US20080142126A1 - Graded metallic structures and method of forming; and related articles - Google Patents

Graded metallic structures and method of forming; and related articles Download PDF

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US20080142126A1
US20080142126A1 US11/610,527 US61052706A US2008142126A1 US 20080142126 A1 US20080142126 A1 US 20080142126A1 US 61052706 A US61052706 A US 61052706A US 2008142126 A1 US2008142126 A1 US 2008142126A1
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metallic structure
grain size
reactant
oxide
metallic
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US11/610,527
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Michael Francis Xavier Gigliotti
Pazhayannur Ramanathan Subramanian
Sundar Amancherla
Krishnamurthy Anand
Dheepa Srinivasan
Canan Uslu Hardwicke
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General Electric Co
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General Electric Co
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Assigned to GENERAL ELECTRIC COMPANY reassignment GENERAL ELECTRIC COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GIGLIOTTI, MICHAEL FRANCIS XAVIER, HARDWICKE, CANAN USLU, SUBRAMANIAN, PAZHAYANNUR RAMANATHAN, AMANCHERLA, SUNDAR (NMN), ANAND, KRISHNAMURTHY (NMN), SRINIVASAN, DHEEPA (NMN)
Publication of US20080142126A1 publication Critical patent/US20080142126A1/en
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C14/00Alloys based on titanium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/07Alloys based on nickel or cobalt based on cobalt
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C32/00Non-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
    • C22C32/001Non-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
    • C22C32/0015Non-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
    • C22C32/0026Matrix based on Ni, Co, Cr or alloys thereof
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C32/00Non-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
    • C22C32/001Non-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
    • C22C32/0015Non-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
    • C22C32/0031Matrix based on refractory metals, W, Mo, Nb, Hf, Ta, Zr, Ti, V or alloys thereof
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00Supplementary information concerning processes or compositions relating to powder metallurgy
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the invention is related to graded metallic structures. More particularly, the invention is related to metallic structures having a gradation in grain size. The invention is also related to a method of making a metallic structure having a gradation in grain size.
  • the present invention meets these and other needs by providing a metallic structure having a gradation in grain size.
  • the smaller grains at one portion of the material may provide thermal fatigue resistance for example, and bigger grains at another portion may provide creep resistance, for example.
  • One embodiment of the invention is a metallic structure having a graded microstructure.
  • the metallic structure comprises a graded region comprising a plurality of grains having a gradient in grain size, varying as a function of position, between a first median grain size at an outer region and a second median grain size at an inner region and a plurality of dispersoids dispersed within the microstructure.
  • the first median grain size is different from the second median grain size.
  • Another embodiment is a method for forming a metallic structure having a graded microstructure.
  • the method comprises: providing a metallic structure comprising at least one reactive species; diffusing at least one reactant at a controlled rate from an outer region of the metallic structure towards an inner region of the metallic structure to form a gradient in reactant activity; reacting the reactant with the reactive species to form a plurality of dispersoids; and heat treating the metallic structure to achieve grain growth so as to form a graded microstructure.
  • the graded microstructure comprises a graded region comprising a plurality of grains having a gradient in grain size.
  • the grain size varies as a function of position between a first median grain size at an outer region and a second median grain size at an inner region.
  • the microstructure further comprises a plurality of dispersoids dispersed within the microstructure.
  • the first median grain size is different from the second median grain size.
  • FIG. 1 is a schematic of a metallic structure having a graded microstructure, according to one embodiment of the invention
  • FIG. 2 is a schematic of a metallic structure having a graded microstructure, according to one embodiment of the invention.
  • FIG. 3 is a flow chart of a method of making a metallic structure having a graded microstructure, according to one embodiment of the invention.
  • FIG. 4 is a schematic representation of an experimental setup to fabricate a metallic structure having a graded microstructure, according to one embodiment of the invention.
  • a graded microstructure is meant to describe a microstructure wherein median grain size varies as a function of position.
  • Median grain size implies a median grain size in a selected region.
  • the gradation is substantially continuous, but this does not always have to be the case.
  • the rate-of-change in grain size may itself vary from region to region, increasing slightly in some regions, and decreasing slightly in others. Any and all of these variations in gradations are meant to be encompassed by the term “graded”.
  • the specific grain size profile for a given metallic structure may depend on various factors, e.g., required mechanical and elastic properties, thermal cycling ranges; material composition, actual grain size, and thickness of the metallic structure.
  • FIG. 1 Schematic representation of a metallic structure according to one embodiment of the present invention is shown in FIG. 1 .
  • the metallic structure 10 of FIG. 1 has a graded microstructure comprising gradient in grain size as a function of position from an outer region 12 of the structure towards inner region 14 of the structure.
  • the metallic structure comprises a graded region, for example region 16 comprising a plurality of grains 18 having a gradient in grain size, varying as a function of position, between a first median grain size at an outer region 12 and a second median grain size at an inner region 14 , and a plurality of dispersoids 20 dispersed within the microstructure.
  • the first median grain size is different from the second median grain size.
  • the composition of the metallic structure depends on the end-use application.
  • the metallic structure comprises any suitable metal or a metal alloy. Examples of some suitable metals include, but are not limited to, cobalt, nickel, iron, titanium, various combinations of these, and alloys thereof.
  • the metallic structure comprises a material selected from the group consisting of a cobalt-based super alloy, a nickel-based super alloy, and a titanium-based alloy.
  • the metallic structure comprises a nickel-based super alloy.
  • alloys include, but are not limited to, alloys designated by Universal Numbering System for Metals and Alloys (UNS) UNS N07718, UNS N13100, UNS N09706; alloys designated by General Electric Company trademarks MX4, RENE104, RENE95, RENE88DT; and UDIMET 720 (a trademark of Special Metals Corporation).
  • the alloy comprises alloy UNS N07718.
  • the alloy comprises RENE88DT.
  • the alloy comprises MX4.
  • the resistance to fatigue crack initiation and propagation, in metals and alloys, is known to be influenced by the grain size.
  • Fatigue endurance limit typically increases with decrease in grain size.
  • Studies on grain size variations in metallic materials, in the nano regime, have shown that nanosized grains exhibit enhanced resistance to high cycle fatigue. Accordingly, the grain sizes in the outer and the inner regions are selected based on the elastic properties required in the two regions.
  • the first median grain size (in the outer region) has a value in the range from about 100 nanometers to about 1 micrometer. In another embodiment, the first median grain size (in the outer region) has a value in the range from about 100 nanometers to about 500 nanometers. In another embodiment, the first median grain size has a value in the range from about 100 nanometers to about 200 nanometers. In one embodiment, the second median grain size (in the inner region-core region) has a value in the range from about 10 micrometers to about 100 micrometers. In another embodiment, the second median grain size has a value in the range from about 10 micrometers to about 50 micrometers.
  • the outer region comprises a region from a top surface of the metallic structure to about 5% of the depth of the structure. In another embodiment, the outer region comprises a region from a top surface of the metallic structure to about 10% of the depth of the structure. In another embodiment, the outer region comprises a region from a top surface of the metallic structure to about 15% of the depth of the structure. In another embodiment, the outer region comprises a region from a top surface of the metallic structure to about 40% of the depth of the structure.
  • Such microstructural designs involving graded transitions, from finer surface grain morphology to relatively coarser interior grain morphology may provide gradual transitions in the properties, from a surface layer resistant to high-cycle fatigue to a core region resistant to fatigue damage and crack growth. Further, a fine-grained surface is expected to yield good thermal fatigue resistance, and coarse grains at the inner region may provide creep resistance.
  • the metallic structure comprises a plurality of dispersoids dispersed within the microstructure.
  • the plurality of dispersoids comprise at least one material selected from the group consisting of an oxide, a nitride, a boride, a carbide, a nitride, an intermetallic, a carbo-nitride, and an oxynitride.
  • the dispersoid comprises an oxide. Examples of suitable oxides include, but are not limited to, alumina, zirconia, yttria, hafnia, thoria, titania, ceria, lanthanum oxide, nickel oxide, and erbium oxide.
  • the dispersoid comprises yttria.
  • Dispersoids of suitable size dispersed within the metallic matrix are expected to pin the grain boundaries and thus provide to desired thermal stability and mechanical strength.
  • at least about 50% of the plurality of dispersoids is disposed at the grain boundaries of the plurality of grains.
  • at least about 90% of the plurality of dispersoids are disposed at the grain boundaries of the plurality of grains.
  • the median size of the dispersoids is selected so as to obtain desirable mechanical strength and thermal stability.
  • the dispersoids have a median size in the range from about 10 nanometers to about 1 micrometer. In a particular embodiment, the dispersoids have a median size in the range from about 10 nanometers to about 50 nanometers. If the dispersoids have too large a size, they may be less effective in grain boundary pinning.
  • the metallic structure is structurally stable up to a high temperature, that is, the metallic structure does not undergo a substantial change in crystal structure, grain growth, or morphology.
  • the temperature up to where the metallic structure is stable depends, in part, on the material composition of the metallic structure. In certain embodiments, the metallic structure is structurally stable at a temperature up to about 600° C., in other embodiments, the metallic structure is structurally stable at a temperature up to about 800° C., in yet other embodiments, the metallic structure is structurally stable at a temperature up to about 1000° C., and in yet other embodiments, the metallic structure is structurally stable at a temperature up to about 1100° C.
  • the metallic structure is a bulk monolithic structure.
  • a “bulk monolithic structure” means a three-dimensional bulk structure constituting a single unit without joint. This is in contrast to a body formed of multiple components, such as a laminated, or a multi-layered structure, or a thin film, or a coated layer deposited on a substrate.
  • the metallic structure comprises the metal or metal alloy having the composition and the microstructure as discussed in the structure embodiments above.
  • the structure may be in the form of a sheet, a plate, a disc, an annular ring, or a bar, or any other useful form.
  • the metallic structures described herein may be coated with other materials as required for particular applications.
  • the metallic structure is in the form of an annular ring 30 as shown in FIG. 2 .
  • the metallic structure may be processed such that they have several graded regions.
  • the annular ring 30 has gradation in grain size both from the outer surface 34 and the interior surface 36 .
  • the annular ring may be processed such that finer grains are present towards both surfaces 34 and 36 , and coarser grains towards the middle region 38 .
  • the metallic structures of the embodiments with substantially high mechanical strength, structural stability, fatigue and creep resistant properties are suitable for various structural components. They are especially suited for aeroengine components such as discs that require multifunctional properties. For example, the central portion of a disc may require high creep resistance, whereas, the periphery of an aeroengine disc faces high thermal fatigue damage. It is expected that the grain size gradation would ensure that the component optimizes itself well to the differential properties across its thickness. This may result in improved life as well as enhanced high temperature performance of the disc.
  • the metallic structure comprises a gas turbine component.
  • the metallic structure comprises a turbine airfoil.
  • the metallic structure comprises an aircraft engine disc. It is expected that a fine-grained microstructure of the metallic structure at the periphery may provide desired thermal fatigue resistance. The coarser grains at the core may provide the desired creep resistance.
  • Another aspect of the invention is to provide a method for preparing a metallic structure having a graded microstructure.
  • a flow diagram of the method for making a membrane structure is shown in FIG. 3 .
  • the method 40 begins with step 42 , wherein a metallic structure comprising at least one reactive species is provided.
  • step 44 at least one reactant is diffused, at a controlled rate, from an outer region of the metallic structure towards an inner region of the metallic structure, to form a gradient in reactant activity.
  • the reactant is reacted with the reactive species to form a plurality of dispersoids, and in step 48 , the metallic structure is heat treated to achieve grain growth, so as to form a graded microstructure.
  • the step of heat treating to achieve grain growth may be conducted simultaneously with the diffusion step or may be conducted subsequent to the diffusion step.
  • the nature of the gradient in reactant activity may be selected by controlling the partial pressure of the reactant.
  • a metallic structure comprising at least one reactive species is provided in step 42 .
  • the selection of reactive species depends on the thermodynamics of the process. Specifically, the more negative the value is for the free energy of formation (i.e. ⁇ G o ) for a particular dispersoids material, the greater the tendency (i.e. the thermodynamic driving force) to form the dispersoid at a given temperature within the matrix metal or metal alloy.
  • the reactive species comprises a material selected from the group consisting of an oxide former, a carbide former, a nitride former, a carbo-nitride, and an intermetallic.
  • the reactive species comprises a plurality of oxide formers.
  • the reactive species comprises at least one selected from the group consisting of aluminum, yttrium, zirconia, hafnium, cerium, erbium, and lanthanum.
  • the reactive species comprises yttrium.
  • Yttrium has a strong tendency to form oxides (substantially low free energy of formation).
  • yttria is effective in pinning the grain boundaries of the metallic structure. Therefore, a yttria dispersed metallic structure is expected to yield a desired graded grain structure, on subjecting to a suitable oxidizing atmosphere and temperature treatment.
  • a metallic structure thus processed comprises a graded microstructure such as a metallic structure 10 as shown in FIG. 1 .
  • the graded microstructure comprises a graded region comprising a plurality of grains having a gradient in grain size varying as a function of position between a first median grain size at an outer region 12 and a second median grain size at an inner region 14 , and a plurality of dispersoids 20 dispersed within the microstructure.
  • the first median grain size is different from the second median grain size.
  • the metallic structure may comprise any suitable metal or a metal alloy.
  • suitable metals are cobalt-based super alloys, nickel-based super alloys, and titanium-based alloys.
  • the metallic structure comprises a titanium-based alloy.
  • diffusing a reactant comprises exposing the metallic structure to an effective activity of the reactant.
  • the metallic structure may be exposed to a gaseous phase of the reactant.
  • the metallic structure may be exposed to a solid phase of the reactant.
  • concentration of the reactants at any region within the metallic structure depends on the solubility of the reactant within the metallic structure and its diffusivity.
  • the nature of the gradient in reactant activity may be achieved by controlling the partial pressure of the reactant. Any specific microstructure or grain size gradation may be achieved by controlling the reactive species dispersed within the matrix, their volume fraction, partial pressure of the reactant, temperature, and time duration of heat treatment, among other parameters.
  • the metallic structure may be exposed to a gaseous phase of the reactant.
  • the parent metallic matrix comprising one or more reactive species is produced by casting or any other suitable process.
  • Such a metallic structure may be subjected to a reactant by immersing the sample in a mixture of materials capable of releasing the desired reactant.
  • the sample may be subjected to an oxygen partial pressure by exposing to oxide powders at the desired temperature in a controlled atmosphere.
  • the surrounding oxide at least partially decomposes to yield oxygen that can diffuse into the material to form oxide particles dispersed in the matrix by the process of internal oxidation.
  • the extent of the formation of these oxides with respect to the depth of penetration is a function of the partial pressure, temperature and the surface area exposed.
  • the partial pressure of oxygen may be controlled by adjusting the surrounding oxide mixture, its relative proportions as well as the temperature.
  • An apparatus 50 for carrying out such a process is shown in FIG. 4 .
  • the article 52 to be processed may be placed within a chamber 56 , with the help of fixtures 53 .
  • the article 52 may be surrendered by one or more materials 54 capable of releasing the desired reactant on heating.
  • article 52 is a metallic matrix comprising yttrium surrounded by a nickel oxide powder 54 :
  • the existing partial pressure at 1000° C. is computed analyzing the reactions.
  • the oxygen concentration at 1000° C. would be 0.0024%. This would also mean a partial pressure of 3.56 ⁇ 10 ⁇ 8 torr. Typically, about 10 ⁇ 5 torr oxygen partial pressure would be needed to form a surface layer. (About 10 ⁇ 5 torr oxygen partial pressure would be needed to form a surface layer of aluminum oxide). The passive layer may hinder the flow of reactants through the surface of the structure. Since the partial pressure is three orders of magnitude smaller, partial pressure may be increased using gaseous oxygen to increase the penetration depth.
  • C o is the concentration of the reactant
  • v is the stoichiometric value of the reactive species to the reactant
  • C s is the concentration of the reactive species
  • D t is the diffusivity of the reactive species.
  • Diffusing the reactant at a controlled rate comprises providing the reactant at a controlled partial pressure.
  • the partial pressure required for any reactant-metallic system may be computed, as discussed in detail below.
  • heat treating the metallic structure to achieve grain growth comprises heating at a temperature greater than about 2 ⁇ 3 rd of the melting temperature, as measured on an absolute scale. In some embodiments, the temperature is in a range from about 600° C. to about 1200° C. The exact temperature profile chosen depends on the composition of the metallic structure.
  • the reactant comprises a material selected from the group consisting of oxygen, boron, carbon, and nitrogen.
  • the dispersoid comprises a material selected from the group consisting of an oxide, a nitride, a boride, and an oxynitride.
  • the first median grain size has a value in the range from about 100 nanometers to about 1 micrometer.
  • the second median grain size has a value in the range from about 10 micrometers to about 50 micrometers.
  • the reactant for reacting with the reactive species may be obtained by decomposing a plurality of precursor particles dispersed within the metallic structure.
  • the precursor particles are chemically less stable than the dispersoids.
  • the precursor particles decompose into a product comprising a plurality of secondary reactive species and secondary reactants.
  • the secondary reactants may be further reacted with the reactive species to form dispersoids.
  • Dispersion of precursor particles within the metallic structure gives an additional degree of freedom in altering the reactant activity profile within the metallic structure. This change in the reactant activity profile may be utilized for altering the microstructure of the processed metallic structure.
  • the metallic structures and methods disclosed herein provide many advantages over conventionally used methods.
  • the method is capable of providing a material having a gradient microstructure. These graded metallic structures may provide multifunctional capabilities in a single component and may also enable high temperature performance of the metallic structure.
  • Metallic structures with a hole (rotating parts) or multiple holes (internal cooling holes) may be processed using the disclosed method to achieve several graded regions.
  • the embodiments of the present invention are fundamentally different from those conventionally known in the art. There have been reports of graded metallic structured layers. In such cases, the layers are extremely thin (less than a few micrometers).
  • the metallic structures disclosed herein provide bulk structures with the right balance of creep and fatigue properties within the same monolithic structure. The embodiments of the invention provide simpler and versatile methods to obtain bulk structures of graded metallic structures.
  • Example Method for fabricating a graded metallic structure by internal oxidation of yttria using nickel oxide.
  • the part made of Ni based superalloy with nano-structured grains is placed in a bath of nickel oxide powder.
  • the superalloy has the reactant solutes such as yttria that would readily oxidize.
  • This whole set up is placed in an inert gas furnace (if the component is big) or encapsulated in a glass fixture (for small components).
  • the excess partial pressure could be supplied by passing O 2 gas through the furnace or the fixture.
  • the internal oxidation results in the reactant solute getting oxidized to form the oxide particles in the alloy matrix preferrably at grain boundaries due to enhanced rates of diffusion.
  • the extent of the depth of oxidation is proportional to the temperature and the partial pressure of oxygen. The combination is optimized to get the correct size distribution of the oxide particles up to required depths.

Abstract

A metallic structure having a graded microstructure is provided. The metallic structure comprises a graded region comprising a plurality of grains having a gradient in grain size varying as a function of position between a first median grain size at an outer region and a second median grain size at an inner region and a plurality of dispersoids dispersed within the microstructure. The first median grain size is different from the second median grain size. A method of forming a metallic structure having a graded microstructure is also provided. The method comprises: providing a metallic structure comprising at least one reactive species; diffusing at least one reactant at a controlled rate from an outer region of the metallic structure towards an inner region of the metallic structure to form a gradient in reactant activity; reacting the reactant with the reactive species to form a plurality of dispersoids; and heat treating the metallic structure to achieve grain growth so as to form a graded microstructure.

Description

    BACKGROUND OF THE INVENTION
  • The invention is related to graded metallic structures. More particularly, the invention is related to metallic structures having a gradation in grain size. The invention is also related to a method of making a metallic structure having a gradation in grain size.
  • Materials having spatial gradients in microstructure or composition are of considerable interest in disciplines as diverse as tribology, geology, optoelectronics, biomechanics, fracture mechanics, and nanotechnology. The potential for improved mechanical properties in graded metallic structures is attractive for many high temperature applications. In particular, metallic structures with graded grain size may achieve a desirable balance of thermal fatigue resistance and creep resistance in a single material. Achieving metallic structures with fine grain size and a systematic gradation in grain size has proven to be a very challenging task. Many deposition techniques such as thermal spraying, electrodeposition, and electrophoretic deposition have been explored as means for preparing ultra-fine grained, graded metallic coatings. These methods generally have not been successful in producing bulk metallic structures having high strength and high temperature stability. There remains a demand for materials having a graded microstructure, especially for materials with a proper balance of thermal fatigue resistance and creep resistance. There is also a demand for methods to produce bulk metallic structures having an engineered gradation in grain size.
  • BRIEF DESCRIPTION OF THE INVENTION
  • The present invention meets these and other needs by providing a metallic structure having a gradation in grain size. The smaller grains at one portion of the material may provide thermal fatigue resistance for example, and bigger grains at another portion may provide creep resistance, for example.
  • One embodiment of the invention is a metallic structure having a graded microstructure. The metallic structure comprises a graded region comprising a plurality of grains having a gradient in grain size, varying as a function of position, between a first median grain size at an outer region and a second median grain size at an inner region and a plurality of dispersoids dispersed within the microstructure. The first median grain size is different from the second median grain size.
  • Another embodiment is a method for forming a metallic structure having a graded microstructure. The method comprises: providing a metallic structure comprising at least one reactive species; diffusing at least one reactant at a controlled rate from an outer region of the metallic structure towards an inner region of the metallic structure to form a gradient in reactant activity; reacting the reactant with the reactive species to form a plurality of dispersoids; and heat treating the metallic structure to achieve grain growth so as to form a graded microstructure. The graded microstructure comprises a graded region comprising a plurality of grains having a gradient in grain size. The grain size varies as a function of position between a first median grain size at an outer region and a second median grain size at an inner region. The microstructure further comprises a plurality of dispersoids dispersed within the microstructure. The first median grain size is different from the second median grain size.
  • DESCRIPTION OF THE DRAWINGS
  • These and other features, aspects, and advantages of the present invention will become better understood when the following detailed description is read with reference to the accompanying drawings in which like characters represent like parts throughout the drawing, wherein:
  • FIG. 1 is a schematic of a metallic structure having a graded microstructure, according to one embodiment of the invention;
  • FIG. 2 is a schematic of a metallic structure having a graded microstructure, according to one embodiment of the invention;
  • FIG. 3 is a flow chart of a method of making a metallic structure having a graded microstructure, according to one embodiment of the invention; and
  • FIG. 4 is a schematic representation of an experimental setup to fabricate a metallic structure having a graded microstructure, according to one embodiment of the invention.
  • DETAILED DESCRIPTION OF THE INVENTION
  • In the following description, like reference characters designate like or corresponding parts throughout the several views shown in the figures. It is also understood that terms such as “top,” “bottom,” “outward,” “inward,” “first,” “second,” and the like are words of convenience and are not to be construed as limiting terms. Furthermore, whenever a particular aspect of the invention is said to comprise or consist of at least one of a number of elements of a group and combinations thereof, it is understood that the aspect may comprise or consist of any of the elements of the group, either individually or in combination with any of the other elements of that group.
  • Referring to the drawings in general, it will be understood that the illustrations are for the purpose of describing one embodiment of the invention and are not intended to limit the invention thereto.
  • For the purposes of understanding the invention, the term “a graded microstructure” is meant to describe a microstructure wherein median grain size varies as a function of position. “Median grain size”, implies a median grain size in a selected region. In some embodiments, the gradation is substantially continuous, but this does not always have to be the case. For example, the rate-of-change in grain size may itself vary from region to region, increasing slightly in some regions, and decreasing slightly in others. Any and all of these variations in gradations are meant to be encompassed by the term “graded”. The specific grain size profile for a given metallic structure may depend on various factors, e.g., required mechanical and elastic properties, thermal cycling ranges; material composition, actual grain size, and thickness of the metallic structure.
  • Schematic representation of a metallic structure according to one embodiment of the present invention is shown in FIG. 1. The metallic structure 10 of FIG. 1 has a graded microstructure comprising gradient in grain size as a function of position from an outer region 12 of the structure towards inner region 14 of the structure. In particular, the metallic structure comprises a graded region, for example region 16 comprising a plurality of grains 18 having a gradient in grain size, varying as a function of position, between a first median grain size at an outer region 12 and a second median grain size at an inner region 14, and a plurality of dispersoids 20 dispersed within the microstructure. The first median grain size is different from the second median grain size.
  • The composition of the metallic structure depends on the end-use application. The metallic structure comprises any suitable metal or a metal alloy. Examples of some suitable metals include, but are not limited to, cobalt, nickel, iron, titanium, various combinations of these, and alloys thereof. In a particular embodiment, the metallic structure comprises a material selected from the group consisting of a cobalt-based super alloy, a nickel-based super alloy, and a titanium-based alloy. In one exemplary embodiment, the metallic structure comprises a nickel-based super alloy. Examples of some suitable alloys include, but are not limited to, alloys designated by Universal Numbering System for Metals and Alloys (UNS) UNS N07718, UNS N13100, UNS N09706; alloys designated by General Electric Company trademarks MX4, RENE104, RENE95, RENE88DT; and UDIMET 720 (a trademark of Special Metals Corporation). In a particular embodiment, the alloy comprises alloy UNS N07718. In another embodiment, the alloy comprises RENE88DT. In yet another embodiment, the alloy comprises MX4.
  • The resistance to fatigue crack initiation and propagation, in metals and alloys, is known to be influenced by the grain size. Fatigue endurance limit typically increases with decrease in grain size. Studies on grain size variations in metallic materials, in the nano regime, have shown that nanosized grains exhibit enhanced resistance to high cycle fatigue. Accordingly, the grain sizes in the outer and the inner regions are selected based on the elastic properties required in the two regions.
  • In one embodiment, the first median grain size (in the outer region) has a value in the range from about 100 nanometers to about 1 micrometer. In another embodiment, the first median grain size (in the outer region) has a value in the range from about 100 nanometers to about 500 nanometers. In another embodiment, the first median grain size has a value in the range from about 100 nanometers to about 200 nanometers. In one embodiment, the second median grain size (in the inner region-core region) has a value in the range from about 10 micrometers to about 100 micrometers. In another embodiment, the second median grain size has a value in the range from about 10 micrometers to about 50 micrometers. In one embodiment, the outer region comprises a region from a top surface of the metallic structure to about 5% of the depth of the structure. In another embodiment, the outer region comprises a region from a top surface of the metallic structure to about 10% of the depth of the structure. In another embodiment, the outer region comprises a region from a top surface of the metallic structure to about 15% of the depth of the structure. In another embodiment, the outer region comprises a region from a top surface of the metallic structure to about 40% of the depth of the structure.
  • Such microstructural designs involving graded transitions, from finer surface grain morphology to relatively coarser interior grain morphology may provide gradual transitions in the properties, from a surface layer resistant to high-cycle fatigue to a core region resistant to fatigue damage and crack growth. Further, a fine-grained surface is expected to yield good thermal fatigue resistance, and coarse grains at the inner region may provide creep resistance.
  • Typically, the metallic structure comprises a plurality of dispersoids dispersed within the microstructure. The plurality of dispersoids comprise at least one material selected from the group consisting of an oxide, a nitride, a boride, a carbide, a nitride, an intermetallic, a carbo-nitride, and an oxynitride. In one embodiment, the dispersoid comprises an oxide. Examples of suitable oxides include, but are not limited to, alumina, zirconia, yttria, hafnia, thoria, titania, ceria, lanthanum oxide, nickel oxide, and erbium oxide. In an exemplary embodiment, the dispersoid comprises yttria. Dispersoids of suitable size dispersed within the metallic matrix, are expected to pin the grain boundaries and thus provide to desired thermal stability and mechanical strength. Typically, at least about 50% of the plurality of dispersoids is disposed at the grain boundaries of the plurality of grains. In a particular embodiment, at least about 90% of the plurality of dispersoids are disposed at the grain boundaries of the plurality of grains.
  • The median size of the dispersoids is selected so as to obtain desirable mechanical strength and thermal stability. The dispersoids have a median size in the range from about 10 nanometers to about 1 micrometer. In a particular embodiment, the dispersoids have a median size in the range from about 10 nanometers to about 50 nanometers. If the dispersoids have too large a size, they may be less effective in grain boundary pinning.
  • The metallic structure is structurally stable up to a high temperature, that is, the metallic structure does not undergo a substantial change in crystal structure, grain growth, or morphology. The temperature up to where the metallic structure is stable depends, in part, on the material composition of the metallic structure. In certain embodiments, the metallic structure is structurally stable at a temperature up to about 600° C., in other embodiments, the metallic structure is structurally stable at a temperature up to about 800° C., in yet other embodiments, the metallic structure is structurally stable at a temperature up to about 1000° C., and in yet other embodiments, the metallic structure is structurally stable at a temperature up to about 1100° C.
  • The metallic structure is a bulk monolithic structure. As used herein, a “bulk monolithic structure” means a three-dimensional bulk structure constituting a single unit without joint. This is in contrast to a body formed of multiple components, such as a laminated, or a multi-layered structure, or a thin film, or a coated layer deposited on a substrate. Accordingly, in some embodiments, the metallic structure comprises the metal or metal alloy having the composition and the microstructure as discussed in the structure embodiments above. The structure may be in the form of a sheet, a plate, a disc, an annular ring, or a bar, or any other useful form. Of course, those skilled in the art recognize that the metallic structures described herein may be coated with other materials as required for particular applications.
  • In an exemplary embodiment, the metallic structure is in the form of an annular ring 30 as shown in FIG. 2. When the metallic structure has a plurality of holes, they may be processed such that they have several graded regions. In such cases, the annular ring 30 has gradation in grain size both from the outer surface 34 and the interior surface 36. The annular ring may be processed such that finer grains are present towards both surfaces 34 and 36, and coarser grains towards the middle region 38.
  • The metallic structures of the embodiments with substantially high mechanical strength, structural stability, fatigue and creep resistant properties are suitable for various structural components. They are especially suited for aeroengine components such as discs that require multifunctional properties. For example, the central portion of a disc may require high creep resistance, whereas, the periphery of an aeroengine disc faces high thermal fatigue damage. It is expected that the grain size gradation would ensure that the component optimizes itself well to the differential properties across its thickness. This may result in improved life as well as enhanced high temperature performance of the disc. In one embodiment, the metallic structure comprises a gas turbine component. In an exemplary embodiment, the metallic structure comprises a turbine airfoil. In an exemplary embodiment, the metallic structure comprises an aircraft engine disc. It is expected that a fine-grained microstructure of the metallic structure at the periphery may provide desired thermal fatigue resistance. The coarser grains at the core may provide the desired creep resistance.
  • Another aspect of the invention is to provide a method for preparing a metallic structure having a graded microstructure. A flow diagram of the method for making a membrane structure is shown in FIG. 3. The method 40 begins with step 42, wherein a metallic structure comprising at least one reactive species is provided. In step 44, at least one reactant is diffused, at a controlled rate, from an outer region of the metallic structure towards an inner region of the metallic structure, to form a gradient in reactant activity. In step 46, the reactant is reacted with the reactive species to form a plurality of dispersoids, and in step 48, the metallic structure is heat treated to achieve grain growth, so as to form a graded microstructure.
  • The step of heat treating to achieve grain growth may be conducted simultaneously with the diffusion step or may be conducted subsequent to the diffusion step. The nature of the gradient in reactant activity may be selected by controlling the partial pressure of the reactant.
  • A metallic structure comprising at least one reactive species is provided in step 42. The selection of reactive species depends on the thermodynamics of the process. Specifically, the more negative the value is for the free energy of formation (i.e. ΔGo) for a particular dispersoids material, the greater the tendency (i.e. the thermodynamic driving force) to form the dispersoid at a given temperature within the matrix metal or metal alloy. As discussed above, the reactive species comprises a material selected from the group consisting of an oxide former, a carbide former, a nitride former, a carbo-nitride, and an intermetallic. In a particular embodiment, the reactive species comprises a plurality of oxide formers. In specific embodiments, the reactive species comprises at least one selected from the group consisting of aluminum, yttrium, zirconia, hafnium, cerium, erbium, and lanthanum. In a particular embodiment, the reactive species comprises yttrium. Yttrium has a strong tendency to form oxides (substantially low free energy of formation). Further, yttria is effective in pinning the grain boundaries of the metallic structure. Therefore, a yttria dispersed metallic structure is expected to yield a desired graded grain structure, on subjecting to a suitable oxidizing atmosphere and temperature treatment.
  • The gradient in reactant activity formed in step 44 is expected to create a gradient in precipitation concentration, in step 46. The dispersoids pin the grain boundaries of the metallic structure and hence may control the grain sizes of the metallic material. A gradient in grain size may be obtained by controlling the precipitation formation and the grain growth rate. As discussed in detail above, a metallic structure thus processed comprises a graded microstructure such as a metallic structure 10 as shown in FIG. 1. The graded microstructure comprises a graded region comprising a plurality of grains having a gradient in grain size varying as a function of position between a first median grain size at an outer region 12 and a second median grain size at an inner region 14, and a plurality of dispersoids 20 dispersed within the microstructure. The first median grain size is different from the second median grain size.
  • As discussed in detail in the above embodiments, the metallic structure may comprise any suitable metal or a metal alloy. Examples of some suitable metals are cobalt-based super alloys, nickel-based super alloys, and titanium-based alloys. In an exemplary embodiment, the metallic structure comprises a titanium-based alloy.
  • Generally, diffusing a reactant comprises exposing the metallic structure to an effective activity of the reactant. In some embodiments, the metallic structure may be exposed to a gaseous phase of the reactant. In other embodiments, the metallic structure may be exposed to a solid phase of the reactant. The concentration of the reactants at any region within the metallic structure, in part, depends on the solubility of the reactant within the metallic structure and its diffusivity. Hence for a given metallic structure and reactant system, the nature of the gradient in reactant activity may be achieved by controlling the partial pressure of the reactant. Any specific microstructure or grain size gradation may be achieved by controlling the reactive species dispersed within the matrix, their volume fraction, partial pressure of the reactant, temperature, and time duration of heat treatment, among other parameters.
  • In certain embodiments, the metallic structure may be exposed to a gaseous phase of the reactant. Typically, the parent metallic matrix comprising one or more reactive species is produced by casting or any other suitable process. Such a metallic structure may be subjected to a reactant by immersing the sample in a mixture of materials capable of releasing the desired reactant. For example, the sample may be subjected to an oxygen partial pressure by exposing to oxide powders at the desired temperature in a controlled atmosphere. The surrounding oxide at least partially decomposes to yield oxygen that can diffuse into the material to form oxide particles dispersed in the matrix by the process of internal oxidation. The extent of the formation of these oxides with respect to the depth of penetration is a function of the partial pressure, temperature and the surface area exposed. The partial pressure of oxygen may be controlled by adjusting the surrounding oxide mixture, its relative proportions as well as the temperature. An apparatus 50 for carrying out such a process is shown in FIG. 4. The article 52 to be processed may be placed within a chamber 56, with the help of fixtures 53. The article 52 may be surrendered by one or more materials 54 capable of releasing the desired reactant on heating.
  • The various processing parameters may be evaluated for any specific material system. It is explained, by way of example, where article 52 is a metallic matrix comprising yttrium surrounded by a nickel oxide powder 54:
  • If the alloy with yttrium is surrounded by NiO, without any additional partial pressure of O2, the existing partial pressure at 1000° C. is computed analyzing the reactions.

  • NiO→Ni+½O2  [1]

  • ½O2→[O]alloy  [2]

  • 2Y+3[O]alloy→Y2O3  [3]
  • Gibbs energy for the above mentioned reactions are shown below.

  • ΔG 1=234300+85.2T J/mol

  • ΔG 2=85353+18.5T J/mol

  • ΔG 3=−1640382.24+245.31T J/mol
  • From reactions [1] and [2], using the rate constant calculations, it can be computed that the oxygen concentration at 1000° C. would be 0.0024%. This would also mean a partial pressure of 3.56×10−8 torr. Typically, about 10−5 torr oxygen partial pressure would be needed to form a surface layer. (About 10−5 torr oxygen partial pressure would be needed to form a surface layer of aluminum oxide). The passive layer may hinder the flow of reactants through the surface of the structure. Since the partial pressure is three orders of magnitude smaller, partial pressure may be increased using gaseous oxygen to increase the penetration depth.
  • From a similar analysis, it can be shown that very small quantity (10−39 torr) of oxygen is needed to react with yttria to form Y2O3. This would mean that Y2O3 would form instantaneously.
  • To estimate the penetration distance X, the following equation may be used:

  • X=(2C o /vC s *D t)½  [4]
  • where, Co is the concentration of the reactant, v is the stoichiometric value of the reactive species to the reactant, Cs is the concentration of the reactive species, and Dt is the diffusivity of the reactive species. Using the value of oxygen concentration at the surface and the bulk diffusivity of O in Ni as 1.54×10−8 cm2/sec, the penetration distance would be about 40 micrometers. By varying the temperature and the mixture of the oxides to change the partial pressure of oxygen, the penetration distance may be optimized.
  • Diffusing the reactant at a controlled rate comprises providing the reactant at a controlled partial pressure. The partial pressure required for any reactant-metallic system may be computed, as discussed in detail below. Typically, heat treating the metallic structure to achieve grain growth comprises heating at a temperature greater than about ⅔rd of the melting temperature, as measured on an absolute scale. In some embodiments, the temperature is in a range from about 600° C. to about 1200° C. The exact temperature profile chosen depends on the composition of the metallic structure.
  • As discussed above, the reactant comprises a material selected from the group consisting of oxygen, boron, carbon, and nitrogen. The dispersoid comprises a material selected from the group consisting of an oxide, a nitride, a boride, and an oxynitride. The first median grain size has a value in the range from about 100 nanometers to about 1 micrometer. The second median grain size has a value in the range from about 10 micrometers to about 50 micrometers.
  • In an alternative embodiment, the reactant for reacting with the reactive species may be obtained by decomposing a plurality of precursor particles dispersed within the metallic structure. The precursor particles are chemically less stable than the dispersoids. On decomposition, the precursor particles decompose into a product comprising a plurality of secondary reactive species and secondary reactants. The secondary reactants may be further reacted with the reactive species to form dispersoids. Dispersion of precursor particles within the metallic structure gives an additional degree of freedom in altering the reactant activity profile within the metallic structure. This change in the reactant activity profile may be utilized for altering the microstructure of the processed metallic structure.
  • The metallic structures and methods disclosed herein provide many advantages over conventionally used methods. The method is capable of providing a material having a gradient microstructure. These graded metallic structures may provide multifunctional capabilities in a single component and may also enable high temperature performance of the metallic structure. Metallic structures with a hole (rotating parts) or multiple holes (internal cooling holes) may be processed using the disclosed method to achieve several graded regions.
  • The embodiments of the present invention are fundamentally different from those conventionally known in the art. There have been reports of graded metallic structured layers. In such cases, the layers are extremely thin (less than a few micrometers). The metallic structures disclosed herein provide bulk structures with the right balance of creep and fatigue properties within the same monolithic structure. The embodiments of the invention provide simpler and versatile methods to obtain bulk structures of graded metallic structures.
  • The following example serves to illustrate the features and advantages offered by the present invention, and not intended to limit the invention thereto.
  • EXAMPLES
  • The following examples describe the preparation method a graded metallic structures.
  • Example: Method for fabricating a graded metallic structure by internal oxidation of yttria using nickel oxide.
  • The part made of Ni based superalloy with nano-structured grains is placed in a bath of nickel oxide powder. The superalloy has the reactant solutes such as yttria that would readily oxidize. This whole set up is placed in an inert gas furnace (if the component is big) or encapsulated in a glass fixture (for small components). Depending on the partial pressure of oxygen required to form the surface oxide layer such as AlO (about 10−5 torr), the excess partial pressure could be supplied by passing O2 gas through the furnace or the fixture. The internal oxidation results in the reactant solute getting oxidized to form the oxide particles in the alloy matrix preferrably at grain boundaries due to enhanced rates of diffusion. The extent of the depth of oxidation is proportional to the temperature and the partial pressure of oxygen. The combination is optimized to get the correct size distribution of the oxide particles up to required depths.
  • While the invention has been described with reference to exemplary embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. While only certain features of the invention have been illustrated and described herein, many modifications and changes will occur to those skilled in the art. For example, it should be understood that though the above embodiments are discussed with respect to a airfoil disc, the embodiments of the invention may be utilized in any other metallic component, in which the excellent creep and fatigue resistant of these graded metallic structures are essentially beneficial. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.

Claims (36)

1. A metallic structure having a graded microstructure comprising:
a graded region comprising a plurality of grains having a gradient in grain size varying as a function of position between a first median grain size at an outer region and a second median grain size at an inner region, wherein the first median grain size is different from the second median grain size; and
a plurality of dispersoids dispersed within the microstructure.
2. The metallic structure of claim 1, wherein the metallic structure comprises a material selected from the group consisting of cobalt, nickel, iron, and titanium.
3. The metallic structure of claim 2, wherein the metallic structure comprises a material selected from the group consisting of a cobalt-based super alloy, a nickel-based super alloy, and a titanium-based alloy.
4. The metallic structure of claim 3, wherein the metallic structure comprises a nickel-based super alloy.
5. The metallic structure of claim 1, wherein the metallic structure comprises an alloy selected from the group selected from the group consisting of UNS N07718, UNS N13100, UNS N09706, MX4, RENE104, RENE95, RENE88DT, and UDIMET 720.
6. The metallic structure of claim 1, wherein the first median grain size has a value in the range from about 100 nanometers to about 1 micrometer.
7. The metallic structure of claim 6, wherein the first median grain size has a value in the range from about 100 nanometers to about 500 nanometers.
8. The metallic structure of claim 1, wherein the second median grain size has a value in the range from about 10 micrometers to about 100 micrometers.
9. The metallic structure of claim 8, wherein the second median grain size has a value in the range from about 10 micrometers to about 50 micrometers.
10. The metallic structure of claim 1, wherein the dispersoid comprises a material selected from the group consisting of an oxide, a nitride, a boride, a carbide, an oxynitride, a carbo-nitride.
11. The metallic structure of claim 10, wherein the dispersoid comprises an oxide.
12. The metallic structure of claim 11, wherein the oxide comprises an oxide selected from the group consisting of alumina, yttria, hafnia, lanthanum oxide, nickel oxide, thoria, titania, zirconia, erbium oxide, ceria, and yttrium aluminum oxide.
13. The metallic structure of claim 12, wherein the dispersoids comprise yttria.
14. The metallic structure of claim 1, wherein the dispersoids have a median size in the range from about 10 nanometers to about 1 micrometer.
15. The metallic structure of claim 1, wherein the dispersoids have a median size in the range from about 10 nanometers to about 100 nanometers
16. The metallic structure of claim 1, wherein the metallic structure is structurally stable in a temperature about 600° C. to about 1100° C.
17. The metallic structure of claim 1, wherein the metallic structure is a bulk monolithic structure.
18. A gas turbine component comprising the metallic structure of claim 1.
19. A turbine airfoil comprising the metallic structure of claim 1.
20. An aircraft engine disc comprising the metallic structure of claim 1.
21. A method of forming a metallic structure having a graded microstructure, comprising:
providing a metallic structure comprising at least one reactive species;
diffusing at least one reactant, at a controlled rate, from an outer region of the metallic structure towards an inner region of the metallic structure, to form a gradient in reactant activity;
reacting the reactant with the reactive species to form a plurality of dispersoids; and
heat treating the metallic structure to achieve grain growth, so as to form a graded microstructure,
wherein the graded microstructure comprises a graded region comprising a plurality of grains having a gradient in grain size varying as a function of position between a first median grain size at an outer region and a second median grain size at an inner region, wherein the first median grain size is different from the second median grain size; and
a plurality of dispersoids dispersed within the microstructure.
22. The method of claim 21, wherein the metallic structure comprises a material selected from the group consisting of a cobalt-based super alloy, a nickel-based super alloy, and a titanium-based alloy.
23. The method of claim 22, wherein the metallic structure comprises a titanium-based alloy.
24. The method of claim 21, wherein diffusing a reactant comprises exposing the metallic structure to an effective activity of the reactant.
25. The method of claim 24, wherein exposing the metallic structure to an effective activity of the reactant comprises exposing the metallic structure to a gaseous phase of the reactant.
26. The method of claim 24, wherein exposing the metallic structure to an effective activity of the reactant comprises exposing the metallic structure to a liquid phase of the reactant.
27. The method of claim 21, wherein diffusing the reactant, at a controlled rate, comprises providing the reactant at a controlled partial pressure.
28. The method of claim 21, wherein heat treating the metallic structure to achieve grain growth comprises heating at a temperature in a range from about 600° C. to about 1200° C.
29. The method of claim 21, wherein the reactive species comprises a material selected from the group consisting of an oxide former, a carbide former, a nitride former, and a boride former.
30. The method of claim 29, wherein the reactive species comprises a plurality of oxide formers.
31. The method of claim 21, wherein the reactive species comprises at least one selected from the group consisting of aluminum, yttrium, hafnium, lanthanum, erbium, thorium, titanium, magnesium, cerium, and erbium.
32. The method of claim 21, wherein the reactant comprises a material selected from the group consisting of oxygen, boron, carbon, and nitrogen.
33. The method of claim 21, wherein the dispersoids comprise a material selected from the group consisting of an oxide, a nitride, a boride, a carbide, a oxynitride, an intermetallic, and a carbo-nitride.
34. The method of claim 21, wherein the first median grain size has a value in the range from about 100 nanometers to about 1 micrometer.
35. The method of claim 21, wherein the second median grain size has a value in the range from about 10 micrometers to about 50 micrometers.
36. The method of claim 21, wherein reacting the reactant with the reactive species comprises:
decomposing a precursor particles, dispersed within the metallic structure, into a product comprising a secondary reactive species and a secondary reactant; and
reacting the secondary reactant with the reactive species.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100043597A1 (en) * 2008-08-19 2010-02-25 Arrell Douglas J Method of making rare-earth strengthened components
WO2013037502A1 (en) * 2011-09-15 2013-03-21 Universität Bayreuth Method for producing a metal matrix composite material
US20150004044A1 (en) * 2013-06-28 2015-01-01 General Electric Company Nanostructured ferritic alloy and method of forming
US20150004043A1 (en) * 2013-06-28 2015-01-01 General Electric Company Precipitate strengthened nanostructured ferritic alloy and method of forming
CN104711441A (en) * 2013-12-12 2015-06-17 通用电气公司 Particulate strengthened alloy articles and methods of forming
EP3081321A1 (en) * 2015-04-14 2016-10-19 Honeywell International Inc. Methods of producing dispersoid hardened metallic materials
CN108588498A (en) * 2018-05-30 2018-09-28 哈尔滨理工大学 A kind of method that Ni-based functionally gradient material (FGM) and precinct laser fusion method prepare Ni-based functionally gradient material (FGM)
CN113862589A (en) * 2021-09-29 2021-12-31 成都大学 Method for forming reverse grain size gradient microstructure in pure copper

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3578443A (en) * 1969-01-21 1971-05-11 Massachusetts Inst Technology Method of producing oxide-dispersion-strengthened alloys
US3779714A (en) * 1972-01-13 1973-12-18 Scm Corp Dispersion strengthening of metals by internal oxidation
US4752333A (en) * 1985-05-10 1988-06-21 Trefimetaux Alloys having high electrical and mechanical characteristics, the production thereof and the uses thereof in particular in the electrical, electronic and connection arts
US5147728A (en) * 1990-01-26 1992-09-15 Seiichi Tanaka Ag-SnO2 electrical contact materials
US5415704A (en) * 1992-02-07 1995-05-16 Smith & Nephew Richards Inc. Surface hardened biocompatible metallic medical implants

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3578443A (en) * 1969-01-21 1971-05-11 Massachusetts Inst Technology Method of producing oxide-dispersion-strengthened alloys
US3779714A (en) * 1972-01-13 1973-12-18 Scm Corp Dispersion strengthening of metals by internal oxidation
US4752333A (en) * 1985-05-10 1988-06-21 Trefimetaux Alloys having high electrical and mechanical characteristics, the production thereof and the uses thereof in particular in the electrical, electronic and connection arts
US5147728A (en) * 1990-01-26 1992-09-15 Seiichi Tanaka Ag-SnO2 electrical contact materials
US5415704A (en) * 1992-02-07 1995-05-16 Smith & Nephew Richards Inc. Surface hardened biocompatible metallic medical implants

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100043597A1 (en) * 2008-08-19 2010-02-25 Arrell Douglas J Method of making rare-earth strengthened components
WO2010021641A1 (en) * 2008-08-19 2010-02-25 Siemens Energy, Inc. Method of making rare-earth strengthened components
US8029596B2 (en) 2008-08-19 2011-10-04 Siemens Energy, Inc. Method of making rare-earth strengthened components
WO2013037502A1 (en) * 2011-09-15 2013-03-21 Universität Bayreuth Method for producing a metal matrix composite material
US20150004044A1 (en) * 2013-06-28 2015-01-01 General Electric Company Nanostructured ferritic alloy and method of forming
US20150004043A1 (en) * 2013-06-28 2015-01-01 General Electric Company Precipitate strengthened nanostructured ferritic alloy and method of forming
CN104711441A (en) * 2013-12-12 2015-06-17 通用电气公司 Particulate strengthened alloy articles and methods of forming
EP3081321A1 (en) * 2015-04-14 2016-10-19 Honeywell International Inc. Methods of producing dispersoid hardened metallic materials
US9764384B2 (en) 2015-04-14 2017-09-19 Honeywell International Inc. Methods of producing dispersoid hardened metallic materials
CN108588498A (en) * 2018-05-30 2018-09-28 哈尔滨理工大学 A kind of method that Ni-based functionally gradient material (FGM) and precinct laser fusion method prepare Ni-based functionally gradient material (FGM)
CN113862589A (en) * 2021-09-29 2021-12-31 成都大学 Method for forming reverse grain size gradient microstructure in pure copper

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