US20160207110A1 - Corrosion resistant article and methods of making - Google Patents

Corrosion resistant article and methods of making Download PDF

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US20160207110A1
US20160207110A1 US14/600,083 US201514600083A US2016207110A1 US 20160207110 A1 US20160207110 A1 US 20160207110A1 US 201514600083 A US201514600083 A US 201514600083A US 2016207110 A1 US2016207110 A1 US 2016207110A1
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Prior art keywords
phase
article
weight percent
matrix
duplex
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Shenyan Huang
Raul Basilio Rebak
Richard DiDomizio
Emanuele Pietrangeli
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General Electric Co
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General Electric Co
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Priority to US14/600,083 priority Critical patent/US20160207110A1/en
Assigned to GENERAL ELECTRIC COMPANY reassignment GENERAL ELECTRIC COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DIDOMIZIO, RICHARD, HUANG, SHENYAN, PIETRANGELI, EMANUELE, REBAK, RAUL BASILIO
Priority to CN201680006503.7A priority patent/CN107429368A/zh
Priority to RU2017123555A priority patent/RU2735179C2/ru
Priority to JP2017536015A priority patent/JP2018508652A/ja
Priority to EP16701383.8A priority patent/EP3247517A1/en
Priority to PCT/US2016/012977 priority patent/WO2016118358A1/en
Publication of US20160207110A1 publication Critical patent/US20160207110A1/en
Abandoned legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B22F3/15—Hot isostatic pressing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/16—Both compacting and sintering in successive or repeated steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/17—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by forging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0026—Matrix based on Ni, Co, Cr or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C22C33/0285—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/17—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by forging
    • B22F2003/175—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by forging by hot forging, below sintering temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/001—Austenite
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/004—Dispersions; Precipitations
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/005—Ferrite
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2241/00—Treatments in a special environment
    • C21D2241/01—Treatments in a special environment under pressure
    • C21D2241/02—Hot isostatic pressing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni

Definitions

  • the invention relates generally to a nanostructured ferritic alloy comprising a duplex microstructure (referred to as the duplex NFA) and articles made of such alloys. More particularly, the invention relates to an article having a duplex nanostructured ferritic alloy surface with good corrosion resistance, and methods of forming the article.
  • a duplex microstructure referred to as the duplex NFA
  • Material selection is especially important in equipment components used in sour and acid environments commonly associated with oil and gas extraction installations.
  • Sour gas wells may contain carbon dioxide, chlorides, hydrogen sulfides, and free sulfur, and may operate at temperatures up to 400° C. This type of corrosive environment requires carefully designed alloys to enable components to maintain their structural integrity over their service life.
  • Conventional corrosion resistant steels include ferritic, austenitic, and ferritic/austenitic duplex steels.
  • ferritic steels have improved stress corrosion cracking resistance in chloride-containing environments, but the strength is relatively low.
  • Austenitic and duplex steels have good corrosion resistance, low to intermediate strength, but inferior stress corrosion cracking resistance.
  • Nickel-based super alloys have high strength, corrosion resistance, and stress-corrosion cracking resistance.
  • Ni-based super alloys generally include nickel (Ni), as well as other elements such as iron (Fe), chromium (Cr), molybdenum (Mo), tungsten (W), and copper (Cu).
  • Nickel provides resistance to aqueous chloride stress corrosion cracking and provides resistance to alkalis, while iron is generally added to reduce the use of nickel, where appropriate.
  • Molybdenum and tungsten are beneficial for pitting corrosion resistance and provides general corrosion resistance in reducing acids. Chromium improves general corrosion resistance in oxidizing acidic media. Copper is found to be beneficial for general corrosion resistance in non-oxidizing corrosion environments.
  • Ni—Fe—Cr—Mo—Cu Relative concentrations of Ni—Fe—Cr—Mo—Cu, along with alloy processing and service history of the component, in part determine overall corrosion resistance in oil and gas applications. Because higher nickel content increases the cost of raw materials, there is a need for alloys with lower nickel content than typical superalloys but having mechanical strength and corrosion resistance in sour and acid environment superior to conventional steels.
  • One embodiment of the invention is directed to an article.
  • the article has a surface, and this surface includes a duplex nanostructured ferritic alloy.
  • the alloy includes a plurality of nanofeatures disposed in an iron-bearing alloy matrix; this plurality includes complex oxide particles that include yttrium, titanium, and optionally other elements.
  • the iron-bearing alloy matrix includes both a ferrite phase and an austenite phase. Further, a concentration of a chi phase or a sigma phase in the duplex nanostructured ferritic alloy disposed at the surface is less than about 5 volume percent.
  • the method generally includes the steps of milling, thermo-mechanically consolidating, annealing, and cooling.
  • an iron-bearing alloy powder is milled in the presence of yttrium oxide until the oxide is substantially dissolved into the alloy.
  • the milled powder is consolidated, often under an inert environment, to form a consolidated component, which is then annealed above the solvus temperature of chi and sigma phases and cooled at a rate that prevents the formation of chi and sigma phases to form a processed component having the characteristics noted previously for the article.
  • FIG. 1 is a schematic cross section of an article in accordance with an embodiment of the present invention.
  • FIG. 2 is a comparison of room-temperature tensile properties of an as-forged duplex NFA with two baseline steels and a Ni-based alloy 718, in accordance with one embodiment of the invention.
  • FIG. 3 is a comparison of corrosion properties of the as-forged duplex NFA with two baseline steels and a Ni-based alloy 718 in NACE TM0177 Solution A (5% NaCl and 0.5% CH 3 COOH, deaerated), in accordance with one embodiment of the invention.
  • Embodiments of the invention described herein address the noted shortcomings of the state of the art.
  • One or more specific embodiments of the present invention will be described below. In an effort to provide a concise description of these embodiments, all features of an actual implementation may not be described in the specification. It should be appreciated that in the development of any such actual implementation, as in any engineering or design project, numerous implementation-specific decisions must be made to achieve the developers' specific goals, such as compliance with system-related and business-related constraints, which may vary from one implementation to another. Moreover, it should be appreciated that such a development effort might be complex and time consuming, but would nevertheless be a routine undertaking of design, fabrication, and manufacture for those of ordinary skill having the benefit of this disclosure.
  • the articles “a,” “an,” and “the” are intended to mean that there are one or more of the elements.
  • the terms “comprising,” “including,”, “involving,”, and “having” (and their associated tense forms) are intended to be inclusive and mean that there may be additional elements other than the listed elements. All ranges disclosed herein are inclusive of the endpoints, and the endpoints are combinable with each other.
  • Approximating language may be applied to modify any quantitative representation that could permissibly vary without resulting in a change in the basic function to which it may be related. Accordingly, a value modified by a term such as “about” is not limited to the precise value specified. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value.
  • embodiments of this invention are directed to the formation of Fe—Cr—Ni—Mo-based nanostructured ferritic alloy (NFA) comprising a duplex microstructure (“duplex NFA”) with mechanical strength and corrosion resistance superior to conventional steels in sour and acid environments.
  • FFA Fe—Cr—Ni—Mo-based nanostructured ferritic alloy
  • duplex NFA duplex microstructure
  • This material has potential application for structural components used in sour and acid environments at temperatures below 400° C., which enables better lifetime at higher operating stress levels and harsher environments than typically observed for conventional steels.
  • NFA is a new class of oxide dispersion-strengthened alloys fabricated by mechanical alloying, as described in patent U.S. Pat. No. 8,357,328B2 and patent application with Ser. No. 14/334742 titled “Corrosion resistant Articles and Methods of Making” filed on 18 Jul. 2014.
  • Appropriate milling and subsequent processing generate a unique microstructure of fine grains and densely distributed inter- and intra-granular nanofeatures; this microstructure is responsible in large part for NFA's high strength and good ductility.
  • the NFA composition includes a plurality of nanofeatures disposed in an iron-bearing alloy matrix having a duplex structure.
  • the NFA composition generally includes at least about 30 weight percent iron, with the particular amount often depending on the degree of alloying (that is, the amount of other elements added to the iron) needed to achieve the desired balance of properties; in some embodiments the composition includes at least about 50 weight percent iron, and at least about 70 weight percent iron in particular embodiments.
  • Duplex NFA (alternately “nanostructured duplex alloy”) has a duplex structure of two iron based matrix phases.
  • a “duplex structure” has two principal parts or portions that are structurally, microstructurally, or compositionally different from each other.
  • the duplex NFA disclosed hereinabove typically includes a duplex structure of an alloy matrix that includes the ferritic body-centered cubic (BCC) phase (known in the art as ferrite or “alpha iron” or “bcc iron” or simply “alpha”) and an austenitic face-centered cubic (FCC) phase (known in the art as austenite or “gamma iron” or “fcc iron” or simply “gamma”).
  • BCC ferritic body-centered cubic
  • FCC austenitic face-centered cubic
  • the ferrite and austenite phases may be in any desirable ratios depending on the composition and processing of the alloy.
  • the ferrite phase in the matrix of the duplex NFA is in a range from about 10 volume percent to about 90 volume percent of the matrix.
  • the ferrite phase in the matrix of the duplex NFA is in a range from about 20 volume percent to about 40 volume percent of the matrix.
  • the austenite phase in the matrix of the duplex NFA is in a range from about 10 volume percent to about 90 volume percent of the matrix.
  • the austenite phase in the matrix of the duplex NFA is in a range from about 60 volume percent to about 80 volume percent of the matrix.
  • the article 100 includes a surface 110 that includes a corrosion resistant duplex NFA.
  • the alloy includes a plurality of nanofeatures that includes complex oxide particles comprising yttrium, titanium, and possibly other elements, disposed in an iron-bearing alloy matrix having a duplex structure of ferrite and austenite phases of iron. Further, a concentration of a chi phase or a sigma phase at the surface 110 is less than about 5 volume percent.
  • the corrosion resistance of the duplex NFA in many environments is generally proportional to the concentrations of molybdenum and chromium dissolved within the matrix of the alloy.
  • concentrations of these elements are increased in iron-bearing alloys, the thermodynamics of the alloy chemistry increasingly favor the formation of intermetallic phases, such as the above-mentioned chi phase and sigma phase that are rich in molybdenum and/or chromium and/or iron.
  • these phases remove molybdenum and chromium from the matrix, sequestering these desirable elements into the intermetallic compounds and leaving behind a depleted matrix that is substantially less corrosion resistant than it would be if the elements remained in solution.
  • the article 100 of the present invention is engineered to provide a surface 110 made of the described duplex NFA and yet, at least at surface 110 , maintains high levels of molybdenum and chromium dissolved within the matrix, often levels in excess of the solubility limits that would be expected for thermodynamic equilibrium.
  • Surface 110 of article 100 is a surface that is disposed proximate to, or in actual contact with, the ambient environment 120 . As corrosion is typically a surface-driven phenomenon, it is this surface 110 whose characteristics are often very important in determining the corrosion resistance of the article 100 . In certain embodiments of the present invention, at least this surface 110 has the above-described composition, although it should be appreciated that the composition need not be limited to only the very surface 110 of the article; any volume fraction of the article 100 , including substantially all of article 100 , may include the duplex NFA, and any volume fraction of the duplex NFA, including substantially all of the alloy present in article 100 , may include the composition and other characteristics described herein.
  • surface 110 need not be the outermost surface 130 of article 100 (that is, the surface in contact with ambient environment 120 ); optionally, one or more outer layers 140 , such as, for instance, a paint layer, a conversion coating, a thermal barrier coating, or other layer or combination of layers, may be disposed over surface 110 .
  • outer layers 140 such as, for instance, a paint layer, a conversion coating, a thermal barrier coating, or other layer or combination of layers, may be disposed over surface 110 .
  • nanofeature means a feature, such as a particulate phase, that has a longest dimension less than about 50 nanometers in size. Nanofeatures may have any shape, including, for example, spherical, cuboidal, lenticular, and other shapes.
  • the mechanical properties of the duplex NFA may be controlled by controlling, for example, the density (meaning the number density, that is, the number of particles per unit volume) of the nanofeatures in the matrix; the grain size, determined by size and distribution of nanofeatures and processing conditions; the composition of the nanofeatures; the composition and fraction of chi or sigma phases; and the processing methods used to form the article.
  • the nanofeatures have a number density of at least about 10 18 nanofeatures per cubic meter of the duplex NFA. In another embodiment, the nanofeatures have a number density of at least about 10 20 per cubic meter of the duplex NFA. In yet another embodiment, the nanofeatures have a number density in a range from about 10 21 to 10 24 per cubic meter of the duplex NFA.
  • the nanofeatures may act to impede dislocation motion.
  • the nanofeatures have an average size in a range from about 1 nanometer to about 50 nanometers.
  • the nanofeatures have an average size in a range from about 1 nanometer to about 25 nanometers.
  • the nanofeatures have an average size in a range from about 1 nanometer to about 10 nanometers.
  • Nanofeatures present in the duplex NFA described herein include oxides.
  • the composition of the oxides will depend in part on the composition of the alloy matrix, composition of the raw materials used in processing the material, and the processing methods used to prepare the duplex NFA, which will be discussed in more detail below.
  • the plurality of nanofeatures includes a plurality of complex oxide particles.
  • a “complex oxide” as used herein is an oxide phase that includes more than one non-oxygen element.
  • the complex oxide particles comprise yttrium and titanium, and in certain embodiments one or more additional elements may be present as well.
  • Such elements include, but are not limited to, aluminum, zirconium, and hafnium, as well as other elements that may be present in the matrix, such as, for example, iron, chromium, molybdenum, tungsten, manganese, silicon, niobium, nickel, tantalum.
  • the alloy matrix of the duplex NFA comprises titanium, and at least about 35 weight percent iron.
  • the titanium is present in the range from about 0.1 weight percent to about 2 weight percent.
  • the alloy matrix comprises from about 0.1 weight percent titanium to about 1 weight percent titanium.
  • titanium plays a role in the formation of the oxide nanofeatures, as described above.
  • the concentration of titanium in the nanoferritic alloy is in a range from about 0.15 wt % to about 2 wt %.
  • the plurality of nanofeatures of the duplex NFA may further include simple or complex oxides other than the specific complex oxides described above.
  • a “simple oxide” as used herein is an oxide phase that has one non-oxygen element, such as, for example, yttrium or titanium.
  • the surface 110 of the article 100 has outstanding corrosion resistance, which is a result of the high concentration of chromium and molybdenum in the ferritic phase and chromium, molybdenum, and nitrogen in the austenite phase.
  • the percentage of molybdenum and/or chromium may exceed the equilibrium solubility in the matrix, which makes the alloy thermodynamically metastable.
  • thermodynamic equilibrium in particular the precipitation kinetics of molybdenum-, chromium-, and iron-enriched secondary phases such as chi phase and sigma phase, is expected to be extremely slow at relatively low temperatures (below 400° C.), such that substantial molybdenum will stay in the supersaturated matrix to provide improved corrosion resistance during the lifetime of the article.
  • the iron-bearing alloy matrix may include a chromium concentration of about 15 weight percent to about 30 weight percent. In one embodiment, the concentration of chromium in the iron-bearing alloy matrix of the duplex NFA is in a range from about 20 weight percent to about 27 weight percent.
  • the iron-bearing alloy matrix includes about 0.5 weight percent to about 10 weight percent of molybdenum.
  • the concentration of molybdenum in the iron-bearing alloy matrix of the duplex NFA is in a range from about 0.5 weight percent to about 10 weight percent. In another embodiment, the concentration of molybdenum in the iron-bearing alloy matrix of the duplex NFA varies in a range from about 1 weight percent to about 5 weight percent.
  • the stabilization of the austenitic phase of the duplex structured matrix may be aided by the addition of certain alloying elements, such as manganese, nickel, nitrogen, carbon, cobalt. Therefore, a small amount of manganese, nickel or any combination of these is desirable in the matrix of the duplex NFA.
  • the matrix of the duplex NFA includes nickel in an amount from about 4 weight percent to about 10 weight percent.
  • the matrix of duplex NFA includes nickel in an amount from about 5 weight percent to about 8 weight percent.
  • the matrix of the duplex NFA includes nitrogen in an amount from about 0.2 weight percent to about 0.3 weight percent.
  • the iron-bearing alloy matrix may further include one or more additional minor elements such as tungsten, silicon, manganese, or cobalt, for example.
  • the duplex NFA matrix includes tungsten ⁇ 1 wt %, silicon ⁇ 0.5 wt %, manganese ⁇ 0.5 wt %, phosphorous ⁇ 0.005 wt %, sulfur ⁇ 0.005 wt %, copper ⁇ 0.08 wt %, and/or cobalt ⁇ 0.1 wt %.
  • a concentration of precipitated chromium- and/or molybdenum-containing secondary phases in the duplex NFA is engineered to be low.
  • the chromium or molybdenum upon exceeding local equilibrium solubility levels, precipitate as chi phase or sigma phase in the ferritic matrix.
  • Chi phase and sigma phase are intermetallic phases enriched in chromium, molybdenum, and iron. They are well-known in the art of ferrous metallurgy, and are usually found in high chromium and molybdenum steels as a result of heat treatment or thermo-mechanical processing in the temperature range from about 500° C.
  • Chi phase generally has a body centered cubic crystal structure and sigma phase has tetragonal crystal structure. Chi phase is formed in lower chromium and molybdenum composition space, while sigma phase is formed in higher chromium and molybdenum composition space.
  • the chi phase and sigma phase may coexist in duplex steels under certain thermomechanical processing conditions.
  • a concentration of chi phase or sigma phase in the duplex NFA at surface 110 of the disclosed article 100 is less than about 5 volume percent. In another embodiment, a total concentration of the chi phase and sigma phase in the duplex NFA is less than about 5 volume percent. In a specific embodiment, surface 110 is substantially free of both chi phase and sigma phase.
  • the nanofeatures used herein are typically formed in-situ in the duplex NFA by the dissolution of an initially added oxide, typically after milling with sufficient time and energy, and the precipitation, typically during a consolidation step, of nanometer-sized clusters of a complex oxide. These complex oxide particles can serve to pin the grain structure, thus providing enhanced mechanical properties.
  • a desirable grain size distribution of the duplex NFA matrix may be achieved by controlling the processing parameters during preparation of the alloy.
  • the desired strength, ductility, and corrosion resistance of the surface of the article are achieved by careful control of the composition and processing of the duplex NFA.
  • chromium and molybdenum are kept as solid solution elements in the ferritic matrix by using proper milling conditions (speed, time, mill kinetic energy), and post-forge annealing at sufficiently high temperature (higher than the solvus temperature of chromium and molybdenum-enriched phases such as sigma and chi) followed by cooling at a rate rapid enough to inhibit precipitation of chromium or molybdenum-enriched secondary phases.
  • a method for preparation of an article such as article 100 , having a surface 110 comprising n duplex NFA with the specific features described in various embodiments presented above.
  • the method generally includes the steps of milling, consolidating, annealing, and cooling at a rate rapid enough to inhibit precipitation of sigma and chi phases.
  • a feedstock of an iron-bearing alloy powder is milled in the presence of yttrium oxide, typically in a particulate form, until the oxide is substantially dissolved into the alloy.
  • the iron-bearing alloy powder is milled in the presence of yttrium oxide until substantially all the yttrium oxide is dissolved into the alloy.
  • the feedstock of the iron-bearing alloy powder may also contain titanium, chromium, molybdenum, and nitrogen or iron nitride, as well as any of the other additional elements described above as being potentially useful in the alloy of article 100 .
  • the feedstock may have to be milled with high speed and energy to obtain the desired levels of yttrium dissolution during milling, in accordance with practices known in the art.
  • Different factors that may influence the milling energy and the final milled materials include strength, hardness, size, speed, and ratio of the milling media with respect to the feedstock material, and overall time and temperature of milling.
  • the milling atmosphere may vary.
  • the milling is carried out in an inert gas environment such as, for example, argon or nitrogen.
  • the milling environment of the feedstock is free of purposefully added carbon and nitrogen.
  • the feedstock is milled under a rough vacuum.
  • a “rough vacuum” as used herein indicates an environmental pressure less than the atmospheric pressure in the process volume of the container.
  • the pressure inside the milling container in the processing volume is less than about 10 4 atmosphere.
  • the milling is carried out in an inert gas environment such as, for example, nitrogen. In this case, less amount of nitride powder is needed to intentionally add for milling, since powder will pick up the environmental nitrogen gas during milling which also contribute to stabilize the austenite phase in the matrix.
  • thermo-mechanical consolidation step such as compaction, hot isostatic pressing, extruding, hot forging, cold forging, or combinations of these processes, to form a consolidated component.
  • the powder feedstock may be thermo-mechanically consolidated by first subjecting the powder to hot isostatic pressing, followed by forging or extruding.
  • the forging step used may be hot forging, cold forging or hot forging followed by cold forging.
  • the powder feedstock may be mechanically compacted and then the compacted feedstock may be extruded.
  • This thermo-mechanical consolidation step is performed at a sufficiently high temperature, and for sufficient time, to allow precipitation of the desired complex oxide nanofeatures within the alloy matrix, as described above.
  • the time and temperature selected for this step can be readily designed based on the desired size and density of nanofeatures, and can be controlled to provide dispersions much finer than generally achieved by purely mechanical alloying processes.
  • the consolidating step is performed at a temperature of greater than about 800° C. This consolidation may occur in an inert environment or a rough vacuum to avoid incorporation of undue amounts of oxygen into the alloy.
  • the consolidated component is annealed at a temperature that is above the solvus temperatures of chi phase and sigma phase present in the alloy, and is held at the annealing temperature for sufficient time to dissolve these phases.
  • the solvus temperatures for these phases depend in part on the relative amounts of the elements present and can be readily determined in any particular instance using techniques familiar to those of ordinary skill in the art. For instance, published phase diagrams of the chromium-iron-molybdenum system show that the solvus temperature for sigma and/or chi phases can range from about 600° C., for alloys with low amounts of chromium and molybdenum, to above 1100° C. for more highly alloyed material.
  • the annealed component is then cooled to form a processed component having the characteristics noted previously for article 100 .
  • the cooling is performed at a rate rapid enough to limit or prevent formation of chi and sigma phases at least at a surface, such as surface 110 , of the processed component; low cooling rates afford more time for the alloy to approach thermodynamic equilibrium, and thus may result in precipitation of chi or sigma phases during cooling, thereby reducing the corrosion resistance of the material.
  • a cooling rate is deemed to be sufficiently rapid if it results in a concentration of chi phase or sigma phase at surface 110 less than about 5 volume percent.
  • a cooling rate of the component that sufficiently inhibits formation of chi and sigma phase may be readily determined for any particular instance using techniques familiar to those of ordinary skill in the art.
  • the annealed component is water quenched from the annealing temperature.
  • the zone of reduced chi and sigma phase precipitation relative to equilibrium that results from the annealing and quenching steps may extend further into the alloy than just surface 110 , and may include any volume fraction of the alloy, up to and including substantially the entire alloy, depending in part on the method employed to achieve the quenching, the size of the alloy section being quenched, and other factors.
  • the processed component may itself be used as article 100 , or the processed component may be used in further fabrication and/or assembly techniques to form article 100 , oriented such that surface 110 is the surface noted above having the reduced concentration of sigma and/or chi phases due at least in part to the rapid cooling step.
  • the iron-bearing alloy powder that is used as the feedstock for the formation of the article surface herein may be prepared using different routes. For example, an iron-bearing alloy may be melted, such as by vacuum induction melting, and then made into powder, such as by atomization in inert gas.
  • pre-alloyed steel (Fe—Cr) powders doped with elemental metal powders (Cr, Mo, Ni, W, Ti) and iron nitride powder as necessary to match the nominal composition of the desired duplex NFA were taken as starting materials and mixed with Y 2 O 3 powder.
  • Nominal composition of the desired duplex NFA in this example was Fe-25Cr-3.5Mo-7Ni-0.25N-0.75W-0.4Ti-0.25Y 2 O 3 .
  • pre-alloyed powders containing a mixture of 3 or more elements selected from Fe, Cr, Mo, Ni, W, and Ti may also be used as starting powders.
  • Powders were mixed with 420 stainless steel balls ( ⁇ 4.5 mm in diameter) with a 10:1 ratio and milled in a high energy attrition mill for about 20 hours in an argon environment. During milling, the Y 2 O 3 particles were dissolved and homogeneously redistributed in the metal matrix.
  • the as-milled powders were in flake shapes with a size of about 50 ⁇ m to about 150 ⁇ m.
  • the powders may be milled in vacuum. Alternatively, powders may be milled in nitrogen environment with reduced amount of nitride powder to achieve the same composition.
  • the powders were packed in a stainless steel can, evacuated, and then hot isostatic pressed (HIP) at about 920° C. temperature and about 170 ⁇ 200 MPa pressure for about 4 hours.
  • HIP hot isostatic pressed
  • the HIP process consolidates the powders into bulk materials and recrystallizes the microstructure to yield low-strain equiaxial grains.
  • Complex oxide nanofeatures here, ultrafine oxides including Y, Ti, and O (less than about 10 nm), form homogeneously inside grains and on grain boundaries during the heating stage of the HIP process.
  • the NFA produced had a duplex grain structure, having a ferrite phase rich in chromium, and an austenite phase rich in nickel. Nanofeatures as complex Y—Ti oxides were observed to be present in both ferrite and austenite phases. It was found that molybdenum-enriched chi phase or sigma phase existed in the as-forged duplex NFA, as their solvus temperatures were higher than 920° C. As expected, the amount of chi or sigma phase was found to vary with molybdenum and chromium level in different duplex NFA compositions.
  • FIG. 2 summarizes room-temperature tensile properties as-forged NFA (without a subsequent heat treatment) compared with 2 widely used baseline steels—F6NM and super duplex 2507, and Ni-based alloy 718.
  • the as-forged duplex NFA showed approximately 2.5 ⁇ higher yield strength and ultimate tensile strength than baseline steels and slightly higher strength than Ni-based alloy 718.
  • Ductility of the duplex NFA in the as-forged state was observed to be lower than steels.

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