WO2004022794A1 - Procede de production d'acier a austenite residuelle - Google Patents

Procede de production d'acier a austenite residuelle Download PDF

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Publication number
WO2004022794A1
WO2004022794A1 PCT/US2003/027825 US0327825W WO2004022794A1 WO 2004022794 A1 WO2004022794 A1 WO 2004022794A1 US 0327825 W US0327825 W US 0327825W WO 2004022794 A1 WO2004022794 A1 WO 2004022794A1
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WIPO (PCT)
Prior art keywords
austenite
temperature
carbon
steel alloy
steel
Prior art date
Application number
PCT/US2003/027825
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English (en)
Inventor
John G. Speer
David K. Matlock
Matthew F. Gallagher
Original Assignee
Colorado School Of Mines
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Colorado School Of Mines filed Critical Colorado School Of Mines
Priority to US10/526,840 priority Critical patent/US20060011274A1/en
Priority to AU2003270334A priority patent/AU2003270334A1/en
Publication of WO2004022794A1 publication Critical patent/WO2004022794A1/fr

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Classifications

    • 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
    • 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
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18Hardening; Quenching with or without subsequent tempering
    • 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
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18Hardening; Quenching with or without subsequent tempering
    • C21D1/19Hardening; Quenching with or without subsequent tempering by interrupted quenching
    • 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
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18Hardening; Quenching with or without subsequent tempering
    • C21D1/185Hardening; Quenching with or without subsequent tempering from an intercritical temperature
    • 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
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18Hardening; Quenching with or without subsequent tempering
    • C21D1/19Hardening; Quenching with or without subsequent tempering by interrupted quenching
    • C21D1/20Isothermal quenching, e.g. bainitic hardening
    • 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
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18Hardening; Quenching with or without subsequent tempering
    • C21D1/19Hardening; Quenching with or without subsequent tempering by interrupted quenching
    • C21D1/22Martempering
    • 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
    • C21D2211/005Ferrite
    • 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
    • C21D2211/008Martensite
    • 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
    • C21D8/0273Final recrystallisation annealing

Definitions

  • the invention is directed to a method for producing steels with microstructures containing retained austenite.
  • the difficulty that this invention seeks to address is that of creating a microstructure in steel, (e.g., but not limited to, low carbon sheet steel) that contains austenite at the ambient temperature at which the steel is to be used in some application, typically room temperature.
  • austenite usually must be enriched with carbon (or sometimes nitrogen) in order to stabilize it to room temperature. (Actually, it is metastable, and undergoes subsequent transformation to martensite during deformation, a key component of its utility in service.)
  • the problem is to enrich some austenite in the microstructure with carbon, by controlling microstructure evolution and carbon partitioning, without having to use a much higher carbon-containing steel, which is usually undesired for reasons such as reduced weldability.
  • the present invention recognizes that the carbon partitioning and growth of the body- centered phase are decoupled in martensite transformations and that this decoupling provides a mechanism for controlling the austenite fraction and its carbon concentration (the kinetics of carbon partitioning are separate from the mechanisms of ferrite formation), since the extent of martensite transformation is controlled primarily by temperature only, rather than both time and temperature.
  • This new concept provides additional flexibility for implementing more convenient or less costly processing strategies or methodologies for producing steel with retained austenite.
  • a steel alloy is subjected to a heating step to produce austenite.
  • the temperature to which the alloy is brought during the heating step is selected to achieve either full or partial austenitization.
  • the steel alloy is subjected to a quenching step that brings the alloy to a temperature within the temperature range at which martensite is produced.
  • the alloy is subjected to a carbon partitioning step by bringing the alloy to a carbon partitioning temperature, i.e., a temperature at which there is substantial carbon mobility.
  • a carbon partitioning temperature i.e., a temperature at which there is substantial carbon mobility.
  • there is a range of temperatures at which there is substantial carbon mobility there is a range of temperatures at which there is substantial carbon mobility.
  • carbon is transferred from the martensite to the austenite to enrich the austenite so that when the alloy is cooled to the ambient application temperature, typically room temperature, the austenite is stable.
  • Figure 1 depicts a time vs. temperature schematic of the conventional transformation induced plasticity (TRIP) steel bainite processing to produce steel with retained austenite;
  • TRIP transformation induced plasticity
  • Figure 2 depicts a time vs. temperature schematic of a process for producing steel with retained austenite that comprises a step of partitioning carbon to austenite; and Figure 3 depicts the austenite volume fraction for various partition times for a sheet steel.
  • the present invention is directed to a process to produce steels with carbon-enriched retained austenite based on a new understanding of the fundamentals of carbon partitioning in martensite/austenite mixtures. It should be appreciated that the process is broadly applicable to steels that contain more than just martensite plus austenite (and indeed the TRIP steels that are used in the following example of the method contain substantial fractions of equiaxed ferrite). It should further be appreciated that although some bainitic transformation of the retained austenite could also occur in parallel with the carbon partitioning step of the present invention, such bainitic transformation processes can be controlled by alloying so as to influence bainite transformation kinetics to provide an additional variant to the microstructures achieved with the process of the present invention.
  • the process involves: (a) heating the steel to form austenite (either completely or partially); (b) quenching the steel to a temperature, usually above ambient, that is in the temperature range at which martensite forms (M s to M f , where M s defines the upper temperature boundary of the range and M f defines the lower temperature boundary of the range) to create controlled amounts of martensite and retained austenite; and (c) thermally treating the steel to partition carbon into the austenite, and thereby increase the chemical stability of the austenite.
  • the present invention differs profoundly from the conventional quenching and tempering processes. Namely, conventional quenching and tempering processes are designed to temper the martensite, typically combining the available carbon in the form of carbides, and decomposing the retained austenite. Further, there is no intent to partition the carbon to austenite in these treatments. In contrast, in the present invention, formation of iron carbides is intentionally suppressed, and the austenite is intentionally stabilized rather than decomposed.
  • the present invention is believed to have potential application wherever carbon- enriched retained austenite offers improved product characteristics.
  • Several applications are envisioned, including (1) high strength sheet steel; (2) high strength bar and forging steels; (3) higher carbon steels, such as carburized gears and bearings; and (4) austempered ductile cast iron.
  • these types of steel are particularly applicable to ground transportation vehicles.
  • TRIP sheet steels are of great current interest for automotive sheet applications and high strength products that make use of controlled amounts of retained austenite, typically on the order of 10% austenite.
  • TRIP sheet steel with retained austenite such as that produced by processes that use bainite transformation, typically in excess of 1% carbon (by weight) in the austenite, are capable of undergoing martensite transformation during deformation. This capability provides several advantages that are useful in various applications. For example, TRIP sheet steel with retained austentite has improved formability, and increased energy absorbance (such as would apply to a vehicle collision in automotive application).
  • the microstructures for the TRIP sheet steel of this example also contain equiaxed ferrite, along with different amounts of high strength constituents such as bainite and pearlite, which provide various desired properties known to those skilled in the art. It should, however, be appreciated that the present invention does not require any of these additional constituents to realize a TRIP sheet steel with carbon enriched austenite that is stable or metastable at room temperature or an application temperature. Further, to the extent that additional constituents are employed, a greater or lesser number of constituents can be employed and the relative amounts of such constituents can be varied depending on the desired microstructure. Further, the use of additional constituents to achieve desired properties is applicable to steels other than TRIP sheet steel.
  • the present process offers an alternative approach to conventional TRIP sheet production, and a method is explained here, to design steel alloys and processing parameters (i.e. especially the temperatures used during the present process), to achieve desired microstructures.
  • the range of microstructures available via the present process is also greater than may be achieved via conventional bainitic processing.
  • a schematic for the present process is shown in Figure 2, which would apply to processing of cold-rolled and coated sheet products that use an annealing process.
  • the schematic diagram includes the annealing temperature (AT), the quench temperature (QT), and the partitioning temperature PT.
  • AT annealing temperature
  • QT quench temperature
  • PT partitioning temperature
  • an alloy of composition 0.15C is considered, typical of TRIP products where the carbon level is limited somewhat by weldability constraints.
  • the alloy might also contain manganese (and possibly other hardenability additions), perhaps 1%, to suppress undesired reactions during cooling, and significantly elevated silicon levels, perhaps 1.5%, to suppress carbide formation.
  • manganese and possibly other hardenability additions
  • silicon levels perhaps 1.5%, to suppress carbide formation.
  • Other elements such as N, Al, S, are also contained in typical sheet steels, but are not considered in detail for this example.
  • the annealing step causes recrystallization of the cold-rolled structure, and establishes the initial austenite.
  • the annealing temperature can be above the A 3 , providing full austenitization, or in the intercritical regime between Ai and A 3 (Ai being the temperature at which austenite begins to form), providing both ferrite and austenite.
  • the amounts of ferrite and austenite, and their carbon concentrations are established by the applicable phase equilibrium at the selected temperature.
  • a 3 (°C) 910 - 203VC - 15.2 + 44.7S/ + 104F + 31.5M> + 13.1fF (1)
  • C carbon by weight percentage
  • Ni nickel by weight percentage
  • Si silicon by weight percentage
  • V vanadium by weight percentage
  • Mo molybdenum by weight percentage
  • W Tungsten by weight percentage
  • f ⁇ is the amount of ferrite by weight percentage
  • C ⁇ is the carbon by weight percentage in the austenite phase
  • f ⁇ is the amount of austenite by weight percentage
  • C ⁇ is carbon by weight percentage in the ferrite phase
  • C a ⁇ 0 y is the carbon content in the steel overall, by weight percentage.
  • the carbon content in ferrite is low, and C ⁇ ⁇ 0 can be used to give an approximate solution for the purpose of illustration in this example. At 810°C in the 0.15C, l .OMn, 1.5Si steel, about 78% ferrite, plus 22% austenite, are anticipated.
  • the ferrite During the quenching step, which occurs after the annealing step, the ferrite remains essentially unchanged and the austenite transforms partially to martensite, depending on the relationship between the quenching temperature (QT), and the M s temperature of the remaining austenite.
  • QT quenching temperature
  • M s and M f define the temperature range over which martensite forms. See Figure 2.
  • the M s temperature can be estimated using another correlation of Andrews:
  • C carbon by weight percentage
  • Mn manganese by weight percentage
  • Cr chromium by weight percentage
  • Ni nickel by weight percentage
  • Mo molybdenum by weight percentage.
  • the M s temperature is about 456°C, although for austenite at an intercritical annealing temperature of 810°C (C ⁇ ⁇ 0.68%), the M s temperature is about 355°C.
  • / ⁇ r is the amount of austenite just prior to quenching, i.e. 22% in this example.
  • the quench temperature is 150°C, then about 12% martensite is formed during the quench, along with the remaining 10% austenite, and 78% equiaxed ferrite.
  • Constrained paraequilibrium defines the endpoint of carbon partitioning in the absence of either short- or long-range diffusion of iron or substitutional atoms, which applies to martensite/austenite mixtures at low temperatures where the ⁇ / ⁇ interface is stationary.
  • the recently developed CPE theory indicates that the austenite in the present example could be enriched in carbon to a level of approximately 1.5% at a partitioning temperature (PT) of about 450°C, while the martensite is depleted to quite low carbon levels.
  • PT partitioning temperature
  • the essence of the CPE theory involves a condition where the chemical potential of carbon is equal in the ⁇ and ⁇ phases, in the absence of substantial carbide formation, and the ⁇ / ⁇ interface is effectively stationary, i.e. constrained, at usual partitioning temperatures.)
  • the austenite is stable after final cooling to room temperature.
  • the partitioning kinetics are also temperature dependent, but suitable partitioning should be able to be accomplished under time/temperature conditions that are usually employed for bainitic transformation (the required time is also dependent upon microstructural and other factors).
  • bainitic ferrite growth in addition to carbon partitioning is required for conventional bainitic processing.
  • the steel composition and processing parameters used here produce a final microstructure of 78% equiaxed ferrite, 12% carbon-depleted martensite, and 10% retained austenite (having approximately 1.5% carbon).
  • Such a microstructure is expected to represent a commercially viable TRIP product.
  • other microstructure variants can be designed by altering the steel composition and critical processing parameters. Some of these microstructures would be difficult to achieve by conventional processing, and the new process allows the potential for higher levels of carbon enrichment in the austenite, increasing strength via formation of lath martensite in the microstructure, and application to Si/Al-containing iron castings.
  • Example results are shown in Figure 3, obtained for a 0.19C, 1.46Mn, 1.96 AI sheet steel., intercritical ly annealed for 180 s at 805°C to create a ferrite/austenite starting microstructure, followed by quenching to 284°C, and then partitioning for various times and temperatures (between 300 and 450°C) shown in the figure. The final austenite fraction after complete processing is shown. This example shows that substantial quantities of retained austenite are achieved by Q&P processing, where the quenching temperature was carefully selected to control the transformed microstructure prior to quenching.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Sheet Steel (AREA)

Abstract

L'invention concerne un procédé de production d'acier à austénite résiduelle. Dans un mode de réalisation, le procédé comprend les étapes consistant à chauffer un alliage d'acier pour produire de l'austénite, à tremper l'acier pour produire du martensite, et à séparer du carbone pour le transférer du martensite à l'austénite.
PCT/US2003/027825 2002-09-04 2003-09-04 Procede de production d'acier a austenite residuelle WO2004022794A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US10/526,840 US20060011274A1 (en) 2002-09-04 2003-09-04 Method for producing steel with retained austenite
AU2003270334A AU2003270334A1 (en) 2002-09-04 2003-09-04 Method for producing steel with retained austenite

Applications Claiming Priority (2)

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US31952102P 2002-09-04 2002-09-04
US60/319,521 2002-09-04

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