Nickel-chromium alloys having a dispersed phase

Description

[0001] 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.

Background and Problem

[0002] A modern, advanced design industrial gas turbine (IGT) has hot stage blades and vanes which are required to perform for lives of 5 x 10⁴ to 10⁵ hours in a corroding environment resulting from the combustion of reratively low grade fuels and, in the case of blades, under high stress. Naturally, in order to increase efficiency, it is desired to operatre such IGT blades and vanes at the highest practical operating temperatures consistent with achieving the design lifetimes. When considering operating temperatures, it is necessary to take into account not only the highest temperature to which a turbine blade is exposed, but also a range of temperatures below that highest temperature. 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.

[0003] Over the long design lives of IGT blades and vanes, corrosion resistance and oxidation resistance become more important factors than they are in the well-developed field of aircraft gas turbine (AGT) alloys. Although in neither the case of AGT nor IGTtur- bine blades or vanes would it be advisable to select an oxidation or corrosion prone alloy, the longer (by an order of magnitude) time exposure of IGT components to a more corroding atmosphere make oxidation and corrosion resistance very important features of IGT alloy structures. IGT alloy structures such as hot stage blades and vanes can be coated with conventional coatings to enhance oxidation and corrosion resistance but these coatings are subject to cracking, spalling and the like. Over the long design lives of IGT components, it is more likely that coating failures will occur in comparison to such failures with AGT coated components used for shorter time periods. Thus, even if coated, 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.

[0004] In designing alloy structures for IGT turbine blades it is natural to investigate nickel-base alloys which are used conventionally in AGT turbine blades. Even the strongest conventional, y' strengthened nickel-base alloys rapidly lose strength at temperatures above about 900°C (see Figure 2 of U.S. Patent No. 4 386 976). It is disclosed in U.S. Patent No. 4 386 976 however that nickel-base alloys combining y' strengthening and strengthening by a uniform dispersion of microfine refractory oxidic particles can provide adequate mechanical properties in the temperature range of 750°C up to 1100°. However, the alloys disclosed in U.S. patent No. 4 386 976 are deemed to have inadequate oxidation and corrosion resistance for use in advanced design IGTs. It is also known, for example, from U.S. Patent No. 4 039 330 that y' strengthened nickel-base alloys containing in ther vicinity of 21 to 24 weight percent chromium along with some aluminum have excellent corrosion resistance, of the character needed for IGT usage. At very high temperatures, e.g. over 1000°C, the oxidation resistance of alloys as disclosed in U.S. Patent No. 4 039 330 tends to fail off. Strength at temperatures in excess of 900°C of the alloys disclosed in U.S. Patent NO. 4 039 330, as with all y' strengthened nickel-base alloys is inadequate for components of advanced design IGTs.

[0005] From the background in the immediately preceding paragraph one might be tempted to declare that the solution to providing turbine blades for advanced design IGTs is obvious. Either increase the chromium and/or aluminium content of y' and dispersion strengthened alloys disclosed in U.S. Patent No. 4 386 976 or add dispersion strengthening to the alloys disclosed in U.S. Patent No. 4 039 330. These appealing, seemingly logical solutions to the existing problem are overly simplistic.

[0006] The first possibility i.e., increasing the chromium and/or the aluminum content of a known 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 (NisAl-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. Because the existence of y' phase is essential to component strength at temperatures up to about 900°C, it is necessary to carefully control alloy mofidication to avoid phase instability over the long term usage characteristic of IGTs where a minimum acceptable ductility is essential. From another point of view, indiscriminate alloy modification especially in the realm of increasing aluminum and/or chromium contents presents a difficulty in providing the component microstructure essential to strength of dispersion strengthened alloys at high temperature. Referring again to U.S. Patent No. 4 386 976 Column 1, line 58 et seq., it is disclosed that ODS (oxide dispersion strengthened) alloys must be capable of developing a coarse, elongated grain structure in order to obtain good elevated temperature properties therein. 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 solu- tioned, 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 20° and 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.

[0007] The same difficulty applies to the possible idea of providing oxide dispersion strengthening to a known, high strength y' oxidation and corrosion- resistant alloy. There is no way of predicting whether nor not the theoretical ODS- y' strengthened alloy can be made on a commercial basis.

[0008] The foregoing makes it clear that the provision of alloy components suitable for hot stage advanced design IGT usage is a problem that requires critical metallurgic balancing to at least provide an adequate window for thermal treatment necessary for practical production of such components. In addition, the alloy composition must be capable of undergoing the practical mechanical and thermomechanical processing required to rearch the stage of directional recrystallization.

[0009] The present invention provides alloy bodies suitable for use in advance design IGTs which can be produced in a practical manner.

Brief description of the drawing

[0010] The figure is a photograph showing the grain structure of an alloy body of the invention.

Summary of the invention

[0011] 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 1000°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 ration of said metallic crystals is at least about 7. These metallic crystals (1) have a y' phase dispersed therein at a temperature lower than about 1160°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 19 to 24% chromium, about 1 to 3.4% aluminum, about 1.75 to 5% titanium, about 0.5 to 3% tantalum, up to, i.e. 0 to 1 % niobium, about 1 to 5% tungsten, up to 4% rhenium in replacement of an equal weight percentage of molybdenum or tungsten, up to 25% cobalt, up to 2% hafnium, up to 0.2% carbon, about 0.4 to 0.7% oxygen, about 0.4 to 1 % yttrium, up to about 0.05, e.g. about 0.005 to 0.05% boron, up to 0.5, e.g. about 0.05 to 0.25% zirconium, up to about 1 or 2% iron, up to about 0.3 or 0.5% nitrogen, up to about 1 % molybdenum, the balance except for impurities being nickel. In these alloy bodies, substantially all of the yttrium and a part of the aluminum exist as oxides forming the principal part of the dispersed stable oxidic phase. Depending upon the exact conditions of manufacture and use, the dispersed oxidic phase can comprise yttria and alumina or alumina-yttria mixed oxides such as Al₂O₃. 2Y₂O₃, A1₂0₃ - Y₂0₃ or 5Ab03 - 3Y₂0₃ and comprises about 2.5 to about 4 volume percent of the metallic crystals.

[0012] Generally speaking, the alloy of the present invention is produced by mechanically alloying powdered elemental and/or master alloy constituents along with oxidic yttrium in an attritor or 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. For best results, the milling charge should include powder of an omnibus master alloy, i.e., an alloy containing all non-oxidic 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.

[0013] 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. After extrusion or equivalent hot compaction, 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. Once this is done, 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. If required, 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. It has been found that for alloys having a composition within the range as disclosed hereinbefore, the overall grain coarsening interval, i.e., T_ic (temperature of incipient melting) - Toy's (y' solvus temperature) is at least 20° in Celsius units thereby providing an adequate processing window for commercial production of alloy bodies having coarse elongated grains of high GAR. For alloy bodies of the present invention, solution treatment can be for 1 to 20 hours at 1050 to 1300°C followed by an aging treatment involving maintaining the alloy body for 1 to 24 hours at a temperature in the range of 600 to 950°C. An intermediate aging treatment consisting of maintaining the body for 1 to 16 hours in the range of 800 to 1150°C between solutioning and final aging can be advantageous.

Description of the preferred embodiment

[0014] Alloy bodies of the present invention advantageously contain, in combination or singly, the following preferred amounts of alloying ingredients:

[0015] The composition, (except for nickel balance and from 0.2 to 0.25% N) 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.

[0016] 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% Al master alloy, nickel-28% zirconium master alloy, nickel-16.9% boron master alloy and yttria. In each case 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 cans which were evacuated and sealed. Up to four extrusion cans 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 1200°C to 1300 °C and at total reductions up to about 60% (pass reductions of about 20%) with no difficulties being encountered.

[0017] 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.

[0018] Tensile tests, stress-rupture tests oxidation tests and sulfidation tests were conducted on alloy bodies having a coarse grain structure of high GAR in accordance with the invention with the results shown in the following Tables. The tensile and stress-rupture tests were all conducted in the longitudinal direction as determined by the grain structure of the alloy body. Prior to testing, the alloys as set forth in Table I were formed into alloy bodies of the invention by the zone annealing treatment set forth in Table II. Particular heat treatments employed are also set forth in Table II.

[0019] Some of the alloy bodies of the invention as zone annealed and heattreated as set forth in Table II were tensile tested at various temperatures as reported in Table III.

[0020] Samples of Alloy body 1 tested under stress for creep-rupture exhibited the characteristics as reported in Table IV.

[0021] Alloy bodies of the present invention exhibited results in terms of metal loss and maximum attack along a diameter as set forth in Table VI when sub-

[0022] Other tests have established the rupture stress capabilities of alloy bodies 2 to 5 as set forth in Table V.

jected to the burner rig hot corrosion tests specified therein.

[0023] In addition to the hot corrosion tests specified in Table VI, alloy bodies of the invention were subjected to cyclic oxidation tests in which alloy body specimens were held at the temperatures specified in Table VII in air containing 5% water for 24 hour cycles and then cooled in air on completion of the cycle. Table VII reports results in terms of descaled weight change (mg/cm²) of these tests.

[0024] In order to assess the stability of alloy bodies of the invention, they 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 VIII.

[0025] Tables III through VIII 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 provided the maximum temperature exposure is abouth 1000 °C. For example, Tables III to V show that in strength characteristic, the alloy bodies of the present invention parallel the strength characteristics of IN-CONEL™ 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 optial photograph of the Figure shows the etched outline of coarse metallic grains bound together by grain boundary material.

[0026] In view of the total aluminum and chromium contents of the alloy bodies of the invention, it is expected that these alloy bodies 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. By use of such coating the already high corrosion and oxidation resistance of alloy bodies of the invention can be further enhanced.

[0027] Those skilled in the art will appreciate that 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. For example, in a turbine blade structure, part on all of the root portion can have a grain structure differing from the coarse, elongated, longitudinally oriented grain structure of the blade portion.

[0028] While the present invention has been described with respect to specific embodiments, those skilled in the art will appreciate that alterations and modifications within the scope of the invention can be made. Such alterations and modifications are intended to be within the ambit of the appended claims.

Claims

1. An alloy body especially useful in hot stages of industrial gas turbines having improved resistance to long term stress at temperatures in the range 800°C to 1000°C combined with enhanced oxidation and corrosion resistance comprising, in at least part, an aggreagtion 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, said metallic crystals (1) having a y' phase dispersed therein at a temperature lower than about 1160°C and (2) having dispersed therethrough particles in the range of about 5 to 500 nanometers in major dimension of a stable yttrium-containing oxidic phase, said metallic crystals and grain boundary material consisting in weight percent of about 19 to about 24% chromium, about 1 to about 3.4% aluminum, about 1.75% to about 5% titanium, about 0.5 to about 3% tantalum, up to about 1% niobium, up to about 1% molybdenum, about 1 to about 5% tungsten, up to about 25% cobalt, up to about 2% hafnium, about 0.4 to about 0.7% oxygen, about 0.4 to about 1 % yttrium, up to about 0.2% carbon, up to about 0.05% boron, up to about 0.5% zirconium, up to about 2% iron, up to about 0.5% nitrogen, up to about 4% rhenium in replacement of an equal weight percentage of molybdenum ortungsten, the balance, except for impurities being nickel.

2. An alloy body as in claim 1 containing about 19 to 23% chromium.

3. An alloy body as in claim 1 containing about 1.5 to 3% aluminum.

4. An alloy body as in claim 1 containing about 2 to 4% titanium.

5. An alloy body as in claim 1 containing about 1 to 2% tantalum.

6. An alloy body as in claim 1 containing about 1.8 to 2.5% tungsten.

7. An alloy body as in claim 1 containing about 5 to 25% cobalt.

8. An alloy body as in claim 1 containing up to about 0.7% hafnium.

9. An alloy body as in claim 1 containing up to 0.1% carbon.

10. An alloy body as in claim 1 containing about 0.05 to 0.25% zirconium and about 0.005to 0.05% boron.

11. An alloy body as in claim 1 containing up to about 1 % iron, up to about 0.3% nitrogen and being essentially devoid of rhenium.

Ansprüche

1. Legierungskörper besonders zweckmässig in heissen Stufen von Industriegasturbinen mit verbesserter Beständigkeit gegen Langzeitbelastung bei Temperaturen im Bereich von 800° bis 1000°C kombiniert mit erhöhter Oxidations- und Korrosionsbeständigkeit, umfassend zumindest teilweise eine Aggregation von langsgestreckten, im wesentlichen parallelen metallischen Kristallen mit dazwischenliegenden Korngrenzen, worin das durchschnittliche Sichtflächenverhältnis der genannten metallischen Kristalle mindestens ungefähr 7 ist, wobei die genannten metallischen Kristalle (1) eine in ihnen bei einer Temperatur von weniger als ungefähr 1160°C dispergierte y' Phase haben und (2) darin dispergierte Teilchen im Bereich von ungefähr 5 bis 500 Nanometer in der Hauptdimension einer stabilen yttriumhältigen Oxidphase haben, wobei die genannten metallischen Kristalle und das Korngrenzmaterial in Gew.-% besteht aus ungefähr 19 bis ungefähr 24% Chrom, ungefähr 1 bis ungefähr 3,4% Aluminium, ungefähr 1,75% bis ungefähr 5% Titan, ungefähr 0,5 bis ungefähr 3% Tantal, bis zu ungefähr 1 % Niob, bis zu ungefähr 1 % Molybdän, ungefähr 1 bis ungefähr 5% Wolfram, bis zu ungefähr 25% Kobalt, bis zu ungefähr 2% Hafnium, ungefähr 0,4 bis ungefähr 0,7% Sauerstoff, ungefähr 0,4 bis ungefähr 1 % Yttrium, bis zu ungefähr 0,2% Kohlenstoff, bis zu ungefähr 0,05% Bor, bis zu ungefähr 0,5% Zirkon, bis zu ungefähr 2% Eisen, bis zu ungefähr 0,5% Stickstoff, bis zu ungefähr 4% Rhenium als Ersatz für einen gleichen Prozentsatz Molybdän oder Wolfram, wobei der Rest, abgesehen von Verunreinigungen, Nickel ist.

2. Legierungskörper nach Anspruch 1 enthaltend ungefähr 19 bis 23% Chrom.

3. Legierungskörper nach Anspruch 1 enthaltend ungefähr 1,5 bis 3% Aluminium.

4. Legierungskörper nach Anspruch 1 enthaltend ungefähr 2 bis 4% Titan.

5. Legierungskörper nach Anspruch 1 enthaltend ungefähr 1 bis 2% Tantal.

6. Legierungskörper nach Anspruch 1 enthaltend ungefähr 1,8 bis 2,5% Wolfram.

7. Legierungskörper nach Anspruch 1 enthaltend ungefähr 5 bis 25% Kobalt.

8. Legierungskörpert nach Anspruch 1 enthaltend bis zu ungefähr 0,7% Hafnium.

9. Legierungskörper nach Anspruch 1 entahltend bis zu 0,1 % Kohlenstoff.

10. Legierungskörper nach Anspruch 1 enthaltend ungefähr 0,05 bis 0,25% Zirkon und ungefähr 0,005 bis 0,05% Bor.

11. Legierungskörpre nach Anspruch 1 enthaltend bis zu ungefähr 1 % Eisen, bis zu ungefähr 0,3% Stickstoff und im wesentlichen ohne Rhenium.

Revendications

1. Alliage spécialement utile dans les étages à haute température des turbines à gaz industrielles ayant une résistance améliorée à la contrainte de longue durée à des températures comprises entre 800 et 1000°C, liée à une résistance améliorée à l'oxydation et à la corrosion comprenant, au moins en partie, une aggrégation de cristaux métalliques allongés essentiellement parallèles, ayant des joints de grains entre eux, pour lesquels le rapport de forme de grains moyen desdits cristaux métalliques est d'au moins 7, lesdits cristaux métalliques (1) ayant une phase y dispersée à l'intérieur à une température inférieure à environ 1160°C et (2) ayant des particules d'une phase oxyde stable contenant de l'yttrium, dispersées à l'intérieur, dans la zone de taille comprise entre 5 et 500 nanomètres pour leur plus grande dimension, lesdits cristaux et le matériau de joint de grain constitué en pourcents en poids d'environ 19 à environ 24% de chrome, d'environ 1 à environ 3,4% d'aluminium, d'environ 1,75 à 5% environ de titane, d'environ 0,5 à environ 3% de tantale, jusqu'à environ 1% de niobium, jusqu'à environ 1 % de molybdène, d'environ 1 à environ 5% de tungstène, jusqu'à environ 25% de cobalt, jusqu'à environ 2% de hafnium, d'environ 0,4à environ 0,7% d'oxygène, d'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 pondéral équivalent de molybdène ou de tungstène, le complément, sauf les impurétés, étant du nickel.

2. Alliage selon la revendication 1, contenant environ 19 à 23% de chrome.

3. Alliage selon la revendication 1, contenant environ 1,5 à 3% d'aluminium.

4. Alliage selon la revendication 1, contenant environ 2 à 4% de titane.

5. Alliage selon la revendication 1, contenant environ 1 à 2% de tantale.

6. Alliage selon la revendication 1, contenant environ 1,8 à 2,5% de tungstène.

7. Alliage selon la revendication 1, contenant environ 5 à 25% de cobalt.

8. Alliage selon la revendication 1, contenant jusqu'à environ 0,7% de hafnium.

9. Alliage selon la revendication 1, contenant jusqu'à 0,1 % de carbone.

10. Alliage selon la revendication 1, contenant d'environ 0,05 à 0,25% de zirconium et environ 0,005 à 0,05% de bore.

11. Alliage selon la revendication 1, contenant jusqu'à environ 1% de fer, jusqu'à environ 0,3% d'azote et étant essentiellement dépourvu de rhénium.

Drawing