WO2017213781A1 - Aciers cryogéniques à haute résistance et haute teneur en manganèse et leurs procédés de fabrication - Google Patents

Aciers cryogéniques à haute résistance et haute teneur en manganèse et leurs procédés de fabrication Download PDF

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WO2017213781A1
WO2017213781A1 PCT/US2017/031644 US2017031644W WO2017213781A1 WO 2017213781 A1 WO2017213781 A1 WO 2017213781A1 US 2017031644 W US2017031644 W US 2017031644W WO 2017213781 A1 WO2017213781 A1 WO 2017213781A1
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composition
temperature
weight
present disclosure
austenite
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Hyun-Woo Jin
Cary N. Marzinsky
Douglas P. Fairchild
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Exxonmobil Research And Engineering Company
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/38Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D6/00Heat treatment of ferrous alloys
    • C21D6/002Heat treatment of ferrous alloys containing Cr
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D6/00Heat treatment of ferrous alloys
    • C21D6/005Heat treatment of ferrous alloys containing Mn
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/005Modifying the physical properties by deformation combined with, or followed by, heat treatment of ferrous alloys
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226Hot rolling
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0263Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D9/00Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/08Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/04Ferrous alloys, e.g. steel alloys containing manganese
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/06Ferrous alloys, e.g. steel alloys containing aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/20Ferrous alloys, e.g. steel alloys containing chromium with copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D10/00Modifying the physical properties by methods other than heat treatment or deformation
    • C21D10/005Modifying the physical properties by methods other than heat treatment or deformation by laser shock processing
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D2201/00Treatment for obtaining particular effects
    • C21D2201/02Superplasticity
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D2211/00Microstructure comprising significant phases
    • C21D2211/001Austenite
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D2211/00Microstructure comprising significant phases
    • C21D2211/004Dispersions; Precipitations
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D7/00Modifying the physical properties of iron or steel by deformation
    • C21D7/02Modifying the physical properties of iron or steel by deformation by cold working
    • C21D7/04Modifying the physical properties of iron or steel by deformation by cold working of the surface
    • C21D7/06Modifying the physical properties of iron or steel by deformation by cold working of the surface by shot-peening or the like
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D7/00Modifying the physical properties of iron or steel by deformation
    • C21D7/02Modifying the physical properties of iron or steel by deformation by cold working
    • C21D7/04Modifying the physical properties of iron or steel by deformation by cold working of the surface
    • C21D7/08Modifying the physical properties of iron or steel by deformation by cold working of the surface by burnishing or the like

Definitions

  • the present disclosure relates to cost-effective high manganese steels tailored to achieve high yield strength, cryogenic toughness, and low thermal stress. More specifically, the present disclosure pertains to ferrous steel alloyed with a high amount (>8wt.%) of manganese providing high yield strength, cryogenic toughness, and low thermal stress and manufacturing the same.
  • the strength, toughness, elastic modulus, thermal expansion coefficient and thermal conductivity of these steels can be optimized through the control of microstructure and chemistry.
  • the application of the present disclosure includes, but is not limited to liquefied natural gas (LNG) storage, piping, and transfer by pipeline.
  • LNG liquefied natural gas
  • Cryogenic structures such as liquefied natural gas (LNG) container vessels demand steels with specific low temperature properties.
  • the steels need to remain ductile and crack resistant and must retain a high level of safety even at cryogenic temperatures ( ⁇ -50°C). These steels must also possess high strength in order to allow reduction of tank wail thickness which permits low cost construction.
  • Conventional carbon steels lose much of their toughness and become brittle at cryogenic temperatures.
  • Steels commonly used for structural applications at cryogenic temperatures include alloy steels such as Fe-9wt.%Ni steel, austenitic stainless steels (e.g., 304 SS with Fe-18 wt.% Cr-8 wt.% Ni), invar alloys (Fe-36 wt% Ni), and aluminum alloys.
  • Aluminum alloys are used in various cryogenic applications due to their high specific strength and ductility. However, most aluminum alloys have lower strength compared with the strength of alloyed steel and are relatively challenging to weld. Austenitic stainless steels (e.g., 304 SS) and Invar alloys are relatively low strength and high cost. Nickel-alloyed high-strength steels (5% Ni and 9% Ni) provide a combination of high cryogenic strength and toughness and, hence, 9% Ni steels are often preferred for the most demanding low temperature applications. However, because of high Ni content, these alloys are expensive.
  • Ferrous steels with high manganese (Mn) alloying can be a lower-cost alternative to these cryogenic materials.
  • the essential benefits of the inventive steels of the present disclosure are the lower cost by replacing Ni with Mn, and higher strength due to higher carbon (C), and/or nitrogen (N) contents than the steels in the art.
  • Liquefied natural gas is usually transported by specially equipped ships and stored in LNG-terminals.
  • Conventional LNG carrier ships are of two basic types.
  • the first type (Moss type) uses heavy walled self-supporting spherical tanks made of aluminum to contain the LNG.
  • the second type (membrane type) uses a thin membrane of Invar alloy or corrugated austenitic stainless steel supported by the ship's hull (with plywood and insulation in between) to contain the LNG.
  • free standing LNG storage tanks are typically made out of 9%Ni steel.
  • cryogenic steels are joined by fusion welding technology for liquid-tightness.
  • GTAW Gas Tungsten Arc Welding
  • GMAW Gas Metal Arc Welding
  • SMAW shieldded Metal Arc Welding
  • SAW Submerged Arc Welding
  • the inventive concept of using high Mn steels (which can be welded with matching or overmatching weld consuambles) for cryogenic pipeline design allows for numerous advantages including reduced materials and construction cost, increased pipeline security, reduced environmental impact, capital savings associated with jetty constaiction, and reduced operating costs,
  • the present disclosure provides for a method for fabricating a ferrous based component comprising; a) providing a composition having from about 5 to about 40 weight % manganese, from about 0.01 to about 1.2 weight % carbon, and the balance iron; b) heating the composition to a temperature above the austenite recrystallization stop temperature of the composition or to a temperature to homogenize the composition; c) cooling the composition to a rolling start temperature, d) deforming the composition while the composition is at a temperature below the austenite reciystallization stop temperature of the composition; and e) quenching the composition.
  • the present disclosure also provides for a ferrous based component fabricated according to the steps comprising: a) providing a composition having from about 5 to about 40 weight % manganese, from about 0,01 to about 1.2 weight % carbon, and the balance iron; b) heating the composition to a temperature above the austenite reciystallization stop temperature of the composition, c) cooling the composition to a temperature below the austenite recrystallization stop temperature of the composition; d) deforming the composition while the composition is at a temperature below the austenite recrystallization stop temperature of the composition; and e) quenching the composition.
  • Figure J is a diagram of a LNG loading line with expansion loop, as required using
  • Figure 2 is an exemplary diagram of the phase stability and deformation mechanism of high Mn steels as a function of alloy chemistry and temperature; -
  • Figure 3 displays the predicted influence of alloying elements on the SFE values of the FeMnl 3C0,6 reference and the deformation mechanism
  • Figure 4 depicts the effect of carbide precipitates on mechanical properties and deformation mechanism (schematic, not in scale);
  • Figure 5 is a schematic drawing of an exemplary steel fabrication method of the present disclosure
  • Figure 6 depicts a schematic of an exemplary fabrication method for producing ultrafme grained high Mn steels according to the present disclosure.
  • Corrosion resistant alloys can mean, but is in no way limited to, a specially formulated material used for completion components likely to present corrosion problems, Corrosion-resistant alloys may be formulated for a wide range of aggressive conditions.
  • Ductility can mean, but is in no way limited to, a measure of a material's ability to undergo appreciable plastic deformation before fracture; it may be expressed as percent elongation (% EL) or percent area reduction (% AR).
  • Erosion resistance can mean, but is in no way limited to, a material's inherent resistance to erosion when exposed to moving solid particulates striking the surface of the material.
  • Toughness can mean, but is in no way limited to, resistance to fracture initiation.
  • Fatigue can mean, but is in no way limited to, resistance to fracture under cyclic loading.
  • Yield Strength can mean, but is in no way limited to, the ability to bear load without deformation.
  • Cooling rate can mean, but is in no way limited to, the rate of cooling at the center, or substantially at the center, of the plate thickness
  • Austenite can mean, but is in no way limited to, a solid solution of one or more elements in face-centered cubic crystaliographic structure of iron; the solute can be, but not limited to, carbon, nitrogen, manganese, and nickel.
  • Martensite can mean, but is in no way limited to, a generic term for microstructures formed by diffusioniess phase transformation in which the parent (typically austenite) and product phases have a specific orientation relationship.
  • s(epsilon)-martensite can mean, but is in no way limited to, a specific form of martensite having hexagonal close packed crystal structure which forms upon cooling or straining of austenite phase, ⁇ -martensite typically forms on close packed (1 1 1) planes of austenite phase and is similar to deformation twins or stacking fault clusters in morphology.
  • a/ (alpha prime )-martensite can mean, but is in no way limited to, a specific form of martensite having body centered cubic or body centered tetragonal crystal structure which forms upon cooling or straining of austenite phase; ⁇ ' -martensite typically forms as platelets.
  • Ms temperature can mean, but is in no way limited to, the temperature at which transformation of austenite to martensite starts during cooling
  • Mf temperature can mean, but is in no way limited to, the temperature at which transformation of austenite to martensite finishes during cooling.
  • Md temperature can mean, but is in no way limited to, the highest temperature at which a designated amount of martensite forms under defined deformation conditions. Md temperature is typically used to characterize the austenite phase stability upon deformation.
  • Carbide can mean, but is in no way limited to, a compound of iron/metal and carbon.
  • Cementite can mean, but is in no way limited to, a compound of iron and carbon having approximate chemical formula of Fe 3 C with orthorhombic crystal structure.
  • Pearl ite can mean, but is in no way limited to, typically a lamellar mixture of two- phases, made up of alternate layers of ferrite and cementite (Fe 3 C).
  • Grain can mean, but is in no way limited to, an individual crystal in a polycrystalline material.
  • Grain boundary can mean, but is in no way limited to, a narrow zone in a metal corresponding to the transition from one cry stall ographic orientation to another, thus separating one grain from another.
  • Quenching can mean, but is in no way limited to, accelerated cooling by any means whereby a fluid selected for its tendency to increase the cooling rate of the steel is utilized, as opposed to air cooling,
  • Accelerated cooling start temperature can mean, but is in no way limited to, the temperature reached at the surface of plate, when quenching is initiated.
  • Accelerated cooling finish temperature can mean, but is in no way limited to, the highest, or substantially the highest, temperature reached at the surface of the plate, after quenching is stopped, because of heat transmitted from the mid-thickness of the plate.
  • Slab a piece of steel having any dimensions.
  • Recrystallization the formation of a new, strain-free grain staicture grains from cold- worked metal accomplish by heating through a critical temperature.
  • Tnr temperature the temperature below which austenite does not recrystallize.
  • the present disclosure provides advantageous steel compositions. More particularly, the present disclosure provides improved high manganese (Mn) steel having high yield strength/cryogenic toughness/low thermal stress, and related methods for fabricating steel having enhanced yield strength/cryogenic toughness/low thermal stress.
  • Mn manganese
  • the advantageous steel compositions/components of the present disclosure improve one or more of the following properties: yield strength, cryogenic toughness, thermal stress, elastic modulus, thermal expansion coefficient and/or thermal conductivity.
  • the present disclosure provides for cost-effective high manganese steels having improved performance during cryogenic applications (e.g., yield strength, cryogenic toughness, thermal stress, elastic modulus, thermal expansion coefficient and/or thermal conductivity). More specifically, the present disclosure provides ferrous steel alloyed with a high amount (e.g., greater than or equal to about 5 weight %) of manganese, and where the fabricated steel exhibits increased/improved yield strength/cryogenic toughness/low thermal stress (e.g., improved yield strength, cryogenic toughness, thermal stress, elastic modulus, thermal expansion coefficient and/or thermal conductivity). The present disclosure also provides methods for fabricating such improved steel. In exemplar ⁇ ' embodiments, the high manganese steels of the present disclosure have advantages/potential in applications where strength/toughness is desired/required at cryogenic temperatures.
  • the disclosure provides methods for improving the yield strength, cryogenic toughness, and thermal stress of the steels through the control of microstructure and/or chemistr'.
  • the methods include steps to promote phase transformations (e.g., to alpha prime martensite or epsilon martensite phases), twinning during deformation, and/or introducing hard erosion resistant second phase particles to the compositions,
  • Some exemplary uses/applications of the steel compositions of present disclosure include, without limitation, are use in piping systems, material conveying systems, fluids/solids transport systems, in mining operations, and/or as material for liquefied natural gas (LNG) storage systems, and piping for LNG onloading/offioading piping systems.
  • LNG liquefied natural gas
  • the liquefied natural gas (LNG) storage systems, and piping for LNG onloading/offioading piping systems are waffle-free, wrinkle-free, and/or free of expansion loop piping.
  • the use of the steels of the present disclosure can improve the economics of LNG storage and/or transport. Exemplary Methods for Fabrication
  • the present disclosure provides for a method for fabricating a ferrous based component including: a) providing a composition having from about 5 to about 40 weight % manganese, preferably from about 9 to about 25 weight % manganese, even more preferably from about 12 to about 20 weight % manganese, and from about 0.01 to about 1.2 weight % carbon, preferably from about 0.3% to about 1 .2 weight % carbon, even more preferably from about 0.3% to about 0.7 weight % carbon, and the balance iron, b) heating the composition to a temperature above the austenite recrystallization stop temperature of the composition (e.g., to a temperature to homogenize the composition); c) cooling to a rolling start temperature (RST) d) deforming or hot rolling the composition while the composition is at a temperature above the austenite recrystallization stop temperature of the composition; and e) quenching or accelerated cooling the composition.
  • a temperature above the austenite recrystallization stop temperature of the composition e.g., to
  • the present disclosure provides for a method for fabricating a ferrous based component including: a) providing a composition having from about 5 to about 40 weight % manganese, preferably from about 9 to about 25 weight % manganese, even more preferably from about 12 to about 20 weight % manganese, and from about 0.0 i to about 1.2 weight % carbon, preferably from about 0.3% to about 1 .2 weight % carbon, even more preferably from about 0.3% to about 0.7 weight % carbon, and the balance iron, b) heating the composition to a temperature above the austenite recrystallization stop temperature of the composition (e.g., to a temperature to homogenize the composition); c) deforming the composition while the composition is at a temperature below the austenite recrystallization stop temperature of the composition; and d) quenching or accelerated cooling the composition.
  • the temperature recited in step c) is in the range of 700-1100°C, preferably about 800 ⁇ 1000°C, and more preferably
  • the present disclosure provides for a method for fabricating a ferrous based component wherein after step d), the matrix of the composition is predominantly or substantially in the austenitic phase.
  • the volume percent of austenite in the steel composition is from about 50 volume% to about 100 volume%, more preferably from about 80 volume% to about 99 volume%, even more preferably from about 90 volume% to about 98 volume%.
  • the steel composition is preferably processed into predominantly or substantially austenitic plates using a hot rolling process.
  • a steel billet/slab from the compositions described is first formed, such as, for example, through a continuous casting process.
  • the billet/slab can then be re-heated to a temperature ("reheat temperature") within the range of about 1,000°C to about 1 ,300°C, more preferably within the range of about 1050°C to 1250°C, even more preferably within the range of about 1 100°C to 1200°C.
  • the reheat temperature is sufficient to: (i) substantially homogenize the steel slab/composition, (ii) dissolve substantially all the carbide and/or carbonitrides, when present, in the steel slab/composition, and (iii) establish fine initial austenite grains in the steel slab/composition, [0057]
  • the re-heated slab/composition can then be hot rolled in one or more passes.
  • the rolling or hot deformation can be initiated at a "rolling start temperature".
  • the rolling start temperature is above 1100°C, preferably above 1080°C, even more preferably above 1050°C.
  • the final rolling for plate thickness reduction can be completed at a "rolling finish temperature".
  • the rolling finish temperature is above about 700°C, preferably above about 800°C, more preferably about 850°C.
  • the hot rolled plate can be cooled (e.g.. in air) to a first cooling temperature or accelerated cooling start temperature ("AC ST"), at which an accelerated cooling starts to cool the plates at a rate of at least about 10°C per second to a second cooling temperature or accelerated cooling finish temperature (“ACFT").
  • AC ST accelerated cooling start temperature
  • the steel plate/composition can be cooled to room temperature (e.g., ambient temperature) in ambient air.
  • room temperature e.g., ambient temperature
  • the steel plate/composition is allowed to cool on its own to room temperature.
  • the ACST is about 750°C or more, about 800°C or more, about 850°C or more, or about 900°C or more. In one or more embodiments, the ACST can range from about 700°C to about 1000°C. In one or more embodiments, the ACST can range from about 750°C to about 950°C. Preferably, the ACST ranges from a low of about 650°C, 700°C, or 750°C to a high of about 900°C, 950°C, or 1000°C.
  • the ACST can be about 750°C, about 800°C, about 850°C, about 890°C, about 900°C, about 930°C, about 950°C, about 960°C, about 970°C, about 980°C, or about 990°C.
  • the ACFT can range from about 0°C to about 500°C.
  • the ACFT ranges from a low of about 0°C, 10°C, or 20°C to a high of about 150°C, 200°C, or 300°C.
  • the rapid cooling e.g., more than about 10°C/sec cooling rate
  • ACFT low accelerated cooling finish temperature
  • ACFT high accelerated cooling start temperature
  • the carbon and/or nitrogen atoms from diffusing from the austenite phase of the steel composition to the grain boundary or second phase.
  • the high accelerated cooling start temperature (ACST) retards at least a portion of the carbon and/or nitrogen atoms from forming precipitates such as, for example, carbides, carbonitrides, and/or nitrides during subsequent cooling to the ACFT.
  • the amount of precipitates at the grain boundaries is reduced. Therefore, the steel's fracture toughness and/or resistance to cracking and/or strength at cryogenic temperatures are enhanced.
  • the plate can be formed into pipes or the like (e.g., linepipe). Any suitable method for forming pipe can be used.
  • the precursor steel plate is fabricated into linepipe by a conventional UOE process or JCOE process which is known in the art.
  • the present disclosure also provides for a method for fabricating a ferrous based component including: a) providing a composition having from about 5 to about 40 weight % manganese, from about 0.01 to about 1.2 weight % carbon, and the balance iron; b) heating the composition to a temperature above the austenite recrystailization stop temperature of the composition; c) cooling the composition to a temperature below the austenite recrystailization stop temperature of the composition; d) deforming the composition while the composition is at a temperature below the austenite recrystallization stop temperature of the composition; and e) quenching the composition.
  • the present disclosure also provides for a method for fabricating a ferrous based component wherein after step e), the carbide precipitate fraction volume of the composition is about 3 volume % or less of the composition, preferably about 1.2 volume % or less of the composition, and even more preferably about 0,7 volume % or less of the composition.
  • the present disclosure also provides for a method for fabricating a ferrous based component wherein after step e), the composition has a microstructure having a refined grain size of about 100 ⁇ or less, preferably about ( um or less, even more preferably about 30 ⁇ or less.
  • the present disclosure also provides for a method for fabricating a ferrous based component wherein the microstructure having a refined grain size of about 100 ⁇ or less includes a surface layer of the composition.
  • the present disclosure also provides for a method for fabricating a ferrous based component wherein the thickness of the surface layer is from about lOnm to about SOOOnm.
  • the present disclosure also provides for a method for fabricating a ferrous based component wherein the surface layer is formed prior to or during the use of the composition.
  • the present disclosure provides for a method for fabricating a ferrous based component wherein the surface layer is formed via a surface deformation technique selected from the group consisting of shot peening, laser shock peening, surface burnishing and combinations thereof
  • the present disclosure provides for a method for fabricating a ferrous based component further including after step e) a surface deformation step selected from the group consisting of shot peening, laser shock peening, surface burnishing and combinations thereof.
  • the present disclosure provides for a method for fabricating a ferrous based component wherein prior to step e), the composition is slowly cooled or isothermally held.
  • the present disclosure provides for a method for fabricating a ferrous based component wherein step e) includes rapidly quenching the composition.
  • the present disclosure provides for a method for fabricating a ferrous based component wherein step d) includes deforming the composition while the composition is at a temperature below the austenite recrystallization temperature and above the martensi te transformation start temperature.
  • the present disclosure provides for a method for fabricating a ferrous based component wherein step d) includes deforming the composition to induce martensi te formation of the composition.
  • step d) includes deforming the composition to induce martensi te formation of the composition.
  • step d) includes deforming the composition to induce martensi te formation of the composition.
  • step d) includes deforming the composition to induce martensi te formation of the composition.
  • the present disclosure provides for a method for fabricating a ferrous based component wherein the composition is deformed at a temperature of from about 18° C to about 24° C to induce martensi te formation of the composition.
  • the present disclosure provides for a method for fabricating a ferrous based component further including, after step d), heating the composition to a temperature above the austenite recrystallization stop temperature.
  • the present disclosure provides for a method for fabricating a ferrous based component wherein heating the composition to a temperature above the austenite recrystallization stop temperature after step d) reverses deformation-induced martensite of the composition into ul trail ne grained austenite.
  • the present disclosure provides for a method for fabricating a ferrous based component wherein the martensite start temperature of the ultrafine grained austenite is below about 24° C.
  • the present disclosure provides for a method for fabricating a ferrous based component further including, after step e), heating the composition to a temperature above the austenite recrystallization stop temperature, and then quenching the composition.
  • the present disclosure provides for a method for fabricating a ferrous based component further including, prior to step c), deforming the composition while the composition is at a temperature above the austenite recrystallization stop temperature.
  • the present disclosure provides for a method for fabricating a ferrous based component wherein the composition is deformed at a temperature of from about 700° C to about 1000° C.
  • step b) includes heating the composition to at least about 1000° C.
  • the present disclosure provides for a method for fabricating a ferrous based component wherein step c) includes cooling the composition at a rate of from about 2° C per second to about 60° C per second.
  • the present disclosure provides for a method for fabricating a ferrous based component wherein the composition further includes one or more alloying elements selected from the group consisting of chromium, aluminum, silicon, nickel, cobalt, molybdenum, niobium, copper, titanium, vanadium, nitrogen, boron, zirconium, hafnium and combinations thereof.
  • the present disclosure provides for a method for fabricating a ferrous based component wherein the chromium ranges from 0 to 30 weight % of the total composition, more preferably from 0.5 to 20 weight % of the total composition, even more preferably from 2 to 5 weight % of the total composition; wherein each of the nickel or cobalt ranges from 0 to 20 weight % of the total composition, more preferably from 0.5 to 20 weight % of the total composition, even more preferably from 1 to 5 weight % of the total composition; wherein the aluminum ranges from 0 to 15 weight % of the total composition, more preferably from 0.5 to 10 weight % of the total composition, even more preferably from 1 to 5 weight % of the total composition; wherein each of the molybdenum, niobium, copper, titanium or vanadium ranges from 0 to 10 weight % of the total composition, more preferably from 0.02 to 5 weight % of the total composition, even more preferably from 0.02 to 2 weight % of the total composition
  • the present disclosure provides for a method for fabricating a ferrous based component wherein the composition includes from about 8 to about 20 weight % manganese, from about 0.30 to about 0.7 weight % carbon, from about 0.5 to about 5 weight % chromium, from about 0.0 to about 2.0 weight % copper, from about 0.01 to about J weight % silicon, and the balance iron.
  • step d) includes transformation induced plasticity or twin-induced plasticity.
  • the present disclosure also provides for a ferrous based component including a composition having from about 5 to about 40 weight % manganese, from about 0.01 to about 1 .2 weight % carbon, and the balance iron; and wherein the carbide precipitate fraction volume of the composition is about 2 volume % or less of the composition.
  • the present disclosure also provides for a ferrous based component including a composition having from about 5 to about 40 weight % manganese, from about 0.01 to about 1.2 weight % carbon, and the balance iron; and wherein the composition has a microstructure having a refined grain size of about 30 ⁇ or less.
  • the present disclosure also provides for a ferrous based component fabricated according to the steps comprising: a) providing a composition having from about 5 to about 40 weight % manganese, from about 0.01 to about 1.2 weight % carbon, and the balance iron; b) heating the composition to a temperature above the austenite recrystallization stop temperature of the composition, c) cooling the composition to a temperature below the austenite recrystallization stop temperature of the composition; d) deforming the composition while the composition is at a temperature below the austenite recrystallization stop temperature of the composition; and e) quenching the composition.
  • the present disclosure provides advantageous steel compositions (e.g., having enhanced strength/performance at cryogenic temperatures). More particularly, the present disclosure provides improved high manganese (Mn) steel having high yield strength/cryogenic toughness/low thermal stress, and methods for fabricating high manganese steel compositions having high yield strength/cryogenic toughness/low thermal stress.
  • the advantageous steel compositions/components of the present disclosure improve one or more of the following properties: strength, toughness, elastic modulus, thermal expansion coefficient and/or thermal conductivity.
  • the low elastic modulus of Al alloys maintains the thermal stress at a fairly low level but still above the yield strength of the alloy.
  • the high elastic modulus and thermal expansion coefficient of the 304 austenitic stainless steel and commercial ciyogenic high Mn steel result in high thermal stress well above the yield strength of the materials. While the thermal stress of 9%Ni and the inventive high Mn steels (i.e., high Mn steels of the present disclosure) are comparable, the high strength of the inventive high Mn austenitic steels (i.e., high Mn steels of the present disclosure) makes it more capable as a material for LNG containment system and piping.
  • the high Mn steels can be welded with strength matching welding consumables, a distinguished advantage over 9%Ni steel design which are derated due to the undermatched welds.
  • inventive high Mn austenitic steels of the present disclosure provide numerous advantages over the steels in the art.
  • the disclosure provides methods for improving the yield strength/cryogenic toughness/thermal stress of the steels through the control of microstructure and/or chemistry.
  • the yield strength/cryogenic toughness/thermal stress of the steel compositions of the present disclosure can be improved/increased through the control of microstructure and/or chemistry.
  • Some such possible routes include promoting phase transformations (e.g., to martensite/epsilon phases), twinning during deformation, and/or introducing hard erosion resistant second phase particles to the compositions,
  • the present disclosure provides high manganese steels tailored to resist wear and/or deformation (e.g., having improved wear/deformation resistance properties) at cryogenic temperatures.
  • the high manganese steels of the present disclosure have advantages/potential in applications where wear and/or deformation resistances at ciyogenic temperatures are desired/required (e.g., LNG production, transportation and petrochemical applications).
  • the present disclosure provides high manganese steels tailored to resist wear and/or deformation (e.g., having improved wear/deformation resistance properties) when used in applications that require wear and/or deformation resistance during large temperature variations (e.g., from about -170°C to about room temperature), such as the temperature range experienced by a LNG storage tank and/or LNG piping system when in use (e.g., about -170°C) compared to when not in use (e.g., room temperature).
  • large temperature variations e.g., from about -170°C to about room temperature
  • any of the steel compositions as described or embraced by the present disclosure may be advantageously utilized in many systems/applications (e.g., piping systems, material conveying systems, fluids/solids transport systems, in mining operations, and/or as material for liquefied natural gas (LNG) storage systems, and piping for LNG onioading/offloading piping systems), particularly where wear and/or deformation resistances are important/desired at ciyogenic temperatures.
  • the systems/methods of the present disclosure provide for low-cost and high strength steels (e.g., to be utilized in various cryogenic LNG-related applications).
  • any of the piping systems, material conveying systems, fluids/solids transport systems, in mining operations, and/or as material for liquefied natural gas (LNG) storage systems, and/or piping for LNG onioading/offloading piping systems presented herein may comprise waffle-free or wrinkle-free LNG storage systems and expansion-loop-free piping for LNG onioading/offloading piping systems.
  • LNG liquefied natural gas
  • the high Mn steels from any of the embodiments presented herein exhibit a low coefficient of thermal expansion (CTE), low elastic modulus, and/or low bulk modulus.
  • Thermal stress due to thermal expansion and contraction of materials from room temperature (25°C) to service temperature ( ⁇ 163°C) i.e., liquefied natural gas (LNG) storage and/or LNG onioading/offloading
  • LNG liquefied natural gas
  • the temperature range from room temperature to service temperature.
  • the inventive steels can eliminate the necessity of wrinkled design or expansion loops in cryogenic structures
  • the inventive high Mn austenitic steel provides high yield strength, ⁇ >-, which i s higher than thermal stress for LNG applications.
  • othermai ⁇ ⁇ 3y o&ermai ⁇ x- a y where x is smaller than 1.
  • x can be 0,9, 0.85, 0.8, 0.75, 0.7, 0.65, 0.6, 0.55, or 0.5.
  • x is smaller than 0.8. More preferably, x is smaller than 0.7, liven more preferably, x is smaller than 0.6.
  • the inventive high Mn austenitic steel provides low CTE, approximately lower than 12 (10 '6 m/m°C), and low elastic modulus (e.g., elastic modulus lower than 210 GPa), whilst maintaining high strength (e.g., strength higher than 590MPa).
  • the inventive high Mn austenitic steel comprises about 0.3% to about 1.2% Carbon, and from about 8% to 30% Manganese.
  • the inventive steel is alloyed with microalloying elements such as Nb, V, Ti, Mo, W and other alloying elements such as Cr, C, and N to enhance yield strength.
  • the inventive steels can be welded with Ni-base weld wire (e.g., 625 Ni alloy) and/or high Mn alloyed weld wire.
  • the inventive high Mn austenitic steels have a predominantly austentic structure stabilized at cryogenic temperature.
  • the typical Md3o temperature the highest temperature at which a designated amount of marten site forms under 30% deformation conditions, of the inventive steels are below service temperature of LNG containment system.
  • the fabrication methods/systems of the present disclosure can include one or more of the following steps: (i) providing a high work hardening rate matrix, through transformation induced plasticity (“TRIP”) and/or twin-induced plasticity (“TWIP”); (ii) providing meta-stability to induce phase transformation during service; (iii) providing optimum hardness of marten site (e.g., to be controlled by dissolved carbon content, to provide required erosion resistance); (iv) the dispersion of second phase particles (e.g., carbides, quasi -crystals, etc.) of varying size ranges within the compositions; (v) utilization of advantageous thermo-mechanical controlled process (“TMCP”) fabrication steps/schemes (e.g., to achieve at least some of the steps above); and/or (vi) exemplary joining methods, such as solid state joining (e.g., Friction Stir Welding).
  • TRIP transformation induced plasticity
  • TWIP twin-induced plasticity
  • the high manganese steels of the present disclosure are relatively inexpensive alloys, and have potential applications where wear and/or deformation at cryogenic temperatures or the like of working components is important.
  • the steel compositions have from about 0.30 to about 0.70 weight % carbon, and from about 11 to about 20 weight % manganese.
  • the steel has a fully austenitic structure obtained by quenching from a temperature above about 1000°C. In this condition, the hardness of the material is relatively low.
  • One particularly advantageous feature of the high manganese steel is the strong work hardening capability. Under impact or other mechanical stress, the surface layer can increase its hardness rapidly by martensitic transformation or twinning, whereas other portions/parts of the steel remain substantially soft and/or ductile. This combination of low cost and high work hardening rate makes these steels advantageously suitable to be applied as wear resistant piping material at cryogenic temperatures or the like.
  • the present disclosure provides for steels that exhibit a combination of high strength and erosion resistance. Also, as the result of their good formability , the high manganese steels as described herein can be used in a variety of settings, including, mining and automotive applications.
  • the present disclosure relates to high manganese steel chemistry and/or microstructures tailored to achieve improved strength, toughness, elastic modulus, thermal expansion coefficient and/or thermal conductivity.
  • surface grain refinement may take place in a surface layer of certain high Mn steels either prior to and/or during service/use (e.g., formed in-situ).
  • the grain refinement at the surface can result in the formation of a layer which possesses the unique combinations of high strength and hardness, high ductility, and/or high toughness.
  • Such fine grained (e.g., about lOOnm layer in height) or uitrafine grained (e.g., about lOnm layer in height) surface layer may be formed either prior to and/or during service/use (e.g., formed in-situ), and can impart the desired strength, toughness, elastic modulus, thermal expansion coefficient and/or thermal conductivity to the steel.
  • such fine grained (e.g., about lOOnm layer) or uitrafine grained (e.g., about lOnm layer) surface layer may be formed prior to use/installation of the exemplary steel by such surface deformation techniques such as, without limitation, shot peening, laser shock peening, and/or surface burnishing.
  • surface deformation techniques such as, without limitation, shot peening, laser shock peening, and/or surface burnishing.
  • Current practice provides that the mechanical loads against the pipes in some piping systems are not strong enough to cause the maximum work hardening of the steel.
  • the present disclosure provides high manganese steel with improved wear resistance, which can provide pipes for piping systems with advantageous wear life expectancies.
  • the present disclosure provides for ferrous based components/compositions containing manganese.
  • the components/compositions include from about 5 to about 40 weight % manganese, from about 0,01 to about 1 .2 weight % carbon, and the balance iron.
  • the components/compositions can also include one or more alloying elements, such as, without limitation, chromium, nickel, cobalt molybdenum, niobium, copper, titanium, vanadium, nitrogen, boron and combinations thereof.
  • Exemplary ferrous based components/compositions containing manganese (and optionally other alloying elements) are described and disclosed in U.S. Patent Pub. No. 2012/0160363, the entire contents of which is hereby incorporated by reference in its entirety.
  • the ferrous based compositions include from about 5 to about 40 weight % manganese, from about 0.01 to about 1.2 weight % carbon, and the balance iron.
  • the manganese level in the compositions may range from about 5 to 40 wt % of the total component/composition.
  • the carbon level in the component/composition may range from 0.01 to 1.2 wt % of the total component/composition.
  • iron constitutes the substantial balance of the component/composition
  • the components/compositions can also include one or more alloying elements, such as, without limitation, chromium, aluminum, nickel, cobalt, molybdenum, niobium, copper, titanium, vanadium, nitrogen, boron, zirconium, hafnium and combinations thereof. Weight percentages are based upon the weight of the total component/composition.
  • Chromium may be included in the component from about 0 to about 30 wt % (more preferably from 0.5 to 20 weight % of the total composition, even more preferably from 2 to 5 weight % of the total composition). Nickel may be included in the component from about 0 to about 20 wt % (more preferably from 0.5 to 20 weight % of the total composition, even more preferably from I to 5 weight % of the total composition). Cobalt may be included in the component from about 0 to about 20 wt % (more preferably from 0.5 to 20 weight % of the total composition, even more preferably from 1 to 5 weight % of the total composition).
  • Aluminum may be included in the component from about 0 to about 15 wt % (more preferably from 0.5 to 10 weight % of the total composition, even more preferably from 1 to 5 weight % of the total composition.
  • Molybdenum may be included in the component from about 0 to about 10 wt % (more preferably from 0.2 to 5 weight % of the total composition, even more preferably from 0.1 to 2 weight % of the total composition).
  • Silicon may be included in the component from about 0 to about 10 wt % (more preferably from 0.1 to 6 weight % of the total composition, even more preferably from 0. 1 to 0,5 weight % of the total composition).
  • Niobium, copper, titanium and/or vanadium can each be included in the component from about 0.02 to about 10 wt % (more preferably from 0.02 to 5 weight % of the total composition, even more preferably from 0.02 to 2 weight % of the total composition).
  • Nitrogen can be included in the component from about 0.01 to about 3.0 wt % (more preferably from 0.01 to 2.0 weight % of the total composition, even more preferably from 0,01 to 1 .0 weight % of the total composition).
  • Boron can be included in the component from about 0 to about 0, 1 wt % (more preferably from 0.001 to 0.1 weight % of the total composition).
  • the ferrous based components/compositions containing manganese may also include another alloying element selected from the group consisting of zirconium, hafnium, and combinations thereof. Each of these other alloying elements may be included in the component/composition in ranges from about 0 to about 6 wt % (e.g., 0,2 to 5 wt%) based on the total weight of the component/composition.
  • high Mn steels of the present disclosure are dependent on the characteristics of strain-induced transformation, which is typically controlled by the chemical composition of the steels and/or the processing temperatures.
  • high Mn steels include a metastable austenite phase with a face centered cubic (fee) structure at ambient temperature (e.g., 18-24°C).
  • the metastable austenite phase can transform into several other phases through strain-induced transformation. More particularly, the austenite phase could transform into microtwins (fee) structure (twin aligned with matrix), ⁇ -martensite (hexagonal lattice), and ot'-martensite (body centered tetragonal lattice), depending on steel chemistry and/or temperature.
  • microtwins fee
  • ⁇ -martensite hexagonal lattice
  • ot'-martensite body centered tetragonal lattice
  • FIG. 2 is an exemplary diagram of the phase stability and deformation mechanism of high Mn steels as a function of alloy chemistry and temperature.
  • the letters (A, B, C, and D) indicate the various methods of transformation during deformation.
  • steel A would deform by slip (similar to other metals and alloys), while steels B-D would transform during deformation.
  • Steel in area B which is mildly metastable, can be produced with intermediate manganese content (e.g., from about 15 to about 25 wt % Mn, and about 0.6 wt % C). These steels form twins during deformation. A large amount of plastic elongation can be achieved by the formation of extensive deformation twins along with dislocation slip, a phenomenon known as T winning-Induced Plasticity (TWIP). Twinning causes a high rate of work hardening as the microstructure is effectively refined, as the twin boundaries act like grain boundaries and strengthen the steel due to the dynamic Hall-Petch effect. TWIP steels combine extremely high tensile strength (e.g., greater than 150 ksi) with extremely high uniform elongation (e.g., greater than 95%), rendering them highly attractive for many applications.
  • intermediate manganese content e.g., from about 15 to about 25 wt % Mn, and about 0.6 wt % C.
  • TWIP T winning-Induced Plasticity
  • the moderately metastable steels (Steel in area C) can transform into ⁇ -martensite (hexagonal lattice) upon straining. Upon mechanical straining, these steels would deform predominantly by the formation of ⁇ -martensite, along with dislocation slip and/or mechanical twinning.
  • the highly metastable steels (Steel in area D) will transform to a strong body-centered cubic phase (referred to as ⁇ '-martensite) upon deformation.
  • This strong phase provides resistance to erosion resulting from the impingement of external, hard particles. Since the impact of the external particles results in the deformation of the near surface regions of the steel, these surface regions will transform during service, thereby providing resistance to erosion. Therefore, these steels have a "self-healing" characteristic in the sense that if the hard surface layer gets damaged, it would reform by the impact of the service.
  • the chemistry of the high Mn steels can be tailored to provide a range of properties (e.g., wear resistance, cryogenic toughness, high form ability, erosion resistance) by controlling their transformation during deformation.
  • properties e.g., wear resistance, cryogenic toughness, high form ability, erosion resistance
  • Alloying elements in high Mn steels determine the stability of the austenite phase and strain-induced transformation pathways.
  • manganese is the main alloying element in high Mn steels, and it is important in stabilizing the austenitic structure both during cooling and deformation.
  • the strain induced phase transformation pathway changes from ⁇ '-martensite to ⁇ -martensite and then to micro-twinning.
  • Carbon is an effective austenite stabilizer and the carbon solubility is high in the austenite phase. Therefore, carbon alloying can be used to stabilize the austenite phase during cooling from the melt and during plastic deformation. Carbon also strengthens the matrix by solid solution hardening. As noted, the carbon in the components/compositions of the present disclosure may range from about 0.01 to about 1.2 wt % of the total component/composition.
  • Aluminum is a ferrite stabilizer and thus destabilizes austenite phase during cooling.
  • the addition of aluminum to high Mn steels stabilizes the austenite phase against strain-induced phase transformation during deformation. Furthermore, it strengthens the austenite by solid solution hardening.
  • the addition of aluminum also enhances the corrosion resistance of the high Mn containing ferrous based components disclosed herein due to its high passivity.
  • the aluminum in the components/compositions of the present disclosure may range from about 0.0 to about 15 wt % of the total component.
  • Silicon is a ferrite stabilizer and sustains the ⁇ '-martensite transformation while promoting ⁇ -martensite formation upon deformation at ambient temperature. Due to solid solution strengthening, addition of Si strengthens the austenite phase by about 50 MPa per 1 wt % addition of Si.
  • the silicon in the components/compositions of the present disclosure may range from about 0.01 to about 10 wt % of the total component.
  • Chromium additions to high Mn steel alloys enhance the formation of ferrite phase during cooling and increase corrosion resistance. Furthermore, the addition of Cr to the Fe ⁇ Mn alloy system reduces the thermal expansion coefficient.
  • the chromium in the components/compositions of the present disclosure may range from about 0.5 to about 30 wt %. of the total component.
  • Ms is a critical temperature below which austenite to a ! -martensite transformation occurs
  • M £S is a critical temperature below which austenite to ⁇ -martensite transformation takes place.
  • Ms(K) A 3 -410-200(C+1.4N)-18Ni-22Mn-7Cr-45Si-56Mo ; and U > .
  • ferrous based components/compositions containing manganese may be utilized in a wide variety of applications/uses/systems (e.g., piping systems, material conveying systems, fluids/solids transport systems, in mining operations, and/or as material for liquefied natural gas (LNG) storage systems, and piping for LNG onloading/offloading piping systems, materials for cryogenic gas (e.g., Liquefied petroleum gas, Liquefied Ethylene gas, supercritical C02) storage and piping, and cold liquid processing vessels and piping including amine scrubber, and high pressure heat exchnagers.
  • applications/uses/systems e.g., piping systems, material conveying systems, fluids/solids transport systems, in mining operations, and/or as material for liquefied natural gas (LNG) storage systems, and piping for LNG onloading/offloading piping systems, materials for cryogenic gas (e.g., Liquefied petroleum gas, Liquefied Ethylene gas, supercritical
  • ferrous based components/compositions containing manganese of the present disclosure ma find numerous non-limiting uses/applications in the oil, gas a d/or petrochemical industry or the like (e.g., cryogenic applications, corrosion resistant applications, erosion resistant applications, natural gas li quef acti on/transportation/ storage type structures/components, oil/gas well completion and production structures/components, subterraneous drilling equipment, oil/gas refinery and chemical plant structures/components, coal mining structures/equipment, coal gasification structures/equipment, etc.).
  • cryogenic applications e.g., corrosion resistant applications, erosion resistant applications, natural gas li quef acti on/transportation/ storage type structures/components, oil/gas well completion and production structures/components, subterraneous drilling equipment, oil/gas refinery and chemical plant structures/components, coal mining structures/equipment, coal gasification structures/equipment, etc.
  • the relatively low alloying content (e.g., less than about 20 wt % Mn, and about 0.6 wt % C) produces the highly metastable austenite phase.
  • the highly metastable austenite phase often transforms into hard ⁇ '-martensite upon straining, which typically is an irreversible transformation.
  • a surface layer of the highly metastable austenite phase can transform to ⁇ '-martensite phase.
  • This friction-induced phase transformation leads to the formation of a thin, hard surface layer composed of martensite over an interior that consists of tough, untransformed austenite. This unique combination renders high Mn steels suitable for wear/erosion and impact resistant applications.
  • the joining of the high Mn steels of the present disclosure can be performed using conventional (e.g., fusion, resistance welding, etc.) and emerging joining methods (e.g., laser, electron beam, friction stir welding, etc.), as described and disclosed in U.S. Patent Pub. No. 2012/0160363 noted above.
  • preferred joining methods include solid state welding methods (e.g., resistance welding, friction stir welding), where such welding methods do not require the use of a weld metal, although the present disclosure is not limited thereto.
  • bulk modification is utilized to promote phase transformation (TRIP) and twinning (TWIP) during deformation.
  • TRIP phase transformation
  • TWIP twinning
  • the dispersed particles strengthen the materials/compositions, but have complex effects. It is noted that the dispersed particles may influence the: (i) chemistry of the composition matrix itself, (ii) grain size, and (iii) overall material/composition toughness. In general, the proper balance of these effects is important to exemplary embodiments of the present disclosure.
  • High manganese steel generally has a rapid work hardening rate because of the TRIP/TWIP effects. Their activations are typically triggered by the value of the stacking fault energy ("SFE") of the alloy. It is noted that the plastic deformation is associated with martensitic transformation at low SFE values (e.g., less than about 12 mJ/m 2 ), and by twinning at intermediate SFE values. At even higher SFE values (e.g., greater than 35mJ/m 2 ), plasticity and strain hardening is typically controlled solely by dislocation sliding. As such, the SFE value is an important parameter in steel design,
  • the SFE is a function of alloy chemistry and temperature.
  • the intrinsic stacking fault can be represented as a s-martensite embryo of two planes in thickness.
  • the SFE includes both volume energy and surface energy contributions. It has been demonstrated that the chemistry and temperature dependence of SFE arises largely from the volume energy difference between ⁇ - martensite and austenite. Moreover, the volume free energy of phases can be obtained from available databases or the like.
  • FIG. 3 shows the predicted SFE values when adding each alloying element to FeMnl3C0.6. Stated another way, FIG. 3 displays the predicted influence of alloying elements on the SFE values of the FeMnl3C0.6 reference and the deformation mechanism.
  • the systems/methods of the present disclosure also include the introduction of second phase particles to further improve the wear resistance of the exemplary steel compositions.
  • the exemplary systems/methods are described primarily with respect to carbide/nitride particles.
  • the systems/methods of the present disclosure may utilize, apply to and/or include other particles/precipitates, such as, without limitation, borides and oxides.
  • the grain size refinement can be an additional benefit from the second phase particles.
  • the size and/or spatial distribution of the particles can be adjusted or optimized based on materials service conditions. For example, for compositions for use in a piping system or the like, the wear damage may be caused by sands having wide particle size distribution. Therefore, a bimodal particle distribution could be considered for the steel composition. It is noted that the fabrication or manufacture of high manganese steel with various type and size second phase particle can be achieved through various exemplary therm o- mechanical controlled processes ("TMCP”), as discussed further below.
  • TMCP therm o- mechanical controlled processes
  • the carbide/nitride precipitation can also locally enhance the TRIP or TWIP effects in the austenitic matrix.
  • the interstitial elements (carbon and nitrogen) concentration in carbide/nitride particles is much higher than the average value of the steel. Due to diffusion gradients at the interface, the interstitial elements could be depleted in precipitates surrounding the matrix, which results in a lower activation energy for TRIP or TWIP.
  • FIG. 4 (schematic, not in scale) displays the overall effect of carbide precipitates on mechanical properties and the corresponding deformation mechanism.
  • the high manganese steel with the exemplary carbide/nitride particles can have a higher yield strength and work hardening capability.
  • the combination of hard particles and a work-hardenable material matrix makes the compositions of the present disclosure suitable to withstand and/or reduce the abrasive wear effects caused by operational use (e.g., by hard particle cutting/shearing or the like).
  • the steel compositions/components of the present disclosure can be fabricated or manufactured by various processing techniques including, but not limited to, various exemplary thermo-mechanicai controlled processing ("TMCP") techniques, steps or methods.
  • TMCP thermo-mechanicai controlled processing
  • some TMCP processes have been utilized to produce low alloy steel, particularly where grain size and microstructure refinement is desired,
  • the particles should be in a substantially dissolved state before the deformation, as undissolved particles will suffer relatively rapid coarsening at the elevated temperatures.
  • the controlled deformation should take place below the recry stall izati on stop temperature so that deformation results in elongated austenite grains filled with intra-granular crystalline defects, which are the preferred sites for nucleation.
  • a slow cooling or isothermal holding is then required to promote the particles precipitation. Finally, a rapid quench is applied to keep a fully austenitic matrix.
  • FIG. 5 illustrates an exemplar ⁇ - fabrication schedule for the production of steel compositions/components according to the present disclosure.
  • FIG. 5 is a schematic drawing of an exemplary steel fabrication method of the present disclosure.
  • Tar is the austenite recrystalhzation stop temperature
  • a s is the austenite start temperature.
  • the TMCP methods have a synergistic effect of micro- alloy additions.
  • the appropriate thermo-mechanicai conditions should be selected in order to produce the desired fine particles.
  • the alloying elements utilized in the methods of the present disclosure can have some effect on either the TMCP, or the bulk property modification, or both.
  • carbon is the one of the most effective alloying elements to control the bulk deformation mechanism, promote carbide precipitation and stabilize the austenite phase during cooling. It is noted that the total carbon content of the compositions could be much larger or higher compared to conventional high manganese steel, but the amount of carbon in solution after TMCP steps should be controlled to a much lower level.
  • manganese is the austenite phase stabilizer. This element can be mainly added to the compositions to maintain a fully austenitic matrix during cooling and TMCP. In general, it has little effect on the deformation mechanism .
  • Chromium is a carbide former. It will promote different types of carbide, such as
  • M7C and M23C6 depending on the alloy level and/or thermal treatment temperature.
  • chromium addition is typically important for corrosion resistance enhancement.
  • Niobium and titanium are effective elements to retard the recrystallization during
  • TMCP by forming strain induced (e.g., Ti, Nb C, N) precipitation on the deformed austenite.
  • strain induced e.g., Ti, Nb C, N
  • titanium addition facilitates the bulk carbon concentration modification according to exemplar ⁇ - embodiments of the present disclosure.
  • Aluminum and silicon are added to tune or adjust the SFE of the high manganese steel of the present disclosure. It is noted that aluminum addition can facilitate quasi -crystalline phase formation, as discussed below.
  • high Mn steels utilizing precipitation hardening of quasi-crystals.
  • high Mn steels can be strengthened by the precipitation of quasi-crystals, and such structures can be achieved by heat treating at elevated temperatures (e.g., up to about 700°C).
  • quasi-crystalline materials have periodic atomic structures (e.g., 5-fold or 10-fold rotational symmetry), but usually do not conform to the 3-D symmetry typical of ordinary crystalline materials. Due to their crystallographic structure, quasi-crystalline materials with tailored chemistry exhibit unique properties, which are attractive for the strengthening of high Mn steels.
  • the quasi-crystalline precipitates can provide higher strengthening effects than that of crystalline precipitates (e.g., carbides), because of the difficulty of dislocations to move through quasi-crystal lattices. Furthermore, quasi-crystals usually will not grow beyond certain sizes unlike crystalline precipitates, thereby alleviating over-aging concerns associated with certain crystalline precipitates.
  • crystalline precipitates e.g., carbides
  • improved steel compositions can be fabricated by exemplary thermo-mechanical controlled processes (TMCP).
  • TMCP thermo-mechanical controlled processes
  • the TMCP of the present disclosure includes heavy plastic deformation at ambient (e.g., 18-24°C) or cryogenic (e.g., -196°C) or intermediate temperature to induce martensite formation, and subsequent annealing at elevated temperatures to reverse deformation-induced martensite into ultrafine grained austenite.
  • An exemplary thermo-mechanical controlled process is schematically shown in FIG. 6.
  • FIG. 6 depicts a schematic of an exemplary fabrication method for producing ultrafine grained high Mn steels according to the present disclosure.
  • Af is the austenite finish temperature (austenite recrystallization stop temperature)
  • a s is the austenite start temperature.
  • the metastabie austenite phase of the steel composition is transformed to a strain-induced martensite phase by heavy plastic deformation at ambient (e.g., 18-24°C) or cryogenic (e.g., -196°C) or intermediate temperatures (FIG. 6).
  • the strain-induced martensite phase may be further heavily deformed to destroy lath or plate structures prior to a reversion treatment (e.g., reversion annealing in FIG. 6).
  • the strain-induced martensite phase may be reverted to the austenite phase at temperatures low enough to suppress the grain coarsening of the reverted austenite phase.
  • the chemistry of the steel compositions of the present disclosure can be tailored so that the martensite start temperature (Ms) of reverted austenite is below room temperature (e.g., 18-24°C).
  • Ms martensite start temperature
  • the present disclosure provides for a method for fabricating a ferrous based component including: a) providing a composition having from about 5 to about 40 weight % manganese, preferably from about 9 to about 25 weight % manganese, even more preferably from about 12 to about 20 weight % manganese, and from about 0.01 to about 1.2 weight % carbon, preferably from about 0.3% to about 1.2 weight % carbon, even more preferably from about 0.3% to about 0.7 weight % carbon, and the balance iron, b) heating the composition to a temperature above the austenite recrystallization stop temperature of the composition (e.g., to a temperature to homogenize the composition), c) deforming the composition while the decomposition is at a temperature below the austenite recrystallization stop temperature of the composition; and d) quenching or accelerated cooling the composition.
  • a temperature above the austenite recrystallization stop temperature of the composition e.g., to a temperature to homogenize the composition
  • deforming the composition while the
  • the present disclosure provides for a method for fabricating a ferrous based component wherein after step d), the matrix of the composition is predominantly or substantially in the austenitic phase.
  • the volume percent of austenite in the steel composition is from about 50 wt% to about 100 wt%, more preferably from about 80 wt% to about 99 wt%.
  • the steel composition is preferably processed into predominantly or substantially austenitic plates using a hot rolling process.
  • a steel billet/slab from the compositions described is first formed, such as, for example, through a continuous casting process.
  • the billet slab can then be re-heated to a temperature ("reheat temperature") within the range of about 1,000°C to about 1,300°C, more preferably within the range of about 1050°C to 1250°C, even more preferably within the range of about I i00°C to 1200°C.
  • the reheat temperature is sufficient to; (i) substantially homogenize the steel slab/composition, (ii) dissolve substantially all the carbide and/or carbonitrides, when present, in the steel slab/composition, and (iii) establish fine initial austenite grains in the steel slab/composition.
  • the re-heated slab/composition can then be hot rolled in one or more passes.
  • the reheated slabs/billets can be cooled to the rolling start temperature.
  • the roiling start temperature is above 1100°C, preferably above 1080°C, even more preferably above 1050°C.
  • the final rolling for plate thickness reduction can be completed at a "finish rolling temperature".
  • the finish rolling temperature is above about 700°C, preferably above about 800°C, more preferably about 850°C.
  • the hot rolled plate can be cooled (e.g., in air) to a first cooling temperature or accelerated cooling start temperature ("ACST"), at which an accelerated cooling starts to cool the plates at a rate of at least about 10°C per second to a second cooling temperature or accelerated cooling finish temperature (“ACFT").
  • AFT accelerated cooling start temperature
  • the steel plate/composition can be cooled to room temperature (e.g., ambient temperature) in ambient air.
  • the steel plate/composition is allowed to cool on its own to room temperature.
  • the ACST is about 750°C or more, about 800°C or more, about 850°C or more, or about 900°C or more. In one or more embodiments, the ACST can range from about 700°C to about 1000°C. In one or more embodiments, the ACST can range from about 750 C 'C to about 950°C. Preferably, the ACST ranges from a low of about 650°C, 700°C, or 750°C to a high of about 900°C, 950°C, or 1000°C.
  • the ACST can be about 750°C, about 800°C, about 850°C, about 890°C, about 900°C, about 930°C, about 950°C, about 960°C, about 970°C, about 980°C, or about 990°C.
  • the ACFT can range from about 0°C to about 500°C.
  • the ACFT ranges from a low of about 0°C, 10°C, or 20°C to a high of about 150°C, 200°C, or 300°C.
  • the rapid cooling e.g., more than about 10°C/sec cooling rate
  • ACFT low accelerated cooling finish temperature
  • AC ST high accelerated cooling start temperature
  • the plate can be formed into pipes or the like (e.g., linepipe). Any suitable method for forming pipe can be used.
  • the precursor steel plate is fabricated into linepipe by a conventional UOE process or JCOE process which is known in the art.
  • the present disclosure will be further described with respect to the following examples; however, the scope of the disclosure is not limited thereby.
  • the following examples illustrate improved systems and methods for fabricating or producing improved steel compositions (e.g., improved high Mn steel compositions having enhanced wear and/or deformation resistance at cryogenic temperatures or the like).
  • the present disclosure illustrates that the advantageous steel compositions/components of the present disclosure improve one or more of the following properties: strength, toughness, elastic modulus, thermal expansion coefficient and/or thermal conductivity.
  • the yield strength/cryogenic toughness/thermal stress of the steels of the present disclosure can be improved/increased through the control of microstructure and/or chemistry.
  • some possible routes include promoting phase transformations (e.g., to martensite or epsilon phases), twinning during deformation, and/or introducing hard erosion resistant second phase particles to the compositions.
  • the present disclosure provides for a ferrous based component fabricated according to the steps comprising; a) providing a composition having from about 5 to about 40 weight % manganese, from about 0.01 to about 1.2 weight % carbon, and the balance iron; b) heating the composition to a temperature above the austenite recry stabilization stop temperature of the composition; c) cooling the composition to a temperature below the austenite recrystallization stop temperature of the composition; d) deforming the composition while the composition is at a temperature below the austenite recrystallization stop temperature of the composition; and e) quenching the composition.
  • steel plates having the chemistry shown in Table 2 are fabricated by vacuum induction melting and hot rolling. Steel plates with 25mm thickness were fabricated by finish rolling at around 850°C followed by accelerated cooling to room temperature.
  • Tables 3 and Table 4 show the mechanical properties of inventive steels at cryogenic temperature and ambient temperature (around 25°C), respectively. All of the steel plates were characterized by minimum yield strength ranging from about 600MPa to 630MPa at ambient temperature in the as-rolled condition without cold deformation.
  • Table 5 shows the average coefficient of thermal expansion (CTE), and mechanical properties of inventive steels.
  • CTE coefficient of thermal expansion
  • the measurement of CTE were made with a LVDT (linear variable differential transducer)-based quartz dilatometer measurement system (ASTM standard E228). The change of specimen length has been recorded as the temperature was cycled between -196°C and 25°C at a maximum rate of 2°C/minute. T-type thermocouples were used for temperature measurement in the dilatometer.
  • the CTE (a) were calculated as follows:
  • Lti and Lti are the measured displacements of the specimens at time u, and a respectively;
  • I and Ta are the measured temperatures of the specimens at time u, and a respectively, and
  • Mn alloying in the range of about 12-20 weight % of the total composition stabilizes the austenite phase, and increases the carbon solubility in the steel matrix.
  • the Cr alloying up to about 3 weight % increases the corrosion resistance and the mechanical strength by solution strengthening.
  • the Cu alloying of about 0.5 to about 2 weight % increases carbon solubility and corrosion resistance.
  • the (TMCP) hot rolling parameters can be adjusted to obtain steel compositions having a refined grain sizes of about 200 ⁇ or less, and/or low carbide precipitate fractions of about 5 volume % or less.
  • the methods may include a finish rolling step or steps at lower temperatures, which would introduce deformation banding/dislocations tangles to thereby enhance the formation of fine intra-grain precipitates.
  • the exemplary modified TMCP hot rolling steps/parameters can be combined with the addition of various micro-alloying elements such as, without limitation, V, Nb, Ti, Mo and/or N. It has been found that the micro-alloying elements in high Mn steels can result in the formation of fine carbide/nitride/carbo-nitride precipitates finely dispersed in the steel matrix. The finely dispersed precipitates can retard grain coarsening during reheating and recrystaliization during hot rolling, which thereby advantageously enhances the strength of the steel compositions/components of the present disclosure.
  • a method for fabricating a ferrous based component comprising: a) providing a composition having from 5 to 40 weight % manganese, from 0.01 to 1.2 weight % carbon, and the balance iron; b) heating the composition to a temperature above the austenite recrystaliization stop temperature of the composition or to a temperature to homogenize the composition, c) cooling the composition to a temperature below the austenite recrystallization stop temperature of the composition; d) deforming the composition while the composition is at a temperature below the austenite recrystallization stop temperature of the composition; and e) quenching the composition.
  • the microstructure having a refined grain size of 100 ⁇ or less includes a surface layer of the composition; wherein the thickness of the surface layer is from lOnm to 5000nm; and wherein the surface layer is formed prior to or during use of the composition.
  • step e) The method of any one of clauses 1-5, wherein prior to step e), the composition is slowly cooled or isothermally held; and wherein step e) includes rapidly quenching the composition.
  • step d) includes deforming the composition while the composition is at a temperature below the austenite recrystallization temperature and above the martensite transformation start temperature.
  • step d) includes deforming the composition to induce martensite formation of the composition; wherein the composition is deformed at a temperature of from 18° C to 24° C to induce martensite formation of the composition; and further comprising, after step d), heating the composition to a temperature above the austenite recrystallization stop temperature; wherein heating the composition to a temperature above the austenite recrystallization stop temperature after step d) reverses deformation-induced martensite of the composition into ultrafine grained austenite; and wherein the martensite start temperature of the ultrafine grained austenite is below 24° C.
  • step c) includes cooling the composition at a rate of from 2° C per second to 60° C per second
  • composition further includes one or more alloying elements selected from the group consisting of chromium, aluminum, silicon, nickel, cobalt, molybdenum, niobium, copper, titanium, vanadium, nitrogen, boron, zirconium, hafnium and combinations thereof.
  • each of the zirconium or hafnium ranges from 0.2 to 6 weight % of the total composition.
  • composition includes from 8 to 20 weight % manganese, from 0.30 to 0.7 weight % carbon, from 0.5 to 3 weight % chromium, from 0.5 to 2.0 weight % copper, from 0.1 to 1 weight % silicon, and the balance iron.
  • a ferrous based component fabricated according to the steps comprising: a) providing a composition having from 5 to 40 weight % manganese, from 0.01 to 1.2 weight % carbon, and the balance iron, b) heating the composition to a temperature above the austenite recrystaliization stop temperature of the composition; c) cooling the composition to a temperature below the austenite recrvstallization stop temperature of the composition; d) deforming the composition while the composition is at a temperature below the austenite recrystaliization stop temperature of the composition; and e) quenching the composition.

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Abstract

La présente invention a pour objet des compositions d'acier améliorées et leurs procédés de fabrication. La présente invention concerne plus précisément de l'acier à haute teneur en manganèse (Mn) ayant une résistance et/ou des performances renforcées aux températures cryogéniques, ainsi que des procédés de fabrication de compositions d'acier à teneur élevée en manganèse ayant une résistance et/ou des performances renforcées aux températures cryogéniques. Les compositions ou composants d'acier avantageux de la présente invention améliorent une ou plusieurs des propriétés suivantes : résistance, ténacité, module élastique, coefficient de dilatation thermique et/ou conductivité thermique. D'une façon générale, la présente invention concerne des aciers à teneur élevée en manganèse conçus pour résister à l'usure et/ou à la déformation aux températures cryogéniques.
PCT/US2017/031644 2016-06-06 2017-05-09 Aciers cryogéniques à haute résistance et haute teneur en manganèse et leurs procédés de fabrication WO2017213781A1 (fr)

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CN109234506A (zh) * 2018-10-10 2019-01-18 温州大学激光与光电智能制造研究院 一种激光辅助机械喷丸形成梯度纳米结构的复合方法

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JP6856083B2 (ja) * 2018-03-02 2021-04-07 Jfeスチール株式会社 高Mn鋼およびその製造方法
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WO2023228523A1 (fr) * 2022-05-26 2023-11-30 Jfeスチール株式会社 Acier pour pipeline
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CN115537672B (zh) * 2022-07-19 2023-08-18 燕山大学 一种屈服强度大于1000 MPa的低成本奥氏体钢及其温轧制备工艺
JP2024062502A (ja) * 2022-10-25 2024-05-10 三菱造船株式会社 低温ガス用タンク、低温ガス用タンクの製造方法
KR20240094448A (ko) * 2022-12-16 2024-06-25 주식회사 포스코 내수소취성이 향상된 오스테나이트계 스테인리스강 및 그 제조방법

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CN109136768A (zh) * 2018-10-17 2019-01-04 东北大学 可用于-135℃环境下的3.5%Ni钢板的制备方法

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