériau de joints de grain comprennant en pourcentage en poids environ 18 à environ 25 % de chrome, environ 5,5 à environ 9 % d'aluminium, jusqu'à 1 % de titane à condition que la quantité de titane, s'il y en a, et d'aluminium ne soit pas supérieure à 9 %, jusqu'à environ 4 % de tantale, jusqu'à environ 2 % de niobium, à condition que le tantale, s'il y en a, et le niobium s'il y en a, soient présents seulement lorsque la teneur en aluminium est inférieure à environ 7 %, jusqu'à environ 4,5 % de molybdène, environ 3 à environ 8 % de tungstène, jusqu'à environ 10 % de cobalt, jusqu'à environ 2 % d'hafnium, environ 0,4 % à environ 1 % d'oxygène, environ 0,4 à environ 1 % d'yttrium, jusqu'à environ 0,2 % de carbone, jusqu'à environ 0,05 % de bore, jusqu'à environ 0,5 % de zirconium, jusqu'à environ 2 % de fer, jusqu'à environ 0,5 % d'azote, jusqu'à environ 4 % de rhénium en remplacement d'un pourcentage équivalent de molybdène ou de tuhgstène, le reste, hormis pour les impuretés, étant du nickel.
2. Un corps en alliage selon la revendication 1 contenant environ 19 à 21 % chrome.
3. Un corps en alliage selon la revendication 1 contenant environ 6 à 7 % d'aluminium.
4. Un corps en alliage selon la revendication 3 ne contenant pas de titane, de tantale, de niobium, de cobalt, d'hafnium ni de rhénium.
5. Un corps en alliage selon la revendication 4 contenant environ 1,5 à environ 2,5 % de molybdène et environ 3 à environ 4,5 % de tungstène.
6. Un corps en alliage selon la revendication 1 contenant environ 10 à 21 % de chrome, environ 6 à 7 % d'aluminium, environ 1,5 à 2,5 % de molybdène, environ 3 à 8 % de tungstène, environ 0,005 à 0,05 % de bore, environ 0,05 à 0,25 % de zirconium, jusqu'à environ 0,1 % de carbone, jusqu'à 1 % de fer, et jusqu'à 0,3 % d'azote.
EP86103366A 1985-03-13 1986-03-13 Alliages nickel-chrome à phase dispersée Expired EP0194683B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86103366T ATE36351T1 (de) 1985-03-13 1986-03-13 Nickel-chrom-legierungen mit dispersionsphase.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US71119985A 1985-03-13 1985-03-13
US711199 1985-03-13

Publications (2)

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EP0194683A1 EP0194683A1 (fr) 1986-09-17
EP0194683B1 true EP0194683B1 (fr) 1988-08-10

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EP86103366A Expired EP0194683B1 (fr) 1985-03-13 1986-03-13 Alliages nickel-chrome à phase dispersée

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EP (1) EP0194683B1 (fr)
JP (1) JPS61264146A (fr)
AT (1) ATE36351T1 (fr)
CA (1) CA1255123A (fr)
DE (1) DE3660497D1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH671583A5 (fr) * 1986-12-19 1989-09-15 Bbc Brown Boveri & Cie
US4781772A (en) * 1988-02-22 1988-11-01 Inco Alloys International, Inc. ODS alloy having intermediate high temperature strength
US4877435A (en) * 1989-02-08 1989-10-31 Inco Alloys International, Inc. Mechanically alloyed nickel-cobalt-chromium-iron composition of matter and glass fiber method and apparatus for using same
CN102162049B (zh) * 2011-04-07 2012-12-19 上海大学 一种超超临界汽轮机用镍基合金材料及其制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3926568A (en) * 1972-10-30 1975-12-16 Int Nickel Co High strength corrosion resistant nickel-base alloy
US3909309A (en) * 1973-09-11 1975-09-30 Int Nickel Co Post working of mechanically alloyed products
US4386976A (en) * 1980-06-26 1983-06-07 Inco Research & Development Center, Inc. Dispersion-strengthened nickel-base alloy
US4402746A (en) * 1982-03-31 1983-09-06 Exxon Research And Engineering Co. Alumina-yttria mixed oxides in dispersion strengthened high temperature alloys
JPS58193335A (ja) * 1982-05-06 1983-11-11 Sumitomo Electric Ind Ltd 分散強化型ニツケル基耐熱焼結合金およびその製造法

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Publication number Publication date
DE3660497D1 (en) 1988-09-15
EP0194683A1 (fr) 1986-09-17
CA1255123A (fr) 1989-06-06
JPS61264146A (ja) 1986-11-22
ATE36351T1 (de) 1988-08-15

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