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US20150090372A1 - Recrystallization, Refinement, and Strengthening Mechanisms For Production Of Advanced High Strength Metal Alloys - Google Patents

Recrystallization, Refinement, and Strengthening Mechanisms For Production Of Advanced High Strength Metal Alloys Download PDF

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Publication number
US20150090372A1
US20150090372A1 US14/505,175 US201414505175A US2015090372A1 US 20150090372 A1 US20150090372 A1 US 20150090372A1 US 201414505175 A US201414505175 A US 201414505175A US 2015090372 A1 US2015090372 A1 US 2015090372A1
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alloy
mpa
size
atomic percent
thickness
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Inventor
Daniel James Branagan
Grant G. JUSTICE
Andrew T. BALL
Jason K. Walleser
Brian E. MEACHAM
Kurtis CLARK
Longzhou MA
Igor YAKUBTSOV
Scott LARISH
Sheng Cheng
Taylor L. GIDDENS
Andrew E. Frerichs
Alla V. Sergueeva
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Nanosteel Co Inc
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Nanosteel Co Inc
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Priority to US14/505,175 priority Critical patent/US20150090372A1/en
Assigned to THE NANOSTEEL COMPANY, INC. reassignment THE NANOSTEEL COMPANY, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MA, LONGZHOU, YAKUBTSOV, IGOR, BRANAGAN, DANIEL JAMES, GIDDENS, TAYLOR L., MEACHAM, BRIAN E., BALL, ANDREW T., CHENG, SHENG, CLARK, KURTIS, FRERICHS, ANDREW E., JUSTICE, GRANT G., LARISH, SCOTT, SERGUEEVA, ALLA V., WALLESER, JASON K.
Priority to US14/575,301 priority patent/US9284635B2/en
Publication of US20150090372A1 publication Critical patent/US20150090372A1/en
Assigned to HORIZON TECHNOLOGY FINANCE CORPORATION reassignment HORIZON TECHNOLOGY FINANCE CORPORATION SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: THE NANOSTEEL COMPANY, INC.
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/021—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular fabrication or treatment of ingot or slab
    • C21D8/0215—Rapid solidification; Thin strip casting
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
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    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
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    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
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    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
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    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
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    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • C—CHEMISTRY; METALLURGY
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    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
    • C—CHEMISTRY; METALLURGY
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
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    • C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
    • C—CHEMISTRY; METALLURGY
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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    • 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
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
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    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/56—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.7% by weight of carbon
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    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/001—Austenite
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    • C21D2211/00—Microstructure comprising significant phases
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    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/005—Ferrite

Definitions

  • This application deals with a class of metal alloys with advanced property combinations applicable to metallic sheet production. More specifically, the present application identifies the formation of metal alloys of relatively high strength and ductility and the use of one or more cycles of elevated temperature treatment and cold deformation to produce metallic sheet at reduced thickness with relatively high strength and ductility.
  • LSS Low-Strength Steels
  • HSS High-Strength Steels
  • HSS may be steel defined as exhibiting ultimate tensile strengths from 270 to 700 MPa and include types such as high strength low alloy, high strength interstitial free and bake hardenable steels.
  • Advanced High-Strength Steels (AHSS) steels may have ultimate tensile strengths greater than 700 MPa and include types such as martensitic steels (MS), dual phase (DP) steels, transformation induced plasticity (TRIP) steels, complex phase (CP) steels and twin induced plasticity (TWIP) steels.
  • MS martensitic steels
  • DP dual phase
  • TRIP transformation induced plasticity
  • CP complex phase
  • TWIP twin induced plasticity
  • LSS, HSS and AHSS may indicate tensile elongations at levels of 25% to 55%, 10% to 45% and 4% to 50%, respectively.
  • AHSS have been developed for automotive applications. See, e.g., U.S. Pat. Nos. 8,257,512 and 8,419,869. These steels are characterized by improved formability and crash-worthiness compared to conventional steel grades. Current AHSS are produced in processes involving thermo-mechanical processing followed by controlled cooling. To achieve the desired final microstructures in either uncoated or coated automotive products requires a control of a large number of variable parameters with respect to alloy composition and processing conditions.
  • the present disclosure is directed at alloys and their associated methods of production.
  • the method comprises:
  • the solidified alloy in step (b) and step (c) may have a thickness in the range of 1 mm to 500 mm.
  • the thickness may be reduced to a desired level, without compromising the mechanical properties.
  • the present disclosure also relates to a method comprising:
  • the heating and stressing of the alloy may be repeated in order to achieve a particular reduced thickness for the alloy that is targeted for a selected application.
  • the alloys of the present disclosure have application to continuous casting processes including belt casting, thin strip/twin roll casting, thin slab casting and thick slab casting.
  • the alloys find particular application in vehicles, drill collars, drill pipe, pipe casing, tool joint, wellhead, compressed gas storage tanks or liquefied natural gas canisters.
  • FIGS are provided for illustrative purposes and are not to be considered as limiting any aspect of this invention.
  • FIG. 1 illustrates the formation of Class 1 Steel.
  • FIG. 2 is a stress v. strain diagram illustrating mechanical response of Class 1 Steel with Modal Nanophase Structure.
  • FIG. 3A illustrates the formation of Class 2 Steel.
  • FIG. 3B illustrates the application of Recrystallization and Nanophase Refinement & Strengthening as applied to Structure 3 (Class 2 Steel) and the formation of Refined High Strength Nanomodal Structure.
  • FIG. 4 is a stress v. strain diagram illustrating mechanical response of Class 2 Steel with High Strength Nanomodal Structure.
  • FIG. 5 is a stress v. strain diagram illustrating mechanical response of steel alloys with Refined High Strength Nanomodal Structure.
  • FIG. 6 illustrates Thin Strip Casting showing that the process can be broken up into 3 key process stages.
  • FIG. 7 illustrates an example of commercial sheet sample from Alloy 260 taken from a coil produced by the Thin Strip Casting process.
  • FIG. 8 illustrates tensile properties of industrial sheet from (a) Alloy 260 at different steps of sheet production and (b) Alloy 284 after post-processing with different parameters.
  • FIG. 9 illustrates backscattered SEM micrographs of the as-solidified microstructure in the laboratory cast sheet from Alloy 260 with cast thickness of 1.8 mm in: (a) Outer layer region; (b) Central layer region.
  • FIG. 10 illustrates backscattered SEM micrographs of the as-solidified microstructure in Alloy 260 industrial sheet: (a) Outer layer region; (b) Central layer region.
  • FIG. 11 illustrates backscattered SEM micrographs of the microstructure in the industrial sheet from Alloy 260 after heat treatment at 1150° C. for 2 hr: (a) Outer layer region; (b) Central layer region.
  • FIG. 12 illustrates bright-field TEM images of the microstructure in the industrial sheet from Alloy 260 after heat treatment at 1150° C. for 2 hr.
  • FIG. 13 illustrates backscattered SEM micrographs of the microstructure in the cold-rolled sheet from Alloy 260 with 50% reduction: (a) Outer layer region; (b) Central layer region.
  • FIG. 14 illustrates bright-field TEM images of the microstructure in the cold-rolled sheet from Alloy 260 with 50% reduction.
  • FIG. 15 illustrates x-ray diffraction data (intensity vs two-theta) for Alloy 260 sheet in the cold rolled condition; a) Measured pattern, b) Rietveld calculated pattern with peaks identified.
  • FIG. 16 illustrates backscattered SEM micrographs of the microstructure in the cold-rolled sheet from Alloy 260 after heat treatment at 1150° C. for 5 minutes: (a) Outer layer region; (b) Central layer region.
  • FIG. 17 illustrates backscattered SEM micrographs of the microstructure in the cold-rolled sheet from Alloy 260 after heat treatment at 1150° C. for 2 hr: (a) Outer layer region; (b) Central layer region.
  • FIG. 18 illustrates bright-field TEM micrographs of the microstructure in the cold-rolled sheet from Alloy 260 after heat treatment at 1150° C. for 5 minutes.
  • FIG. 19 illustrates bright-field TEM micrographs of the microstructure in the cold-rolled sheet from Alloy 260 after heat treatment at 1150° C. for 2 hr.
  • FIG. 20 illustrates x-ray diffraction data (intensity vs two theta) for Alloy 260 sheet in the cold rolled and heat treated condition; (a) measured pattern; (b) Rietveld calculated pattern with peaks identified.
  • FIG. 21 illustrates backscattered SEM micrographs of the microstructure in the gage section of tensile specimen from Alloy 260: (a) Outer layer region; (b) Central layer region.
  • FIG. 22 illustrates bright-field (a) and dark-field (b) TEM micrographs of the microstructure in the gage section of tensile specimen from Alloy 260.
  • FIG. 23 illustrates x-ray diffraction data (intensity vs two-theta) for Alloy 260 sheet in the tensile gage of deformed sample; a) Measured pattern, b) Rietveld calculated pattern with peaks identified.
  • FIG. 24 illustrates recovery of tensile properties in the industrial sheet from Alloy 260 after overaging at 1150° C. for 8 hours.
  • FIG. 25 illustrates recovery of tensile properties in the industrial sheet from Alloy 260 after overaging at 1150° C. for 16 hours.
  • FIG. 26 illustrates recovery of tensile properties tensile properties in the industrial sheet from Alloy 284 after over aging at 1150° C. for 8 hours.
  • FIG. 27 illustrates property recovery in Alloy 260 after multiple steps of cold rolling and annealing.
  • FIG. 28 illustrates tensile properties of Alloy 260 sheet after each step of processing described in Table 15 showing that tensile properties fall into two distinct groups determined by the structure in the Alloy 260 sheet prior to tensile testing and that the process may be applied cyclically to transition between the structures utilizing the mechanisms shown.
  • FIG. 29 illustrates continuous slab casting process flow diagram showing slab production steps.
  • FIG. 30 illustrates thin slab casting process flow diagram showing steel sheet production steps that can be broken up into 3 process stages similar to Thin Strip Casting.
  • the steel alloys herein are such that they are initially capable of formation of what is described herein as Class 1 or Class 2 Steel which are preferably crystalline (non-glassy) with identifiable crystalline grain size morphology and mechanical properties.
  • Class 1 or Class 2 Steel which are preferably crystalline (non-glassy) with identifiable crystalline grain size morphology and mechanical properties.
  • the present disclosure focuses upon improvements to the Class 2 Steel and the discussion below regarding Class 1 is intended to provide clarifying context.
  • FIG. 1 The formation of Class 1 Steel herein is illustrated in FIG. 1 .
  • a Modal Structure (Structure #1, FIG. 1 ) is initially formed as a result of starting with a liquid melt of the alloy and solidifying by cooling, which provides nucleation and growth of particular phases having particular grain sizes.
  • Reference herein to “modal” may therefore be understood as a structure having at least two grain size distributions.
  • Grain size herein may be understood as the size of a single crystal of a specific particular phase preferably identifiable by methods such as scanning electron microscopy or transmission electron microscopy.
  • Structure #1 of the Class 1 Steel may be preferably achieved by processing through either laboratory scale procedures as shown and/or through industrial scale methods involving chill surface processing methodology such as twin roll processing, thick or thin slab casting.
  • the Modal Structure of Class 1 Steel will therefore initially possess, when cooled from the melt, the following grain sizes: (1) matrix grain size of 500 nm to 20,000 nm containing austenite and/or ferrite; (2) boride size of 25 nm to 5000 nm (i.e. non-metallic grains such as M 2 B where M is the metal and is covalently bonded to B).
  • the borides may also preferably be “pinning” type phases which is reference to the feature that the matrix grains will effectively be stabilized by the pinning phases which resist coarsening at elevated temperature.
  • metal borides have been identified as exhibiting the M 2 B stoichiometry but other stoichiometry's are possible and may provide pinning including M 3 B, MB (M 1 B 1 ), M 23 B 6 , and M 7 B 3 .
  • the Modal Structure of Class 1 Steel may be deformed by thermomechanical deformation and through heat treatment, resulting in some variation in properties, but the Modal Structure may be maintained.
  • Dynamic Nanophase Precipitation itself may be understood as the formation of a further identifiable phase in the Class 1 Steel which is termed a precipitation phase with an associated grain size. That is, the result of such Dynamic Nanophase Precipitation is to form an alloy with Modal Nanophase Structure (Structure #2, FIG. 1 ), which still possesses identifiable matrix grain size of 500 nm to 20,000 nm, boride pinning phases of 20 nm to 10000 nm in size, along with the formation of precipitations of hexagonal phases with 1.0 nm to 200 nm in size. As noted above, the matrix grains therefore do not coarsen when the alloy is stressed, but do lead to the development of the precipitation as noted.
  • Modal Nanophase Structure Structure #2, FIG. 1
  • references to the hexagonal phases may be understood as a dihexagonal pyramidal class hexagonal phase with a P6 3 mc space group (#186) and/or a ditrigonal dipyramidal class with a hexagonal P6bar2C space group (#190).
  • the mechanical properties of such second type structure of the Class 1 Steel are such that the tensile strength is observed to fall in the range of 630 MPa to 1100 MPa, with an elongation of 10-40%.
  • the second structure type of the Class 1 Steel is such that it exhibits a strain hardening coefficient between 0.1 to 0.4 that is nearly flat after undergoing the indicated yield.
  • the value of the strain hardening exponent n lies between 0 and 1.
  • a value of 0 means that the alloy is a perfectly plastic solid (i.e. the material undergoes non-reversible changes to applied force), while a value of 1 represents a 100% elastic solid (i.e. the material undergoes reversible changes to an applied force).
  • Table 1 below provides a summary on structures and mechanisms in Class 1 Steel herein.
  • metal Non-metallic (e.g. metal boride) boride) Precipitation — 1 nm to 200 nm Sizes Hexagonal phase(s) Tensile Response Intermediate structure; Actual with properties achieved transforms into Structure #2 based on structure type #2 when undergoing yield Yield Strength 300 to 600 MPa 300 to 840 MPa Tensile Strength — 630 to 1100 MPa Total Elongation — 10 to 40% Strain Hardening — Exhibits a strain hardening Response coefficient between 0.1 to 0.4 and a strain hardening coefficient as a function of strain which is nearly flat or experiencing a slow increase until failure
  • Class 2 Steel herein is illustrated in FIG. 3A .
  • Class 2 steel may also be formed herein from the identified alloys, which involves two new structure types after starting with Modal Structure (Structure #1, FIG. 3A ) followed by two new mechanisms identified herein as Nanophase Refinement (Mechanism #1, FIG. 3A ) and Dynamic Nanophase Strengthening (Mechanism #2, FIG. 3A ).
  • the structure types for Class 2 Steel are described herein as Nanomodal Structure (Structure #2, FIG. 3A ) and High Strength Nanomodal Structure (Structure #3, FIG. 3A ).
  • Class 2 Steel herein may be characterized as follows: Structure #1—Modal Structure (Step #1), Mechanism #1—Nanophase Refinement (Step #2), Structure #2—Nanomodal Structure (Step #3), Mechanism #2—Dynamic Nanophase Strengthening (Step #4), and Structure #3—High Strength Nanomodal Structure (Step #5).
  • Modal Structure (Structure #1) is initially formed as the result of starting with a liquid melt of the alloy and solidifying by cooling, which provides nucleation and growth of particular phases having particular grain sizes.
  • Grain size herein may again be understood as the size of a single crystal of a specific particular phase preferably identifiable by methods such as scanning electron microscopy or transmission electron microscopy.
  • Structure #1 of the Class 2 Steel may be preferably achieved by processing through either laboratory scale procedures as shown and/or through industrial scale methods involving chill surface processing methodology such as twin roll processing, thick or thin slab casting.
  • the Modal Structure of Class 2 Steel will therefore initially indicate, when cooled from the melt, the following grain sizes: (1) matrix grain size of 200 nm to 200,000 nm containing austenite and/or ferrite; (2) boride sizes of 20 nm to 10000 nm (i.e. non-metallic grains such as M 2 B where M is the metal and is covalently bonded to B).
  • the borides may also preferably be “pinning” type phases which are referenced to the feature that the matrix grains will effectively be stabilized by the pinning phases which resist coarsening at elevated temperature.
  • metal borides have been identified as exhibiting the M 2 B stoichiometry but other stoichiometry's are possible and may provide pinning including M 3 B, MB (M 1 B 1 ), M 23 B 6 , and M 7 B 3 and which are unaffected by Mechanisms #1 or #2 noted above).
  • Structure #1 of Class 2 steel herein includes austenite and/or ferrite along with such boride phases.
  • the Modal Structure is preferably first created (Structure #1, FIG. 3A ) and then after the creation, the Modal Structure may now be uniquely refined through Mechanism #1, which is a Nanophase Refinement, leading to Structure #2.
  • Nanophase Refinement is reference to the feature that the matrix grain sizes of Structure #1 which initially fall in the range of 200 nm to 200,000 nm are reduced in size to provide Structure #2 which has matrix grain sizes that typically fall in the range of 50 nm to 5000 nm.
  • the boride pinning phase can change size significantly in some alloys, while it is designed to resist matrix grain coarsening during the heat treatments.
  • 3A preferably occurs during elevated temperature heat treatment (optionally with pressure) and thus involves a unique refinement mechanism since grain coarsening rather than grain refinement is the conventional material response at elevated temperature.
  • the pressure applied is such at the elevated temperature yield strength of the material is exceeded which may be in the range of 5 MPa to 1000 MPa
  • Structure #2 is uniquely able to transform to Structure #3 during Dynamic Nanophase Strengthening (Mechanism #2, FIG. 3A ) and indicates tensile strength values in the range from 400 to 1825 MPa with 1.0% to 59.2% total elongation.
  • nano-scale precipitates can form during Nanophase Refinement and the subsequent thermal process in some of the non-stainless high-strength steels.
  • the nano-precipitates are in the range of 1 nm to 200 nm in size, with the majority (>50%) of these phases 10 ⁇ 20 nm in size, which are much smaller than the boride pinning phase formed in Structure #1 for retarding matrix grain coarsening.
  • the borides are found to be in a range from 20 to 10000 nm in size.
  • Structure #3 may be understood as a microstructure having matrix grains sized generally from 25 nm to 2500 nm which are pinned by boride phases which are in the range of 20 nm to 10000 nm and with precipitate phases which are in the range of 1 nm to 200 nm.
  • the initial formation of the above referenced precipitation phase with grain sizes of 1 nm to 200 nm starts at Nanophase Refinement and continues during Dynamic Nanophase Strengthening leading to Structure #3 formation.
  • the volume fraction of the precipitation phase/grains of 1 nm to 200 nm in size in Structure #2 increases during transformation into Structure #3 and assists with the identified strengthening mechanism.
  • the level of gamma-iron is optional and may be eliminated depending on the specific alloy chemistry and austenite stability.
  • dynamic recrystallization is a known process but differs from Mechanism #2 ( FIG. 3A ) since it involves the formation of large grains from small grains so that it is not a refinement mechanism but a coarsening mechanism. Additionally, as new undeformed grains are replaced by deformed grains no phase changes occur in contrast to the mechanisms presented here and this also results in a corresponding reduction in strength in contrast to the strengthening mechanism here. Note also that metastable austenite in steels is known to transform to martensite under mechanical stress but, preferably, no evidence for martensite or body centered tetragonal iron phases are found in the new steel alloys described in this application. Table 2 below provides a summary on structures and mechanisms in Class 2 Steel herein.
  • Nanophase Refinement Dynamic Nanophase Formation solidifying this liquid melt mechanism occurring during Strengthening mechanism and forming directly heat treatment occurring through application of mechanical stress Transformations
  • Grain Refinement Grain size remains refined Size Austenite (50 nm to 5000 nm) at 25 nm to 2500 nm/ Austenite to ferrite and Additional
  • metal boride borides (e.g. metal boride) borides (e.g. metal boride) Precipitation — 1 nm to 200 nm 1 nm to 200 nm Sizes Tensile Actual with properties Intermediate structure; Actual with properties Response achieved based on structure transforms into Structure #3 achieved based on type #1 when undergoing yield formation of structure type #3 and fraction of transformation.
  • Hardening strain softening at initial may vary from 0.2 to 1.0 Response straining as a result of phase depending on amount of transformation, followed by a deformation and significant strain hardening transformation effect leading to a distinct maxima
  • the steel alloys herein are such that they are capable of formation of High Strength Nanomodal Structure (Structure #3, FIG. 3A and Table 2).
  • Structure #1 can be formed at solidification of material at thicknesses range from 1 mm to 500 mm
  • Structure #2 (after Nanophase Refinement) relates to a thicknesses from 1 mm to 500 mm
  • Structure #3 after Dynamic Nanophase Strengthening) forms at a reduced thickness of 0.1 mm to 25 mm.
  • Structure #3 when undergoing heating and recrystallization, followed by stress above yield, which may be realized in sheet processing aimed at reducing thickness, does not, herein, compromise the alloy mechanical strength characteristics (e.g. reductions of more than 10%).
  • Resultant Structure #5 provides similar behavior ( FIG. 5 ) and mechanical properties as initial Structure #3 and depending on the specific alloy and processing conditions can result in improvements in properties.
  • recrystallization (step 6) and subsequent deformation (step 8) can be repeatedly applied to the High Strength Nanomodal Structure, as explained herein.
  • step 6 recrystallization
  • step 8 subsequent deformation
  • step 9 further cycles may be considered and one can end either at Step 7, Step 8, or Step 9 depending on the requirements of a particular end-user application, desired thickness objective (i.e. targeting a final thickness in the range of 0.1 mm to 25 mm) and final tailoring of properties such as cold rolling to an intermediate level without applying subsequent annealing.
  • the Recrystallized Modal Structure (Structure #4, FIG. 3B ) is thus characterized by matrix grain growth to the size of 100 nm to 50,000 nm which are pinned by boride phases with the size in the range of 20 nm to 10000 nm and precipitate phases randomly distributed in the matrix which are in the range of 1 nm to 200 nm in size.
  • Structure analysis shows gamma-Fe (Austenite) is the primary matrix phase (25% to 90%) and that it coincides with a complex mixed transitional metal boride phase typically with the M 2 B 1 stoichiometry present.
  • the strength increases with strain indicating an activation of Mechanism #3 (Nanophase Refinement and Strengthening). With further straining, the strength continues to increase but with a gradual decrease in strain hardening coefficient value up to nearly failure. Some strain softening occurs but only near the breaking point which may be due to reductions in localized cross sectional area at necking.
  • the tensile properties that can be achieved in the alloys herein along with formation of Refined High Strength Nanomodal Structure include tensile strength values in the range from 400 to 1825 MPa and 1.0% to 59.2% total elongation. The level of tensile properties achieved is also dependent on the amount of transformation occurring as the strain increases corresponding to the characteristic stress strain curve for a Class 2 steel.
  • 3B may be understood as a microstructure having matrix grains sized generally from 10 nm to 2000 nm which are pinned by boride phases which are in the range of 20 nm to 10000 nm and with precipitate phases which are in the range of 1 nm to 200 nm.
  • the volume fraction of the precipitation phase of 1 nm to 200 nm in size in Structure #5 increases during transformation through Mechanism #3.
  • the level of gamma-iron is optional and may be eliminated depending on the specific alloy chemistry and austenite stability.
  • the newly identified structure and mechanisms can be applied cyclically in a sequential manner.
  • the High Strength Nanomodal Structure (Structure #3) is formed either partially or completely, it can be recrystallized through high temperature exposure to form the Recrystallized Modal Structure (Structure #4).
  • This structure has the unique ability to be subsequently transformed by cold deformation by a range of processes including cold rolling, cold stamping, hydroforming, roll forming etc. into the Refined High Strength Nanomodal Structure (Structure #5). Once this cycle is complete, the cycle can then be repeated as many times as necessary (i.e.
  • the sheet is now heat treated (heating above 700° C. but below the Tm) and the Recrystallized Modal Structure (Structure #4) is formed.
  • This sheet is then cold rolled another 30% of reduction to a gauge thickness of ⁇ 1.5 mm and the formation of the Refined High Strength Nanomodal Structure (Structure #5). Further cold reduction would again result in breakage of the sheet.
  • a heat treatment is then applied to recrystallize the sheet resulting in a high ductility Recrystallized Modal Structure (Structure #4).
  • the sheet is then cold rolled another 30% to yield a gauge thickness of ⁇ 1.0 mm thickness with a Refined High Strength Nanomodal Structure (Structure #5) obtained. After the gauge thickness target is reached, no further cold rolling reduction is necessary.
  • the sheet may or may not be heated again to be recrystallized.
  • the sheet may or may not be heated again to be recrystallized.
  • This resulting sheet may then be cold stamped by the end user and during the stamping process, would partially or completely transform into the Refined High Strength Nanomodal Structure (Structure #5).
  • Recrystallized Modal Structure #4 Another example after forming the Recrystallized Modal Structure (Structure #4), in one or multiple steps, would be to expose this structure to cold deformation through cold rolling and after exceeding the yield strength to Nanophase Refinement and Strengthening (Mechanism #3).
  • the material could be only partially cold rolled and then not annealed (i.e. recrystallized).
  • a particular sheet material with the Recrystallized Modal Structure (Structure #4) which can be cold rolled up to 40% before breaking for example could instead be only cold rolled 10%, 20% or 30% and then not annealed.
  • metal boride (Borides (e.g metal boride) Precipitation 1 nm to 200 nm 1 nm to 200 nm Sizes Tensile Intermediate structure; transforms into Actual with properties achieved based on Response Structure #5 when undergoing yield formation of Structure # 5 and fraction of transformation Yield Strength 200 MPa to 1650 MPa 200 MPa to 1650 MPa Tensile Strength — 400 MPa to 1825 MPa Total Elongation — 1.0% to 59.2% Strain After yield point, may exhibit a strain Strain hardening coefficient may vary from Hardening softening at initial straining as a result of 0.2 to 1.0 depending upon amount of Response phase transformation, followed by a deformation and transformation significant strain hardening effect leading to distinct maxima
  • the chemical composition of the alloys studied is shown in Table 4 which provides the preferred atomic ratios utilized.
  • Initial studies were done by sheet casting in a Pressure Vacuum Caster (PVC). Using high purity elements (>99 wt %), four 35 g alloy feedstock's of the targeted alloys were weighed out according to the atomic ratios provided in Table 4. The feedstock material was then placed into the copper hearth of an arc-melting system. The feedstock was arc-melted into an ingot using high purity argon as a shielding gas. The ingots were flipped several times and re-melted to ensure homogeneity. After mixing, the ingots were then placed in a PVC chamber, melted using RF induction and then ejected onto a copper die designed for casting 3 inch by 4 inch sheets with thickness of 3.3 mm.
  • the alloys herein that are susceptible to the transformations illustrated in FIGS. 3A and 3B fall into the following groupings: (1) Fe/Cr/Ni/Mn/B/Si (alloys 1 to 63, 66 to 71, 184, 192, 280 to 283); (2) Fe/Cr/Ni/Mn/B/Si/Cu (alloys 64, 72, 74 to 183, 188 to 191, 193 to 229, 233 to 235, 248, 249, 252, 253, 256 to 260, 268 to 279, 284 to 288, 292 to 297, 301); (3) Fe/Cr/Ni/Mn/B/Si/C (alloys 65, 73); (4) Fe/Cr/Ni/Mn/B/Si/Cu/Ti (alloys 185 to 187); (5) Fe/Cr/Mn/B/Si/Cu (alloys 230 to 232,
  • the alloy composition herein would include the following four elements at the following indicated atomic percent: Fe (55.0 to 88.0 at. %); B (0.50 to 8.0 at. %); Si (0.5 to 12.0 at. %); Mn (1.0 to 19.0 at. %).
  • the following elements are optional and may be present at the indicated atomic percent: Ni (0.1 to 9.0 at. %); Cr (0.1 to 19.0 at. %); Cu (0.1 to 6.00 at. %); Ti (0.1 to 1.00 at. %); C (0.1 to 4.0 at. %).
  • Impurities may be present including atoms such as Al, Mo, Nb, S, O, N, P, W, Co, Sn, Zr, Pd and V, which may be present up to 10 atomic percent.
  • the alloys may herein also be more broadly described as Fe-based alloys (with Fe content greater than 50.0 atomic percent) and further including B, Si and Mn, and capable of forming Class 2 steel ( FIG. 3A ) and further capable of undergoing recrystallization (heat treatment to 700° C. but below Tm) followed by stress above yield to provide Refined High Strength Nanomodal Structure (Structure #5, FIG. 3B ), which steps of recrystallization and stress above yield may be repeated.
  • the alloys may be further defined by the mechanical properties that are achieved for the identified structures with respect to yield strength, tensile strength, and tensile elongation characteristics.
  • melting occurs in one or multiple stages with initial melting from ⁇ 1120° C. depending on alloy chemistry and final melting temperature exceeding 1425° C. in some instances (marked N/A in Table 5). Accordingly, the melting point range for the alloys herein capable of Class 2 Steel formation and subsequent recrystallization and cold forming ( FIG. 3B ) may be from 1000° C. to 1500° C. Variations in melting behavior reflect a complex phase formation at solidification of the alloys depending on their chemistry.
  • the density of the alloys was measured on arc-melt ingots using the Archimedes method in a specially constructed balance allowing weighing in both air and distilled water.
  • the density of each alloy is tabulated in Table 6 and was found to vary from 7.30 g/cm 3 to 7.89 g/cm 3 .
  • Experimental results have revealed that the accuracy of this technique is ⁇ 0.01 g/cm 3 .
  • HIP cycle parameters are listed in Table 7.
  • the key aspect of the HIP cycle was to remove macrodefects such as pores and small inclusions by mimicking hot rolling during sheet production by Thin Strip/Twin Roll Casting process or Thick/Thin Slab Casting process.
  • the HIP cycle which is a thermomechanical process allows the elimination of some fraction of internal and external macrodefects while smoothing the surface of the plate.
  • HIP Temperature HIP Time HIP Pressure [° C.] [min] [ksi] HIP 1 1000 60 30 HIP 2 1100 60 30 HIP 3 1125 60 30 HIP 4 1150 60 30 HIP 5 1100 60 45 HIP 6 1125 60 45 HIP 7 1140 60 45 HIP 8 1150 60 45 HIP 9 1165 60 45 HIP 10 1175 60 45
  • the plates were heat treated at parameters specified in Table 8.
  • air cooling the specimens were held at the target temperature for a target period of time, removed from the furnace and cooled down in air, modeling coiling conditions at commercial sheet production.
  • controlled cooling the furnace temperature was lowered at a specified rate, with samples loaded, allowing for a control of the sample cooling rate.
  • Stage 1 Stage 2 Stage 2 Temperature Dwell Temperature Dwell [° C.] [min] Stage 1 Cooling [° C.] [min] Stage 2 Cooling HT1 700 60 Air Normalized — — — HT2 700 — 1° C./min to ⁇ 300° C. — — — — HT3 850 60 Air Normalized — — — HT4 850 240 Air Normalized — — — HT5 850 360 0.75° C./min to ⁇ 300° C. — — — HT6 700 — 1° C./min to ⁇ 300° C.
  • Air Normalized HT7 900 60 Air Normalized — — — HT8 950 360 Air Normalized — — — HT9 1150 120 Air Normalized — — — — HT10 1100 120 Air Normalized — — — — HT11 1050 120 Air Normalized — — HT12 1075 120 Air Normalized HT13 950 360 0.75 ° C./min to ⁇ 500° C. HT14 850 5 Air Normalized
  • the tensile specimens were cut from the plates after HIP cycle and heat treatment using wire electrical discharge machining (EDM). Tensile properties were measured on an Instron mechanical testing frame (Model 3369), utilizing Instron's Bluehill control and analysis software. All tests were run at room temperature in displacement control with the bottom fixture held rigid and the top fixture moving; the load cell is attached to the top fixture. Tensile properties of the alloys after HIPing are listed in Table 9 and this relates to Structure 3 noted above. The ultimate tensile strength values vary from 403 to 1810 MPa with tensile elongation from 1.0 to 33.6%. The yield strength is in a range from 205 to 1223 MPa. The mechanical characteristic values in the steel alloys herein will depend on alloy chemistry and processing/treatment condition.
  • Cast plates from selected alloys listed in Table 4 were thermo-mechanically processed via hot rolling.
  • the plates were heated in a tunnel furnace to a target temperature equal to the nearest 25° C. temperature interval that was at least 50° C. below the solidus temperature previously determined (see Table 5).
  • the rolls for the mill were held at a constant spacing for all samples rolled, such that the rolls were touching with minimal force.
  • the resulting reductions varied between 21.0% and 41.9%.
  • the primary importance of the hot rolling stage is to initiate Nanophase Refinement and to remove macrodefects such as pores and voids by mimicking the hot rolling at Stage 2 of Twin Roll Casting process or at Stage 1 or Stage 2 of Thin Slab Casting process. This process eliminates a fraction of internal macrodefects, in addition to smoothing out the sample surface.
  • Selected alloys from Table 4 were cast into plates with thickness of 50 mm using an Indutherm VTC800V vacuum tilt casting machine. Alloys of designated compositions were weighed out in 3 kilogram charges using designated quantities of commercially-available ferroadditive powders of known composition and impurity content, and additional alloying elements as needed, according to the atomic ratios provided in Table 4 for each alloy. Weighed out alloy charges were placed in zirconia coated silica-based crucibles and loaded into the casting machine. Melting took place under vacuum using a 14 kHz RF induction coil.
  • Cast plates with initial thickness of 50 mm were subjected to hot rolling at the temperatures between 1075 to 1100° C. depending on alloy solidus temperature. Rolling was done on a Fenn Model 061 single stage rolling mill, employing an in-line Lucifer EHS3GT-B18 tunnel furnace. Material was held at the hot rolling temperature for an initial dwell time of 40 minutes to ensure homogeneous temperature. After each pass on the rolling mill, the sample was returned to the tunnel furnace with a 4 minute temperature recovery hold to correct for temperature lost during the hot rolling pass. Hot rolling was conducted in two campaigns, with the first campaign achieving approximately 85% total reduction to a thickness of 6 mm. Following the first campaign of hot rolling, a section of sheet between 150 mm and 200 mm long was cut from the center of the hot rolled material. This cut section was then used for a second campaign of hot rolling for a total reduction between both campaigns of between 96% and 97%.
  • Tensile specimens were cut from hot rolled sheets via EDM. Tensile properties were measured on an Instron mechanical testing frame (Model 3369), utilizing Instron's Bluehill control and analysis software. All tests were run at room temperature in displacement control with the bottom fixture held rigid and the top fixture moving; the load cell is attached to the top fixture.
  • Tensile properties of the alloys in the as hot rolled condition are listed in Table 11.
  • the ultimate tensile strength values may vary from 978 to 1281 MPa with tensile elongation from 14.0 to 29.2%.
  • the yield stress is in a range from 396 to 746 MPa.
  • the mechanical characteristic values in the steel alloys herein will depend on alloy chemistry and hot rolling conditions.
  • Hot-rolled sheets from each alloy were then subjected to further cold rolling in multiple passes down to thickness of 1.2 mm. Rolling was done on a Fenn Model 061 single stage rolling mill. Tensile properties of the alloys after hot rolling and subsequent cold rolling are listed in Table 12. The ultimate tensile strength values in this specific example may vary from 1438 to 1787 MPa with tensile elongation from 1.0 to 20.8%. The yield stress is in a range from 809 to 1642 MPa. The mechanical characteristic values in the steel alloys herein will depend on alloy chemistry and processing conditions. Cold rolling reduction influences the amount of austenite transformation leading to different level of strength in the alloys.
  • alloys were heat treated at the parameters specified in Table 13. Heat treatments were conducted in a Lucifer 7GT-K12 sealed box furnace under an argon gas purge, or in a ThermCraft XSL-3-0-24-1C tube furnace. In the case of air cooling, the specimens were held at the target temperature for a target period of time, removed from the furnace and cooled down in air. In cases of controlled cooling, the furnace temperature was lowered at a specified rate with samples loaded.
  • Tensile properties of the selected alloys after hot rolling with subsequent cold rolling and heat treatment at different parameters are listed in Table 14.
  • the ultimate tensile strength values in this specific case example may vary from 813 MPa to 1316 MPa with tensile elongation from 6.6 to 35.9%.
  • the yield stress is in a range from 274 to 815 MPa.
  • the mechanical characteristic values in the steel alloys herein will depend on alloy chemistry and processing conditions.
  • FIG. 6 A schematic of the Thin Strip Casting process is shown in FIG. 6 . As shown, the process includes three stages; Stage 1—Casting, Stage 2—Hot Rolling, and Stage 3—Strip Coiling.
  • Stage 1 the sheet was formed as the solidifying metal was brought together in the roll nip between the surfaces of the rollers. As solidified sheet thickness was in the range from 1.6 to 3.8 mm.
  • Stage 2 the solidified sheet was hot rolled at 1150° C. with 20 to 35% reduction. The thickness of the hot rolled sheet was varying from 2.0 to 3.5 mm.
  • Produced sheet was collected on the coils.
  • a sample of the produced sheet from Alloy 260 is shown in FIG. 7 .
  • the strips were subjected to rolling using a Fenn Model 061 Rolling Mill and a Lucifer 7-R24 Atmosphere Controlled Box Furnace.
  • the plates were placed in a hot furnace typically from 850 to 1150° C. for 10 to 60 minutes prior to the start of rolling.
  • the strips were then repeatedly rolled at between 10% and 25% reduction per pass and were placed in the furnace for 1 to 2 min between rolling steps to allow then to return to temperature. If the plates became too long to fit in the furnace they were cooled, cut to a shorter length, then reheated in the furnace for additional time before they were rolled again.
  • the strips were subjected to cold rolling using a Fenn Model 061 Rolling Mill with different reduction depending on the post-processing goal.
  • reduction of 10 to 15% per pass with typically 25 to 50% total was applied before intermediate annealing at various temperatures (800 to 1170° C.) and various times (2 minutes to 16 hours).
  • sheet was cold rolled with reduction typically from 2 to 15%.
  • Heat treatment studies were done by using a Lindberg Blue M Model “BF51731C-1” Box Furnace in air to simulate in-line annealing on a hot dip pickling line with temperatures typically from 800 to 1200° C. and times from typically 2 minutes to 15 minutes.
  • a Lucifer 7-R24 Atmosphere Controlled Box Furnace was utilized for heat treatments with temperatures typically from 800 to 1200° C. and times from typically 2 hours up to 1 week.
  • Industrial sheet from Alloy 260 and Alloy 284 was produced by Thin Strip Casting process. As-solidified thickness of the sheet was 3.2 and 3.6 mm, respectively (corresponds to Stage 1 of Thin Strip Casting process, FIG. 6 ). In-line hot rolling at temperatures from 1100 to 1170° C. was applied during sheet production (corresponds to Stage 2 of Thin Strip Casting process, FIG. 6 ) leading to final thickness of produced sheet of 2.2 mm (i.e. 31% reduction) for Alloy 260 and 2.6 mm (i.e. 28% reduction) for Alloy 284.
  • Samples from Alloy 260 industrial sheet were post-processed to mimic processing at commercial scale including (1) homogenization heat treatment at 1150° C. for 2 hr; (2) cold rolling with reduction of 15%; (3) annealing at 1150° C. for 5 min and skin pass with 5% reduction.
  • the tensile specimens were cut from the sheets using a Brother HS-3100 wire electrical discharge machining (EDM).
  • EDM wire electrical discharge machining
  • the tensile properties were measured on an Instron mechanical testing frame (Model 3369), utilizing Instron's Bluehill control and analysis software. All tests were run at room temperature in displacement control with the bottom fixture held rigid and the top fixture moving with the load cell attached to the top fixture.
  • FIG. 8 a Properties of the Alloy 260 sheet at each step of post-processing are shown in FIG. 8 a .
  • the homogenization heat treatment improves sheet properties dramatically due to complete Nanomodal Structure (Structure #2, FIG. 3A ) formation in the sheet volume through Nanophase Refinement (Mechanism #1, FIG. 3A ).
  • Mechanism #1 FIG. 3A
  • the structure was partially transformed by hot rolling into the Nanomodal Structure but an additional heat treatment was needed to cause complete transformation, especially in the center of the sheet. Cold rolling leads to material strengthening through Dynamic Nanophase Strengthening (Mechanism #2, FIG. 3A ) and results in High Strength Nanomodal Structure formation (Structure #3, FIG. 3A ).
  • Samples from Alloy 284 industrial sheet were also post-processed to mimic processing at commercial scale with different post-processing parameters.
  • the post-processing includes (1) homogenization heat treatment at 1150° C. for 2 hr; (2) homogenization heat treatment at 1150° C. for 2 hr+cold rolling with 45% reduction+annealing at 1150° C. for 5 min; (3) homogenization heat treatment at 1150° C. for 8 hr+cold rolling with 15% reduction+annealing at 1150° C. for 5 min; (4) homogenization heat treatment at 1150° C. for 8 hr+cold rolling with 25% reduction+annealing at 1150° C. for 2 hr; (5) homogenization heat treatment at 1150° C.
  • Alloy 284 sheet properties after these post-processing routes are shown in FIG. 8 b .
  • all post-processing routes provide similar strength values between 1140 and 1220 MPa.
  • Ductility varies from 19 to 28% depending on the post-processing parameters, sheet homogeneity, level of structural transformations, etc.
  • industrial sheet from Alloy 284 provides property combination with tensile strength above 1100 MPa and ductility higher than 19%.
  • Modal Structure specified as Structure #1 forms in the alloys listed in Table 4 at solidification as demonstrated herein.
  • Two sheet samples from Alloy 260 are provided for this Case Example.
  • the first sample was cast from Alloy 260 on the laboratory scale in a Pressure Vacuum Caster (PVC).
  • PVC Pressure Vacuum Caster
  • four 35 g alloy feedstocks of the targeted alloy were weighed out according to the atomic ratios provided in Table 4.
  • the feedstock material was then placed into the copper hearth of an arc-melting system.
  • the feedstock was arc-melted into an ingot using high purity argon as a shielding gas.
  • the ingots were flipped several times and re-melted to ensure homogeneity.
  • the ingots were then cast in the form of a finger approximately 12 mm wide by 30 mm long and 8 mm thick.
  • the resulting fingers were then placed in the PVC chamber, melted using RF induction and then ejected onto a copper die designed for casting 3 inches by 4 inches sheets with thickness of 1.8 mm mimicking the Stage 1 of Thin Strip Casting ( FIG. 6 ).
  • the second sample was cut from Alloy 260 industrial sheet produced by Thin Strip Casting process in as-solidified condition without in-line hot rolling (no hot rolling during Thin Strip Casting) and with an as solidified thickness of 3.2 mm.
  • Structural analysis was performed by scanning electron microscopy (SEM) using an EVO-MA10 scanning electron microscope manufactured by Carl Zeiss SMT Inc. To make SEM specimens, the cross-section of the as-cast sheet was cut and ground by SiC paper and then polished progressively with diamond media suspension down to 1 ⁇ m grit. The final polishing was done with 0.02 ⁇ m grit SiO 2 solution. SEM images of microstructure in the outer layer region that is close to the surface and in the central layer region of the as-solidified sheet samples are shown in FIG. 9 and FIG. 10 .
  • dendrite size of the matrix phase is 2 to 5 ⁇ m in thickness and up to 20 ⁇ m in length in the outer layer region, while the dendrites are more round in the central layer region with the size from 4 to 20 ⁇ m ( FIG. 9 ).
  • Very fine structure can be observed in the interdendritic areas in both regions.
  • the industrial sheet also shows a dendritic structure with matrix phase of 2 to 5 ⁇ m in thickness and up to 20 ⁇ m in length in the outer layer region and are more round dendrites in the central layer region with the size from 4 to 20 ⁇ m ( FIG. 10 ).
  • interdendritic borides are well defined in the industrial sheet which are coarser and have needle-type shape in the central layer region as compared to finer and more homogeneous distributed borides in outer layer region. Due to fast cooling rate at laboratory conditions, the microstructure of the 1.8 mm as-cast plate is finer at both the outer layer and the central layer, and the fine boride phase cannot be resolved at the grain boundaries by SEM. In both cases, the large dendrites of the matrix phase with fine boride phase in the interdendritic areas forms the typical Modal Structure in the as-cast state. Coarser microstructure was observed in the central layer region in both laboratory and industrial sheet reflecting slower cooling rate as compared to the outer layers during solidification in both cases.
  • Modal Structure forms in steel alloys herein at solidification during laboratory and industrial casting processes.
  • the distribution of the boride phase is less homogeneous as compared to that in the outer layer, as one can see that some areas are occupied by boride phase more than other areas ( FIG. 11 b ).
  • the borides become more uniform in size.
  • some boride phase shows a length up to 15 to 18 ⁇ m.
  • the longest boride phase is ⁇ 10 ⁇ m and can only be occasionally found.
  • Hot rolling during Thin Strip Casting and additional heat treatment of the industrial sheet led to formation of Nanomodal Structure. Note that the details of the matrix phases cannot be effectively resolved using the SEM due to the nanocrystalline scale of the refined phases which will be shown subsequently using TEM.
  • TEM transmission electron microscopy
  • the boride phase with size of 200 nm to 5 ⁇ m is revealed in the intergranular regions that separate the matrix grains which is consistent with the SEM observation in FIG. 11 .
  • the boride phase re-organized into isolated precipitates of less than 500 nm in size and distributed in the region between matrix grains was additionally revealed by TEM.
  • Matrix grains are very much refined due to Nanophase Refinement at high temperature. Unlike in the as-cast state with micron-sized matrix grains, the matrix grains are typically in the range of 200 to 500 nm in size, as shown in FIG. 12 .
  • Nanomodal Structure (Structure #2, FIG. 3A ) forms in steel alloys herein through Nanophase Refinement (Mechanism #1, FIG. 3A ).
  • FIG. 13 shows the microstructure of industrial sheet from Alloy 260 after cold rolling by 50% thickness reduction.
  • the boride phase is slightly aligned along the rolling direction, but broken up especially in the central layer region where long boride phase commonly forms during solidification. Some of the boride phase may be crushed by the cold rolling down to the size of few microns. At the same time, changes can be found in matrix phase. As shown in FIG. 13 , subtle contrast is visible in the matrix after the cold rolling but not fully resolvable by SEM. Additional structural analysis was performed by TEM that revealed additional details described below.
  • the TEM images of the microstructure in the cold rolled sample are shown in FIG. 14 . It can be seen that the cold rolled sheet has a refined microstructure, with nanocrystalline matrix grains typically from 100 to 300 nm in size. Microstructure refinement observed after cold deformation is a typical result of Dynamic Nanophase Strengthening (Mechanism #2, FIG. 3A ) with formation of High Strength Nanomodal Structure (Structure #3, FIG. 3A ). Small nanocrystalline precipitates can be found scattered in the matrix and grain boundary regions which is typical for High Strength Nanomodal Structure.
  • Alloy 260 sheet structure including the nature of the small nanocrystalline phases were revealed by using x-ray diffraction.
  • X-ray diffraction was done using a Panalytical X'Pert MPD diffractometer with a Cu K ⁇ x-ray tube and operated at 40 kV with a filament current of 40 mA. The scans was run with a step size of 0.01° and from 25° to 95° two-theta with silicon incorporated to adjust for instrument zero angle shift. The resulting scan was then subsequently analyzed by Rietveld analysis using Siroquant software.
  • an x-ray diffraction scan pattern is shown including the measured/experimental pattern and the Rietveld refined pattern for the Alloy 260 sheets in cold rolled condition.
  • good fit of the experimental data was obtained.
  • Analysis of the x-ray patterns including specific phases found, their space groups and lattice parameters are shown in Table 15.
  • the lattice parameters of the identified phases are different than that found for pure phases clearly indicating the effect of substitution/saturation by the alloying elements.
  • the phase composition and structural features of the microstructure are typical for High Strength Nanomodal structure.
  • the fine boride phase is relatively uniform in size and homogeneously distributed in the matrix in the outer layer region.
  • the distribution of boride phase is less homogeneous as at the outer layer, as one can see that some areas are occupied by boride phase more than other areas ( FIG. 16 b ).
  • the boride phase distribution becomes similar at the outer layer region and at the central layer region ( FIG. 17 ).
  • the boride becomes more uniform in size, with a size less than 5 ⁇ m. Additional details of the microstructure were revealed by TEM analysis and will be provided subsequently.
  • TEM specimen preparation procedure includes cutting, thinning, and electropolishing. First, samples were cut with electric discharge machine, and then thinned by grinding with pads of reduced grit size every time. Further thinning to 60 to 70 ⁇ m thickness is done by polishing with 9 ⁇ m, 3 ⁇ m, and 1 ⁇ m diamond suspension solution respectively. Discs of 3 mm in diameter were punched from the foils and the final polishing was fulfilled with electropolishing using a twin-jet polisher. The chemical solution used was a mixture of 30% nitric acid in methanol base.
  • the TEM specimens were ion-milled using a Gatan Precision Ion Polishing System (PIPS).
  • the ion-milling usually was done at 4.5 keV, and the inclination angle is reduced from 4° to 2° to open up the thin area.
  • the TEM studies were done using a JEOL 2100 high-resolution microscope operated at 200 kV.
  • the cold rolled samples show extensive recrystallization. As shown in FIG. 18 , micron size grains are formed after 5 minutes holding at 1150° C. Within the recrystallized grains, there are a number of stacking faults, suggesting formation of austenite phase. At the same time, the boride phases show a certain degree of growth. A similar microstructure is seen in the sample after heat treatment at 1150° C. for 2 hr ( FIG. 19 ). The matrix grains are clean with sharp, large-angle grain boundaries, typical for a recrystallized microstructure. Within the matrix grains, stacking faults are generated and boride phases can be found at grain boundaries, as shown in the 5 minute heat treated sample. Compared to the cold rolled microstructure ( FIG. 14 ), the high temperature heat treatment after cold rolling transforms the microstructure into the Recrystallized Modal Structure (Structure #4, FIG. 3B ) with micron-sized matrix grains and boride phase.
  • Structure #4, FIG. 3B Recrystallized Modal Structure
  • Recrystallized Modal Structure forms in steel alloys herein through structural recrystallization of High Strength Nanomodal Structure (Structure #3, FIGS. 3A and 3B ).
  • Microstructure of industrial sheet from Alloy 260 with Recrystallized Modal Structure (Structure #4, FIG. 3B ) formed during the heat treatment at 1150° C. for 2 hr was studied using SEM, TEM, and X-ray diffraction after taking the sheet and subjecting it to additional tensile deformation. Samples were cut from the gage of tensile specimens after deformation and were metallographically polished in stages down to 0.02 ⁇ m grit to ensure smooth samples for scanning electron microscopy (SEM) analysis. SEM was done using a Zeiss EVO-MA10 model with the maximum operating voltage of 30 kV. Example SEM backscattered electron micrographs of the sheet samples from Alloy 260 after deformation are shown in FIG.
  • the boride phase distribution after tensile deformation is similar to that in the sheet after cold rolling (see FIG. 17 ).
  • the boride phase shows a size of mostly less than 5 ⁇ m and homogeneous distribution in matrix. It suggests that the tensile deformation did not change the boride phase size and distribution. However, the tensile deformation caused substantial structural changes in the matrix phases, which was revealed by TEM studies.
  • TEM specimen preparation procedure includes cutting, thinning, and electropolishing. First, samples were cut using electric discharge machining from the gage section of tensile specimens, and then thinned by grinding with pads of reduced grit size media every time. Further thinning to 60 to 70 ⁇ m thick is done by polishing with 9 ⁇ m, 3 ⁇ m, and 1 ⁇ m diamond suspension solution respectively. Discs of 3 mm in diameter were punched from the foils and the final polishing was fulfilled with electropolishing using a twin-jet polisher. The chemical solution used was a 30% nitric acid mixed in methanol base.
  • the TEM specimens were ion-milled using a Gatan Precision Ion Polishing System (PIPS).
  • the ion-milling was done at 4.5 keV, and the inclination angle was reduced from 4° to 2° to open up the thin area.
  • the TEM studies were done using a JEOL 2100 high-resolution microscope operated at 200 kV.
  • FIG. 22 shows the bright-field and dark-field images of the samples made from the gage section of tensile specimen.
  • Recrystallized Modal Structure (Structure #4, FIG. 3B ) can undergo recrystallization again if subjected to high temperature exposure forming Recrystallized Modal Structure (Structure #4, FIG. 3B ).
  • This ability to go through multiple cycles of recrystallization to the Recrystallized Modal Structure, refinement through NanoPhase Refinement and Strengthening, formation of the Refined High Strength Nanomodal Structure and its recrystallization back to the Recrystallized Modal Structure is applicable in industrial sheet production to produce steel sheet with increasingly finer gauges (i.e. thickness) for specific targeted industrial applications which might be typically found in a range of 0.1 mm to 25 mm.
  • X-ray diffraction was done using a Panalytical X'Pert MPD diffractometer with a Cu K ⁇ x-ray tube and operated at 40 kV with a filament current of 40 mA. The scan was run with a step size of 0.01° and from 25° to 95° two-theta with silicon incorporated to adjust for instrument zero angle shift. The resulting scan was then subsequently analyzed using Rietveld analysis using Siroquant software.
  • Industrial sheet from Alloy 260 was produced by the Thin Strip Casting process. As-solidified thickness of the sheet was 3.2 mm (corresponds to Stage 1 of the Thin Strip Casting process, FIG. 6 ). In-line hot rolling with 19% reduction was applied during production (corresponds to Stage 2 of the Thin Strip Casting process, FIG. 6 ). Final thickness of produced sheet was 2.6 mm.
  • the industrial sheet from Alloy 260 was heat treated at times and temperatures as shown in Table 6 using a Lucifer 7-R24 Atmosphere Controlled Box Furnace. These temperature/time combinations were selected to simulate extreme thermal exposure that may occur within a produced coil during homogenization heat treatment at either the outside or inside of the coil.
  • the sheet was processed according to Steps 2 and 3 in Table 18 to mimic commercial sheet post-processing methods.
  • the sheet was cold rolled with approximately 15% reduction in one rolling pass. This cold rolling simulates the cold rolling necessary to reduce the material thickness to final gauge levels needed for commercial products.
  • Cold rolling was completed using a Fenn Model 061 rolling mill.
  • Tensile samples were cut using a Brother HS-3100 electrical discharge machine (EDM) of hot rolled, heat treated and cold rolled material. Cold rolled tensile samples were heat treated at 1150° C. for 5 minutes in a Lindberg Blue M Model “BF51731C-1” Box Furnace in air to simulate in-line annealing on a cold rolling production line.
  • EDM electrical discharge machine
  • Tensile properties were measured of sheet material in the as hot rolled, overaged, cold rolled, and annealed states. The tensile properties were tested on an Instron mechanical testing frame (Model 3369), utilizing Instron's Bluehill control and analysis software. All tests were run at room temperature in displacement control with the bottom fixture held rigid and the top fixture moving with the load cell attached to the top fixture. Video extensometer was utilized for strain measurements. Tensile properties for industrial sheet from Alloy 260 after overaging heat treatment at 1150° C. for 8 hours and 16 hours and following steps of post-processing are shown in FIG. 24 and FIG. 25 , respectively. Note that despite property improvement as compared to as-produced sheet, tensile properties of the 1150° C.
  • Industrial sheet from Alloy 284 was produced by Thin Strip Casting process with an as-solidified thickness of 3.2 mm (corresponds to Stage 1 of the Thin Strip Casting process, FIG. 6 ). In-line hot rolling with 19% reduction was applied during production (corresponds to Stage 2 of the Thin Strip Casting process, FIG. 6 ). Final thickness of produced sheet was 2.6 mm. Samples from the produced sheet were heat treated at times and temperatures as shown in Table 15 using a Lucifer 7-R24 Atmosphere Controlled Box Furnace. These temperature/time combinations were selected to simulate extreme thermal exposure that may occur within a produced coil during homogenization heat treatment at either the outside or inside of the coil.
  • the sheet was processed according to Steps 2 and 3 in Table 19 to mimic commercial sheet production methods.
  • the sheet was cold rolled approximately 15% in one rolling pass. This cold rolling simulates the cold rolling necessary to reduce the material thickness to reduced levels needed for commercial products.
  • Cold rolling was completed using a Fenn Model 061 rolling mill.
  • Tensile samples were cut using a Brother HS-3100 electrical discharge machine (EDM) of hot rolled, heat treated and cold rolled material.
  • Cold rolled tensile samples were heat treatment at 1150° C. for 5 minutes in a Lindberg Blue M Model “BF51731C-1” Box Furnace in air to simulate in-line annealing on a cold rolling production line. Anneal times were selected to be short so as to be insignificant compared to the time at temperature during the overaging heat treatment.
  • Tensile properties were measured of Alloy 284 sheet in the as hot rolled, overaged, cold rolled, and annealed states. The tensile properties were tested on an Instron mechanical testing frame (Model 3369) utilizing Instron's Bluehill control and analysis software. All tests were run at room temperature in displacement control with the bottom fixture held rigid and the top fixture moving with the load cell attached to the top fixture. Video extensometer was utilized for strain measurements. Tensile properties for industrial sheet from Alloy 284 after overaging heat treatment at 1150° C. for 8 hours are shown in FIG. 26 . Note that despite property improvement as compared to as-hot rolled sheet, tensile properties of over aged (1150° C.
  • the sheet was cold rolled using a Fenn Model 061 rolling mill from 2.4 mm thickness to 1.0 mm thickness with 2 intermittent stress relief annealing steps at 1150° C. for 5 minutes duration in a Lucifer 7-R24 Atmosphere Controlled Box Furnace. Table 20 chronicles the full processing route for this material. Cold rolling percentages are listed as the percentage reduced from the 2.4 mm 1150° C. for 2 hours heat treated thickness. This cold rolling and annealing process simulates the commercial process necessary to reduce the material thickness to final levels needed for commercial products.
  • Tensile samples were cut using a Brother HS-3100 electrical discharge machine (EDM) of hot rolled, heat treated, cold rolled, and annealed material. Following cutting of tensile samples by EDM, the gauge length of each tensile sample was lightly polished with fine grit SiC paper to remove any surface asperities that may cause scatter in the experimental results.
  • EDM electrical discharge machine
  • Step 1 Heat Treatment 1150° C. for 2 hours
  • Step 2 Cold Work Cold Rolling with 26% reduction
  • Step 3 Annealing 1150° C. for 5 minute
  • Step 4 Cold Work Cold Rolling with 22% reduction
  • Step 5 Annealing 1150° C. for 5 minute
  • Step 6 Cold Work Cold Rolling with 12% reduction
  • Step 7 Annealing 1150° C. for 5 minute
  • Tensile properties were measured of the Alloy 260 sheet in the as hot rolled, heat treated, cold rolled, and annealed states. The tensile properties were tested on an Instron mechanical testing frame (Model 3369), utilizing Instron's Bluehill control and analysis software. All tests were run at room temperature in displacement control with the bottom fixture held rigid and the top fixture moving with the load cell attached to the top fixture. Video extensometer was utilized for strain measurements. Tensile properties for Alloy 260 in the initial (as hot rolled and after step 1) and final (after step 6 and 7) state are shown in FIG. 27 .
  • the cold rolled material developed high strength with reduced ductility as a result of strain hardening and the formation of the Refined High Strength Nanomodal Structure (Structure #5, FIG. 3B ) at step 6 (Table 16). After final annealing, the ductility is restored due to the Recrystallized Modal Structure (Structure #4, FIG. 3B ) formation.
  • this process of strain hardening during cold working, followed by recrystallization during annealing, followed by strain hardening by cold rolling again can be applied multiple times as necessary to hit the final gauge thickness target and provide targeted properties in the sheet.
  • cold rolling gauge reduction followed by annealing is used by the steel industry. This process includes the use of cold rolling mills to mechanically reduce the gauge thickness of sheet with intermediate in-line or batch annealing between passes to remove the cold work present in the sheet.
  • the cold rolling gauge reduction and annealing process was simulated for Alloy 260 material that was commercially produced by the Thin Strip casting process. Alloy 260 was cast at 3.65 mm thickness, and reduced 25% via hot rolling at 1150° C. to 2.8 mm thickness. Following hot rolling, the sheet was coiled and annealed in an industrial batch furnace for a minimum of 2 hours at 1150° C. at the coolest part of the coil. The gauge thickness of the sheet was reduced by 13% in one cold rolling pass by tandem mill, then annealed in-line at 1100° C. for 2 to 5 min.
  • the sheet gauge thickness was further reduced by 25% in 4 cold rolling passes by reversing mill to approximately 1.8 mm in thickness and annealed in an industrial batch furnace at 1100° C. for 30 minutes at the coolest part of the coil (i.e. inner windings).
  • Resultant commercially produced sheet with 1.8 mm thickness was used for further cold rolling in multiple steps using a Fenn Model 061 Rolling Mill with intermediate annealing as described in Table 21. All anneals were completed using a Lucifer 7-R24 box furnace with flowing argon. During anneals, the sheet was loosely wrapped in stainless steel foil to reduce the potential of oxidation from atmospheric oxygen.
  • Step 9 Cold Roll: Anneal: Cold Roll: Anneal: Cold Roll: Anneal: Cold Roll: Anneal: Cold Roll: Anneal: Cold Roll: To 1.5 950° C. To 1.3 mm 950° C. To 1.0 mm 950° C. To 0.9 950° C. 10% Skin mm in 2 for 6 hrs in 1 pass for 6 hrs in 2 passes for 6 hrs mm in 1 for 6 hrs pass roll passes pass
  • Tensile properties of the Alloy 260 sheet were measured at each step of processing. Tensile samples were cut using a Brother HS-3100 wire EDM. The tensile properties were tested on an Instron mechanical testing frame (Model 3369), utilizing Instron's Bluehill control and analysis software. All tests were run at room temperature in displacement control with the bottom fixture held ridged and the top fixture moving with the load cell attached to the top fixture. Video extensometer was utilized for strain measurements. Tensile properties of commercially produced 1.8 mm thick sheet and after each step of processing specified in Table 17 are shown below in Table 18 and illustrated in FIG. 28 . It can be seen that the tensile properties shown in FIG. 28 fall into two distinct groups as indicated by ovals that corresponds to two particular structures ( FIG.
  • the tensile properties shown in FIG. 28 demonstrate that the process of recrystallization during annealing followed by Nanophase Refinement and Strengthening (Mechanism #3, FIG. 3B ) is reversible and may be applied in a cyclic manner during processing of Alloy 260 sheet. Comparing tensile properties from Step 1 and Step 2, the properties demonstrate the effect of recrystallization on Alloy 260, increasing the tensile ductility from approximately 10 to 20% to approximately 35%. Ultimate tensile strength decreases from approximately 1300 MPa to 1150 MPa during the recrystallization process. If the tensile properties of Step 2 and 3 are compared, the effect of Nanophase Refinement and Strengthening (Mechanism #3, FIG.
  • the properties of the sheet within the oval corresponds to Structure #4 depends on annealing parameters and falls in a tight range when the same annealing was applied at Steps 2, 4, 6, and 8 (Table 22).
  • the replication of this process numerous times results with the two property clusters remaining consistent and not overlapping.
  • High Strength Nanomodal Structure can be applied in a cyclic nature as often as necessary in order to reach end user gauge thickness requirements typically 0.1 to 25 mm thickness for Structures #3, #4 or #5.
  • Thick slab casting is the process whereby molten metal is solidified into a “semifinished” slab for subsequent rolling in the finishing mills.
  • molten steel flows from a ladle, through a tundish into the mold. Once in the mold, the molten steel freezes against the water-cooled copper mold walls to form a solid shell.
  • Drive rolls lower in the machine continuously withdraw the shell from the mold at a rate or “casting speed” that matches the flow of incoming metal, so the process ideally runs in steady state.
  • the solidifying steel shell acts as a container to support the remaining liquid. Rolls support the steel to minimize bulging due to the ferrostatic pressure.
  • This structure would be applicable to be processed into parts by end-users through many different routes including cold stamping, hydroforming, roll forming etc. and during this processing step would then transform into the partial or full Refined High Strength Nanomodal Structure (Structure #5). Note that a variation of this would include cold rolling to a lower extent (perhaps 2 to 10%) to cause partial Nanophase Refinement & Strengthening to tailor sets of properties (i.e. yield strength, tensile strength, and total elongation) for specific applications.
  • the steel is cast directly to slabs with a thickness between 20 and 150 mm.
  • the method involves pouring molten steel into the Tundish at the top of the slab caster, from a ladle. They are sized with a working volume of about 100 t, which will deliver the steel at a rate of one ladle every 40 minutes to the caster.
  • the temperatures of liquid steel in the tundish as well as the steel purity and chemical composition have a significant impact on the quality of the cast product.
  • the liquid steel passes at a controlled rate into the caster, which is made up of a water cooled mould in which the outer surface of the steel solidifies.
  • the slabs leaving the caster are about 70 mm thick, 1000 mm wide and approximately 40 m long. These are then cut by the shearer to length.
  • a hydraulic oscillator and electromagnetic brakes are fitted to control the molten liquid whilst in the mould.
  • FIG. 30 A schematic of the Thin Slab Casting process is shown in FIG. 30 .
  • the Thin Slab Casting process can be separated into three stages similar to Thin Strip Casting ( FIG. 6 ).
  • Stage 1 the liquid steel is both cast and rolled in an almost simultaneous fashion.
  • the solidification process begins by forcing the liquid melt through a copper or copper alloy mold to produce initial thickness typically from 20 to 150 mm in thickness based on liquid metal processability and production speed. Almost immediately after leaving the mold and while the inner core of the steel sheet is still liquid, the sheet undergoes reduction using a multistep rolling stand which reduces the thickness significantly down to 10 mm depending on final sheet thickness targets.
  • the steel sheet is heated by going through one or two induction furnaces and during this stage the temperature profile and the metallurgical structure is homogenized.
  • the sheet is further rolled to the final gage thickness target is typically in the range of 2 to 5 mm thick. Further gauge reduction would occur normally through subsequent cold rolling which would trigger the identified Dynamic Nanophase Strengthening mechanism. As the coils are often supplied in the annealed condition, annealing of the cold rolled sheet would then result in the formation of the Recrystallized Modal Structure.
  • This structure would be applicable to be processed into parts by many different routes including cold stamping, hydroforming, roll forming etc. and during this processing step would then transform into the partial or full Refined High Strength Nanomodal Structure.
  • the Recrystallized Modal Structure can be partially or fully transformed into the Refined High Strength Nanomodal Structure depending on the specific application and the end-user requirements. Partial transformation occurs with 1 to 25% strain while depending on the specific material, its processing and resulting properties will typically result in complete transformation from 25% to 75% strain. While the three stage process of forming sheet in thin slab casting is part of the process, the response of the alloys herein to these stages is unique based on the mechanisms and structure types described herein and the resulting novel combinations of properties.

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CA2926184C (fr) 2022-11-29
CN105765096A (zh) 2016-07-13
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US20150101714A1 (en) 2015-04-16
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JP2016540113A (ja) 2016-12-22
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