WO2016100839A1 - Hot rolled light-gauge martensitic steel sheet and method for making the same - Google Patents

Hot rolled light-gauge martensitic steel sheet and method for making the same Download PDF

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Publication number
WO2016100839A1
WO2016100839A1 PCT/US2015/066714 US2015066714W WO2016100839A1 WO 2016100839 A1 WO2016100839 A1 WO 2016100839A1 US 2015066714 W US2015066714 W US 2015066714W WO 2016100839 A1 WO2016100839 A1 WO 2016100839A1
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WIPO (PCT)
Prior art keywords
steel sheet
gauge
hot rolled
mpa
less
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Legal status (The legal status 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 status listed.)
Ceased
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PCT/US2015/066714
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French (fr)
Inventor
James W. WATSON
Paul Kelly
David VAN AKINS
Christopher Ronald Killmore
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Nucor Corp
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Nucor Corp
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Filing date
Publication date
Application filed by Nucor Corp filed Critical Nucor Corp
Priority to DE112015005690.4T priority Critical patent/DE112015005690T8/en
Priority to CN201580073870.4A priority patent/CN107438487B/en
Priority to MX2017008027A priority patent/MX2017008027A/en
Priority to KR1020177020061A priority patent/KR102596515B1/en
Priority to GB1709282.6A priority patent/GB2548049B/en
Priority to JP2017532049A priority patent/JP6778943B2/en
Publication of WO2016100839A1 publication Critical patent/WO2016100839A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
    • B22D11/0622—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by two casting wheels
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/002—Heat treatment of ferrous alloys containing Cr
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/005—Heat treatment of ferrous alloys containing Mn
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/008—Heat treatment of ferrous alloys containing Si
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226—Hot rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0263—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese

Definitions

  • This invention relates to the making of hot rolled light-gauge martensitic steel sheet and the method for making the same by a twin roll caster.
  • Martensite is formed in carbon steels by the rapid cooling, or quenching, of austenite.
  • Austenite has a particular crystalline structure known as face-centered cubic (FCC). If allowed to cool naturally, austenite turns into ferrite and cementite. However, when the austenite is rapidly cooled, or quenched, the face-centered cubic austenite transforms to a highly strained body-centered tetragonal (BCT) form of ferrite that is supersaturated with carbon. The shear deformations that result, produce large numbers of dislocations, which is a primary strengthening mechanism of steels.
  • the martensitic reaction begins during cooling when the austenite reaches the martensite start temperature and the parent austenite becomes thermodynamically unstable. As the sample is quenched, an increasingly large percentage of the austenite transforms to martensite until the lower transformation temperature is reached, at which time the transformation is completed.
  • Martensitic steels are increasingly being used in applications that require high strength, for example, in the automotive industry. Martensitic steel provides the strength necessary by the automotive industry while decreasing energy consumption and improving fuel economy.
  • a hot rolled light-gauge martensitic steel sheet made by the steps comprising: (a) preparing a molten steel melt comprising: (i) by weight, between 0.20% and 0.35% carbon, less than 1.0% chromium, between 0.7% and 2.0% manganese, between 0.10% and 0.50% silicon, between 0.1 % and 1.0% copper, less than 0.05% niobium, less than 0.5% molybdenum, and silicon killed containing less than 0.01% aluminum, and (ii) the remainder iron and impurities resulting from melting; (b) solidifying at a heat flux greater than 10.0 MW/m 2 into a steel sheet less than 2.0 mm in thickness and cooling the sheet in a non-oxidizing atmosphere to below 1080 °C and above A3 ⁇ 4 temperature at a cooling rate greater than 15 °C/s; and (c) hot rolling the steel sheet to between 15% and 50% reduction and rapidly cooling to form a steel sheet with a microstructure having by volume at
  • the present steel sheet cannot be made with carbon levels below 0.20% because it is inoperative with peritectic cracking of the steel sheet as explained below.
  • the steel sheet may be tempered at a temperature between 150 °C and 250 °C for between 2 and 6 hours.
  • the martensitic steel sheet may further comprise by weight greater than 0.005% niobium or greater than 0.01 % or 0.02% niobium.
  • the martensitic steel sheet may further comprise by weight greater than 0.05% molybdenum or greater than 0.1 % or 0.2% molybdenum.
  • the molten melt may be solidified at a heat flux greater than 10.0 MW/m 2 into a steel sheet less than 2.0 mm in thickness, and the sheet may be cooled in a non-oxidizing atmosphere to below 1080 °C and above A3 ⁇ 4 temperature at a cooling rate greater than 15 °C/s.
  • a non-oxidizing atmosphere is an atmosphere typically of an inert gas such as nitrogen or argon, or a mixture thereof, which contains less than about 5 % oxygen by weight.
  • the martensite in the steel sheet may come from an austenite grain size of greater than 100 ⁇ . In other embodiments, the martensite in the steel sheet may come from an austenite grain size of greater than 150 ⁇ .
  • the steel sheet may be hot rolled to between 15% and 35% reduction and rapidly cooled to form a steel sheet with a microstructure having at least 75% martensite, a yield strength of between 700 and 1300 MPa, a tensile strength of between 1000 and 1800 MPa and an elongation of between 1 % and 10% .
  • the steel sheet may be hot rolled to between 15% and 50% reduction and rapidly cooled to form a steel sheet with a microstructure having at least 75% martensite plus bainite, a yield strength of between 700 and 1300 MPa, a tensile strength of between 1000 and 1800 MPa and an elongation of between 1 % and 10% .
  • the steel sheet may be hot rolled to between 15% and 35% reduction and rapidly cooled to form a steel sheet with a microstructure having at least 75% martensite plus bainite, a yield strength of between 700 and 1300 MPa, a tensile strength of between 1000 and 1800 MPa and an elongation of between 1 % and 10% .
  • the molten steel used to produce the hot rolled light gauge martensitic steel sheet is silicon killed (i.e., silicon deoxidized).
  • the martensitic steel sheet may further comprise by weight less than 0.008% aluminum or less than 0.006% aluminum.
  • the molten melt may have a free oxygen content between 5 to 70 ppm.
  • the steel sheet may have a total oxygen content greater than 50 ppm.
  • the inclusions include MnOSi02 typically with 50% less than 5 ⁇ in size and have the potential to enhance microstructure evolution and, thus, the strip mechanical properties.
  • a method of making hot rolled light-gauge martensitic steel sheet comprising the steps of: (a) preparing a molten steel melt comprising: (i) by weight, between 0.20% and 0.35% carbon, less than 1.0% chromium, between 0.7% and 2.0% manganese, between 0.10% and 0.50% silicon, between 0.1 % and 1.0% copper, less than 0.05% niobium, less than 0.5% molybdenum, and silicon killed containing less than 0.01% aluminum, and (ii) the remainder iron and impurities resulting from melting; (b) forming the molten melt into a casting pool supported on casting surfaces of a pair of cooled casting rolls having a nip there between; (c) counter rotating the casting rolls and solidifying at a heat flux greater than 10.0 MW/m 2 producing a steel sheet less than 2.0 mm in thickness and cooling the sheet in a non-oxidizing atmosphere to below 1080 °C and above A3 ⁇ 4 temperature at
  • the method of making hot rolled light-gauge martensite steel sheet may comprise the step of tempering the steel sheet at a temperature between 150 °C and 250 °C for between 2 and 6 hours.
  • the martensitic steel sheet may further comprise by weight greater than 0.005% niobium or greater than 0.01 % or 0.02% niobium.
  • the martensitic steel sheet may further comprise by weight greater than 0.05% molybdenum or greater than 0.1% or 0.2% molybdenum.
  • the martensitic steel sheet may be silicon killed containing by weight less than 0.008% aluminum or less than 0.006% aluminum.
  • the molten melt may have a free oxygen content between 5 to 70 ppm.
  • the steel sheet may have a total oxygen content greater than 50 ppm.
  • the molten melt may be solidified at a heat flux greater than 10.0 MW/m 2 into a steel sheet less than 2.0 mm in thickness, and cooled in a non-oxidizing atmosphere to below 1080 °C and above A3 ⁇ 4 temperature at a cooling rate between greater than 15 °C/s.
  • the martensite in the steel sheet may come from an austenite grain size of greater than 100 ⁇ . In other embodiments, the martensite in the steel sheet may come from an austenite grain size of greater than 150 ⁇ .
  • the method of making hot rolled light-gauge martensitic steel sheet may further comprise hot rolling the steel sheet to between 15% and 35% reduction and rapidly cooling to form a steel sheet with a microstructure having at least 75% by volume martensite, a yield strength of between 700 and 1300 MPa, a tensile strength of between 1000 and 1800 MPa and an elongation of between 1 % and 10% .
  • the method of making hot rolled light-gauge martensitic steel sheet may further comprise hot rolling the steel sheet to between 15% and 50% reduction and rapidly cooling to form a steel sheet with a microstructure having at least 75% by volume martensite plus bainite, a yield strength of between 700 and 1300 MPa, a tensile strength of between 1000 and 1800 MPa and an elongation of between 1% and 10% .
  • the method of making hot rolled light- gauge martensitic steel sheet may comprise hot rolling the steel sheet to between 15% and 35% reduction and rapidly cooling to form a steel sheet with a microstructure having at least 75% by volume martensite plus bainite, a yield strength of between 700 and 1300 MPa, a tensile strength of between 1000 and 1800 MPa and an elongation of between 1% and 10% .
  • FIG. 1 illustrates a strip casting installation incorporating an in-line hot rolling mill and coiler
  • FIG. 2 illustrates details of the twin roll strip caster
  • FIG. 3 is a micrograph of a steel sheet with a microstructure having at least 75% martensite.
  • FIGS. 1 and 2 illustrate successive parts of strip caster for continuously casting steel strip of the present invention.
  • a twin roll caster 11 may continuously produce a cast steel strip 12, which passes in a transit path 10 across a guide table 13 to a pinch roll stand 14 having pinch rolls 14A.
  • the strip passes into a hot rolling mill 16 having a pair of work rolls 16A and backing rolls 16B, where the cast strip is hot rolled to reduce a desired thickness.
  • the hot rolled strip passes onto a runout table 17 where the strip enters an intensive cooling section via water jets 18 (or other suitable means).
  • the rolled and cooled strip then passes through a pinch roll stand 20 comprising a pair of pinch rolls 20A and then to a coiler 19..
  • twin roll caster 11 comprises a main machine frame 21, which supports a pair of laterally positioned casting rolls 22 having casting surfaces 22A.
  • Molten metal is supplied during a casting operation from a ladle (not shown) to a tundish 23, through a refractory shroud 24 to a distributor or moveable tundish 25, and then from the distributor or moveable tundish 25 through a metal delivery nozzle 26 between the casting rolls 22 above the nip 27.
  • the molten metal delivered between the casting rolls 22 forms a casting pool 30 above the nip supported on the casting rolls.
  • the casting pool 30 is restrained at the ends of the casting rolls by a pair of side closure dams or plates 28, which may be urged against the ends of the casting rolls by a pair of thrusters (not shown) including hydraulic cylinder units (not shown) connected to the side plate holders.
  • the upper surface of casting pool 30 (generally referred to as the "meniscus" level) usually is above the lower end of the delivery nozzle so that the lower end of the delivery nozzle is immersed within the casting pool 30.
  • Casting rolls 22 are internally water cooled so that shells solidify on the moving casting roll surfaces as they pass through the casting pool, and are brought together at the nip 27 between them to produce the cast strip 12, which is delivered downwardly from the nip between the casting rolls.
  • the twin roll caster may be of the kind that is illustrated and described in some detail in U.S. Patent. Nos. 5,184,668 and 5,277,243 or U.S. Patent. No. 5,488,988, or U.S. Patent Application No. 12/050,987. Reference is made to those patents which are incorporated by reference for appropriate construction details of a twin roll caster that may be used in an embodiment of the present invention.
  • the in-line hot rolling mill 16 provides 15 % to 50 % reductions of strip from the caster.
  • the cooling may include a water cooling section to control the cooling rates of the austenite transformation to achieve desired microstructure and material properties.
  • a light-gauge martensitic steel sheet may be made from a molten melt produced in a twin roll caster.
  • the hot rolled light-gauge martensitic steel sheet may be made by the steps comprising: (a) preparing a molten steel melt comprising: (i) by weight, between 0.20% and 0.35% carbon, less than 1.0% chromium, between 0.7% and 2.0% manganese, between 0.10% and 0.50% silicon, between 0.10% and 1.0% copper, less than 0.05% niobium, less than 0.5% molybdenum, and silicon killed containing less than 0.01% aluminum, and (ii) the remainder iron and impurities resulting from melting; (b) solidifying at a heat flux greater than 10.0 MW/m 2 producing a steel sheet less than 2.0 mm in thickness and cooling in a non-oxidizing atmosphere to below 1080 °C and above A3 ⁇ 4 temperature at a cooling rate greater than 15 °C/s; and (c) hot rolling the
  • a martensitic steel sheet was made of the present invention comprising by weight 0.21% carbon, 1.01 % manganese, 0.12% silicon, 0.19% molybdenum, 0.48% chromium, and 0.017% niobium and having a yield strength of 1000 MP, tensile strength of 1385 MPa and an elongation of 5% following quenching.
  • the present steel sheet composition could not be made with carbon levels below 0.20% because it is inoperative with peritectic cracking of the steel sheet.
  • Table No.l shows the effect of carbon content on sheet cracking. At a carbon content below 0.20% the peritectic reaction proceeds too quickly and it is not possible to prevent cracking.
  • the hot rolled light-gauge martensitic steel sheet may be made by the further tempering the steel sheet at a temperature between 150 °C and 250 °C for between 2 and 6 hours. Tempering the steel sheet provides improved elongation with minimal loss in strength. For example, a steel sheet having a yield strength of 1250 MPa, tensile strength of 1600 MPa and an elongation of 2% was improved to a yield strength of 1250 MPa, tensile strength of 1525 MPa and an elongation of 5% following tempering as described herein.
  • the martensitic steel sheet may further comprise by weight greater than 0.005% niobium or greater than 0.01% or 0.02% niobium.
  • the martensitic steel sheet may comprise by weight greater than 0.05% molybdenum or greater than 0.1% or 0.2% molybdenum.
  • the martensitic steel sheet may be silicon killed containing by weight less than 0.008% aluminum or less than 0.006% aluminum.
  • the molten melt may have a free oxygen content between 5 to 70 ppm.
  • the steel sheet may have a total oxygen content greater than 50 ppm.
  • the inclusions include MnOSi02 typically with 50% less than 5 ⁇ in size and have the potential to enhance microstructure evolution and, thus, the strip mechanical properties.
  • the molten melt may be solidified at a heat flux greater than 10.0 MW/m 2 into a steel sheet less than 2.0 mm in thickness, and cooled in a non-oxidizing atmosphere to below 1080 °C and above A3 ⁇ 4 temperature at a cooling rate greater than 15 °C/s.
  • a non-oxidizing atmosphere is an atmosphere typically of an inert gas such as nitrogen or argon, or a mixture thereof, which contains less than about 5 % oxygen by weight.
  • the martensite in the steel sheet may come from an austenite grain size of greater than 100 ⁇ . In other embodiments, the martensite in the steel sheet may come from an austenite grain size of greater than 150 ⁇ . Rapid solidification at heat fluxes greater than 10 MW/m 2 enables the production of an austenite grain size that is responsive to controlled cooling after subsequent hot rolling to enable the production of crack free sheet.
  • the steel sheet may be hot rolled to between 15% and 50% reduction and rapidly cooled to form a steel sheet with a microstructure having at least 75% martensite plus bainite, a yield strength of between 700 and 1300 MPa, a tensile strength of between 1000 and 1800 MPa and an elongation of between 1% and 10% . Further, the steel sheet may be hot rolled to between 15% and 35% reduction and rapidly cooled to form a steel sheet with a microstructure having at least 75% martensite plus bainite, a yield strength of between 700 and 1300 MPa, a tensile strength of between 1000 and 1800 MPa and an elongation of between 1% and 10% .

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

Abstract

A hot rolled light-gauge martensitic steel sheet made by the steps comprising: (a) preparing a molten steel melt comprising: (i) by weight, between 0.20% and 0.35% carbon, less than 1.0% chromium, between 0.7% and 2.0% manganese, between 0.10% and 0.50% silicon, between 0.1% and 1.0% copper, less than 0.05% niobium, less than 0.5% molybdenum, and silicon killed containing less than 0.01% aluminum, and (ii) the remainder iron and impurities resulting from melting; (b) solidifying at a heat flux greater than 10.0 MW/m2 and cooling the molten melt into a steel sheet less than 2.0 mm in thickness in a non-oxidizing atmosphere to below 1080°C and above Ar3 temperature at a cooling rate greater than 15°C/s; and (c) hot rolling the steel sheet to between 15% and 50% reduction and rapidly cooling to form a steel sheet with a microstructure having by volume at least 75% martensite or martensite plus bainite, a yield strength of between 700 and 1300 MPa, a tensile strength of between 1000 and 1800 MPa and an elongation of between 1% and 10%.

Description

HOT ROLLED LIGHT-GAUGE MARTENSITIC STEEL SHEET AND METHOD FOR
MAKING THE SAME
BACKGROUND AND SUMMARY
[0001] This international patent application claims priority to U.S. Provisional Application No. 62/094,572, filed on December 19, 2014; and to U.S. Provisional Application No. 62/115,343, filed February 12, 2015.
[0002] This invention relates to the making of hot rolled light-gauge martensitic steel sheet and the method for making the same by a twin roll caster.
[0003] In a twin roll caster, molten metal is introduced between a pair of counter- rotated, internally cooled casting rolls so that metal shells solidify on the moving roll surfaces, and are brought together at the nip between them to produce a solidified strip product, delivered downwardly from the nip between the casting rolls. The term "nip" is used herein to refer to the general region at which the casting rolls are closest together. The molten metal is poured from a ladle through a metal delivery system comprised of a tundish and a core nozzle located above the nip to form a casting pool of molten metal, supported on the casting surfaces of the rolls above the nip and extending along the length of the nip. This casting pool is usually confined between refractory side plates or dams held in sliding engagement with the end surfaces of the rolls so as to dam the two ends of the casting pool against outflow.
[0004] Martensite is formed in carbon steels by the rapid cooling, or quenching, of austenite. Austenite has a particular crystalline structure known as face-centered cubic (FCC). If allowed to cool naturally, austenite turns into ferrite and cementite. However, when the austenite is rapidly cooled, or quenched, the face-centered cubic austenite transforms to a highly strained body-centered tetragonal (BCT) form of ferrite that is supersaturated with carbon. The shear deformations that result, produce large numbers of dislocations, which is a primary strengthening mechanism of steels. The martensitic reaction begins during cooling when the austenite reaches the martensite start temperature and the parent austenite becomes thermodynamically unstable. As the sample is quenched, an increasingly large percentage of the austenite transforms to martensite until the lower transformation temperature is reached, at which time the transformation is completed.
[0005] Martensitic steels are increasingly being used in applications that require high strength, for example, in the automotive industry. Martensitic steel provides the strength necessary by the automotive industry while decreasing energy consumption and improving fuel economy.
[0006] Presently disclosed is a hot rolled light-gauge martensitic steel sheet made by the steps comprising: (a) preparing a molten steel melt comprising: (i) by weight, between 0.20% and 0.35% carbon, less than 1.0% chromium, between 0.7% and 2.0% manganese, between 0.10% and 0.50% silicon, between 0.1 % and 1.0% copper, less than 0.05% niobium, less than 0.5% molybdenum, and silicon killed containing less than 0.01% aluminum, and (ii) the remainder iron and impurities resulting from melting; (b) solidifying at a heat flux greater than 10.0 MW/m2 into a steel sheet less than 2.0 mm in thickness and cooling the sheet in a non-oxidizing atmosphere to below 1080 °C and above A¾ temperature at a cooling rate greater than 15 °C/s; and (c) hot rolling the steel sheet to between 15% and 50% reduction and rapidly cooling to form a steel sheet with a microstructure having by volume at least 75% martensite, a yield strength of between 700 and 1300 MPa, a tensile strength of between 1000 and 1800 MPa and an elongation of between 1% and 10% . Here and elsewhere in this disclosure elongation means total elongation. And by "rapidly cooling" is meant to cool at a rate of more than 100 °C/s to between 100 and 20 °C.
[0007] The present steel sheet cannot be made with carbon levels below 0.20% because it is inoperative with peritectic cracking of the steel sheet as explained below.
[0008] Further, the steel sheet may be tempered at a temperature between 150 °C and 250 °C for between 2 and 6 hours. The martensitic steel sheet may further comprise by weight greater than 0.005% niobium or greater than 0.01 % or 0.02% niobium. The martensitic steel sheet may further comprise by weight greater than 0.05% molybdenum or greater than 0.1 % or 0.2% molybdenum.
[0009] The molten melt may be solidified at a heat flux greater than 10.0 MW/m2 into a steel sheet less than 2.0 mm in thickness, and the sheet may be cooled in a non-oxidizing atmosphere to below 1080 °C and above A¾ temperature at a cooling rate greater than 15 °C/s. A non-oxidizing atmosphere is an atmosphere typically of an inert gas such as nitrogen or argon, or a mixture thereof, which contains less than about 5 % oxygen by weight.
[0010] In some embodiments, the martensite in the steel sheet may come from an austenite grain size of greater than 100 μτη. In other embodiments, the martensite in the steel sheet may come from an austenite grain size of greater than 150 μπι.
[0011] The steel sheet may be hot rolled to between 15% and 35% reduction and rapidly cooled to form a steel sheet with a microstructure having at least 75% martensite, a yield strength of between 700 and 1300 MPa, a tensile strength of between 1000 and 1800 MPa and an elongation of between 1 % and 10% . In other embodiments, the steel sheet may be hot rolled to between 15% and 50% reduction and rapidly cooled to form a steel sheet with a microstructure having at least 75% martensite plus bainite, a yield strength of between 700 and 1300 MPa, a tensile strength of between 1000 and 1800 MPa and an elongation of between 1 % and 10% . Further, the steel sheet may be hot rolled to between 15% and 35% reduction and rapidly cooled to form a steel sheet with a microstructure having at least 75% martensite plus bainite, a yield strength of between 700 and 1300 MPa, a tensile strength of between 1000 and 1800 MPa and an elongation of between 1 % and 10% .
[0012] The molten steel used to produce the hot rolled light gauge martensitic steel sheet is silicon killed (i.e., silicon deoxidized). The martensitic steel sheet may further comprise by weight less than 0.008% aluminum or less than 0.006% aluminum. The molten melt may have a free oxygen content between 5 to 70 ppm. The steel sheet may have a total oxygen content greater than 50 ppm. The inclusions include MnOSi02 typically with 50% less than 5 μπι in size and have the potential to enhance microstructure evolution and, thus, the strip mechanical properties.
[0013] Also disclosed is a method of making hot rolled light-gauge martensitic steel sheet comprising the steps of: (a) preparing a molten steel melt comprising: (i) by weight, between 0.20% and 0.35% carbon, less than 1.0% chromium, between 0.7% and 2.0% manganese, between 0.10% and 0.50% silicon, between 0.1 % and 1.0% copper, less than 0.05% niobium, less than 0.5% molybdenum, and silicon killed containing less than 0.01% aluminum, and (ii) the remainder iron and impurities resulting from melting; (b) forming the molten melt into a casting pool supported on casting surfaces of a pair of cooled casting rolls having a nip there between; (c) counter rotating the casting rolls and solidifying at a heat flux greater than 10.0 MW/m2 producing a steel sheet less than 2.0 mm in thickness and cooling the sheet in a non-oxidizing atmosphere to below 1080 °C and above A¾ temperature at a cooling rate greater than 15 °C/s and (d) hot rolling the steel sheet to between 15% and 50% reduction and rapidly cooling to form a steel sheet with a microstructure having at least 75% martensite, a yield strength of between 700 and 1300 MPa, a tensile strength of between 1000 and 1800 MPa and an elongation of between 1 % and 10% . The steel sheet composition cannot be made with carbon levels below 0.20% because it is inoperative with peritectic cracking of the steel sheet. [0014] Further, the method of making hot rolled light-gauge martensite steel sheet may comprise the step of tempering the steel sheet at a temperature between 150 °C and 250 °C for between 2 and 6 hours.
[0015] The martensitic steel sheet may further comprise by weight greater than 0.005% niobium or greater than 0.01 % or 0.02% niobium. The martensitic steel sheet may further comprise by weight greater than 0.05% molybdenum or greater than 0.1% or 0.2% molybdenum. The martensitic steel sheet may be silicon killed containing by weight less than 0.008% aluminum or less than 0.006% aluminum.
[0016] The molten melt may have a free oxygen content between 5 to 70 ppm. The steel sheet may have a total oxygen content greater than 50 ppm. The molten melt may be solidified at a heat flux greater than 10.0 MW/m2 into a steel sheet less than 2.0 mm in thickness, and cooled in a non-oxidizing atmosphere to below 1080 °C and above A¾ temperature at a cooling rate between greater than 15 °C/s.
[0017] In some embodiments, the martensite in the steel sheet may come from an austenite grain size of greater than 100 μτη. In other embodiments, the martensite in the steel sheet may come from an austenite grain size of greater than 150 μπι.
[0018] The method of making hot rolled light-gauge martensitic steel sheet may further comprise hot rolling the steel sheet to between 15% and 35% reduction and rapidly cooling to form a steel sheet with a microstructure having at least 75% by volume martensite, a yield strength of between 700 and 1300 MPa, a tensile strength of between 1000 and 1800 MPa and an elongation of between 1 % and 10% . In some embodiments, the method of making hot rolled light-gauge martensitic steel sheet may further comprise hot rolling the steel sheet to between 15% and 50% reduction and rapidly cooling to form a steel sheet with a microstructure having at least 75% by volume martensite plus bainite, a yield strength of between 700 and 1300 MPa, a tensile strength of between 1000 and 1800 MPa and an elongation of between 1% and 10% . Furthermore, the method of making hot rolled light- gauge martensitic steel sheet may comprise hot rolling the steel sheet to between 15% and 35% reduction and rapidly cooling to form a steel sheet with a microstructure having at least 75% by volume martensite plus bainite, a yield strength of between 700 and 1300 MPa, a tensile strength of between 1000 and 1800 MPa and an elongation of between 1% and 10% . BRIEF DESCRIPTION OF THE DRAWINGS
[0019] The invention may be more fully illustrated and explained with reference to the accompanying drawings in which:
[0020] FIG. 1 illustrates a strip casting installation incorporating an in-line hot rolling mill and coiler;
[0021] FIG. 2 illustrates details of the twin roll strip caster; and
[0022] FIG. 3 is a micrograph of a steel sheet with a microstructure having at least 75% martensite.
DETAILED DESCRIPTION OF THE DRAWINGS
[0023] FIGS. 1 and 2 illustrate successive parts of strip caster for continuously casting steel strip of the present invention. A twin roll caster 11 may continuously produce a cast steel strip 12, which passes in a transit path 10 across a guide table 13 to a pinch roll stand 14 having pinch rolls 14A. Immediately after exiting the pinch roll stand 14, the strip passes into a hot rolling mill 16 having a pair of work rolls 16A and backing rolls 16B, where the cast strip is hot rolled to reduce a desired thickness. The hot rolled strip passes onto a runout table 17 where the strip enters an intensive cooling section via water jets 18 (or other suitable means). The rolled and cooled strip then passes through a pinch roll stand 20 comprising a pair of pinch rolls 20A and then to a coiler 19..
[0024] As shown in FIG. 2, twin roll caster 11 comprises a main machine frame 21, which supports a pair of laterally positioned casting rolls 22 having casting surfaces 22A. Molten metal is supplied during a casting operation from a ladle (not shown) to a tundish 23, through a refractory shroud 24 to a distributor or moveable tundish 25, and then from the distributor or moveable tundish 25 through a metal delivery nozzle 26 between the casting rolls 22 above the nip 27. The molten metal delivered between the casting rolls 22 forms a casting pool 30 above the nip supported on the casting rolls. The casting pool 30 is restrained at the ends of the casting rolls by a pair of side closure dams or plates 28, which may be urged against the ends of the casting rolls by a pair of thrusters (not shown) including hydraulic cylinder units (not shown) connected to the side plate holders. The upper surface of casting pool 30 (generally referred to as the "meniscus" level) usually is above the lower end of the delivery nozzle so that the lower end of the delivery nozzle is immersed within the casting pool 30. Casting rolls 22 are internally water cooled so that shells solidify on the moving casting roll surfaces as they pass through the casting pool, and are brought together at the nip 27 between them to produce the cast strip 12, which is delivered downwardly from the nip between the casting rolls.
[0025] The twin roll caster may be of the kind that is illustrated and described in some detail in U.S. Patent. Nos. 5,184,668 and 5,277,243 or U.S. Patent. No. 5,488,988, or U.S. Patent Application No. 12/050,987. Reference is made to those patents which are incorporated by reference for appropriate construction details of a twin roll caster that may be used in an embodiment of the present invention.
[0026] The in-line hot rolling mill 16 provides 15 % to 50 % reductions of strip from the caster. On the run-out-table 17, the cooling may include a water cooling section to control the cooling rates of the austenite transformation to achieve desired microstructure and material properties.
[0027] A light-gauge martensitic steel sheet may be made from a molten melt produced in a twin roll caster. The hot rolled light-gauge martensitic steel sheet may be made by the steps comprising: (a) preparing a molten steel melt comprising: (i) by weight, between 0.20% and 0.35% carbon, less than 1.0% chromium, between 0.7% and 2.0% manganese, between 0.10% and 0.50% silicon, between 0.1 % and 1.0% copper, less than 0.05% niobium, less than 0.5% molybdenum, and silicon killed containing less than 0.01% aluminum, and (ii) the remainder iron and impurities resulting from melting; (b) solidifying at a heat flux greater than 10.0 MW/m2 producing a steel sheet less than 2.0 mm in thickness and cooling in a non-oxidizing atmosphere to below 1080 °C and above A¾ temperature at a cooling rate greater than 15 °C/s; and (c) hot rolling the steel sheet to between 15% and 50% reduction and rapidly cooling to form a steel sheet with a microstructure having at least 75% martensite, a yield strength of between 700 and 1300 MPa, a tensile strength of between 1000 and 1800 MPa and an elongation of between 1 % and 10% . Figure 3 shows a micrograph of a steel sheet with a microstructure having at least 75% martensite from a prior austenite grain size of at least 100 μπι.
[0028] For example, a martensitic steel sheet was made of the present invention comprising by weight 0.21% carbon, 1.01 % manganese, 0.12% silicon, 0.19% molybdenum, 0.48% chromium, and 0.017% niobium and having a yield strength of 1000 MP, tensile strength of 1385 MPa and an elongation of 5% following quenching.
[0029] The present steel sheet composition could not be made with carbon levels below 0.20% because it is inoperative with peritectic cracking of the steel sheet. Table No.l shows the effect of carbon content on sheet cracking. At a carbon content below 0.20% the peritectic reaction proceeds too quickly and it is not possible to prevent cracking.
[0030] TABLE 1
Relation between carbon and coil quality with cracking
Figure imgf000008_0001
[0031] Additionally, the hot rolled light-gauge martensitic steel sheet may be made by the further tempering the steel sheet at a temperature between 150 °C and 250 °C for between 2 and 6 hours. Tempering the steel sheet provides improved elongation with minimal loss in strength. For example, a steel sheet having a yield strength of 1250 MPa, tensile strength of 1600 MPa and an elongation of 2% was improved to a yield strength of 1250 MPa, tensile strength of 1525 MPa and an elongation of 5% following tempering as described herein.
[0032] The martensitic steel sheet may further comprise by weight greater than 0.005% niobium or greater than 0.01% or 0.02% niobium. The martensitic steel sheet may comprise by weight greater than 0.05% molybdenum or greater than 0.1% or 0.2% molybdenum. The martensitic steel sheet may be silicon killed containing by weight less than 0.008% aluminum or less than 0.006% aluminum. The molten melt may have a free oxygen content between 5 to 70 ppm. The steel sheet may have a total oxygen content greater than 50 ppm. The inclusions include MnOSi02 typically with 50% less than 5 μτη in size and have the potential to enhance microstructure evolution and, thus, the strip mechanical properties.
[0033] The molten melt may be solidified at a heat flux greater than 10.0 MW/m2 into a steel sheet less than 2.0 mm in thickness, and cooled in a non-oxidizing atmosphere to below 1080 °C and above A¾ temperature at a cooling rate greater than 15 °C/s. A non-oxidizing atmosphere is an atmosphere typically of an inert gas such as nitrogen or argon, or a mixture thereof, which contains less than about 5 % oxygen by weight. [0034] In some embodiments, the martensite in the steel sheet may come from an austenite grain size of greater than 100 μτη. In other embodiments, the martensite in the steel sheet may come from an austenite grain size of greater than 150 μπι. Rapid solidification at heat fluxes greater than 10 MW/m2 enables the production of an austenite grain size that is responsive to controlled cooling after subsequent hot rolling to enable the production of crack free sheet.
[0035] The steel sheet may be hot rolled to between 15% and 50% reduction and rapidly cooled to form a steel sheet with a microstructure having at least 75% martensite plus bainite, a yield strength of between 700 and 1300 MPa, a tensile strength of between 1000 and 1800 MPa and an elongation of between 1% and 10% . Further, the steel sheet may be hot rolled to between 15% and 35% reduction and rapidly cooled to form a steel sheet with a microstructure having at least 75% martensite plus bainite, a yield strength of between 700 and 1300 MPa, a tensile strength of between 1000 and 1800 MPa and an elongation of between 1% and 10% .
[0036] While the invention has been illustrated and described in detail in the foregoing drawings and description, the same is to be considered as illustrative and not restrictive in character, it being understood that only illustrative embodiments thereof have been shown and described, and that all changes and modifications that come within the spirit of the invention described by the following claims are desired to be protected. Additional features of the invention will become apparent to those skilled in the art upon consideration of the description. Modifications may be made without departing from the spirit and scope of the invention.

Claims

What is claimed is:
1. A hot rolled light-gauge martensitic steel sheet made by the steps comprising:
(a) preparing a molten steel melt producing through a twin roll caster an as-cast carbon alloy steel sheet less or equal to 2 mm in thickness comprising:
(i) by weight, between 0.20% and 0.35% carbon, less than 1.0% chromium, between 0.7% and 2.0% manganese, between 0.10% and 0.50% silicon, between 0.1 % and 1.0% copper, less than 0.05% niobium, less than 0.5% molybdenum, and silicon killed containing less than 0.01 % aluminum, and
(ii) the remainder iron and impurities resulting from melting;
(b) solidifying the molten melt at a heat flux greater than 10 MW/m2 into a steel sheet less than 2.0 mm in thickness and cooling the steel sheet in a non-oxidizing atmosphere to below 1080 °C and above the A¾ temperature at a cooling rate greater than 15 °C/s; and
(c) hot rolling the steel sheet to between 15% and 50% reduction and rapidly cooling to form a steel sheet with a microstructure having at least 75% by volume martensite or martensite plus bainite, a yield strength of between 700 and 1300 MPa, a tensile strength of between 1000 and 1800 MPa and an elongation of between 1 % and 10% .
2. The hot rolled light-gauge martensitic steel sheet made by the steps as claimed in claim 1 further comprising the step of:
(d) tempering the steel sheet at a temperature between 150 °C and 250 °C for between 2 and 6 hours.
3. The hot rolled light-gauge martensitic steel sheet as claimed in claim 1 wherein the martensite in the steel sheet comes from an austenite grain size of greater than 100 μπι.
4. The hot rolled light-gauge martensitic steel sheet as claimed in claim 1 wherein the martensite in the steel sheet comes from an austenite grain size of greater than 150 μπι.
5. The hot rolled light-gauge martensitic steel sheet as claimed in claim 1 comprising hot rolling the steel sheet to between 15% and 35% reduction and rapidly cooling to form a steel sheet with a microstructure having at least 75% by volume martensite , a yield strength of between 700 and 1300 MPa, a tensile strength of between 1000 and 1800 MPa and an elongation of between 1 % and 10% .
6. The hot rolled light-gauge martensitic steel sheet as claimed in claim 1 comprising hot rolling the steel sheet to between 15% and 35% reduction and rapidly cooling to form a steel sheet with a microstructure having by volume at least 75% martensite plus bainite, a yield strength of between 700 and 1300 MPa, a tensile strength of between 1000 and 1800 MPa and an elongation of between 1% and 10% .
7. The hot rolled light-gauge martensitic steel sheet as claimed in claim 1 comprising inclusions including MnOSiC with 50% less than 5 μπι in size.
8. The hot rolled light-gauge martensitic steel sheet as claimed in claim 1 where the cooled steel sheet has a total oxygen content greater than 50 ppm.
9. The hot rolled light-gauge martensitic steel sheet as claimed in claim 1 where the molten melt has a free oxygen content between 5 and 70 ppm.
10. The hot rolled light-gauge martensitic steel sheet as claimed in claim 1 further comprising hot rolling the steel sheet to between 15% and 50% reduction and rapidly cooling at a rate of more than 100 °C/s to between 100 and 20 °C to form a steel sheet with a microstructure having at least 75% by volume martensite, a yield strength of between 700 and 1300 MPa, a tensile strength of between 1000 and 1800 MPa and an elongation of between 1% and 10% .
11. A method of making hot rolled light-gauge martensitic steel sheet comprising the steps of:
(a) preparing a molten steel melt comprising:
(i) by weight, between 0.20% and 0.35% carbon, less than 1.0% chromium, between 0.7% and 2.0% manganese, between 0.10% and 0.50% silicon, between 0.1% and 1.0% copper, less than 0.05% niobium, less than 0.5% molybdenum, silicon killed with less than 0.01 % aluminum, and
(ii) the remainder iron and impurities resulting from melting;
(b) forming the melt into a casting pool supported on casting surfaces of a pair of cooled casting rolls having a nip there between;
(c) counter rotating the casting rolls and solidifying at a heat flux greater than 10.0 MW/m2 the molten melt into a steel sheet to less than 2.0 mm in thickness delivered downwardly from the nip and cooling the sheet in a non-oxidizing atmosphere to below 1080 °C and above the A¾ temperature at a cooling rate greater than 15 °C/s and;
(d) hot rolling the steel sheet to between 15% and 50% reduction and rapidly cooling to form a steel sheet with a microstructure having at least 75% by volume martensite or martensite plus bainite, a yield strength of between 700 and 1300 MPa, a tensile strength of between 1000 and 1800 MPa and an elongation of between 1% and 10% .
12. The method of making hot rolled light-gauge martensitic steel sheet as claimed in claim 11 further comprising the step of:
(e) tempering the steel sheet at a temperature between 150 °C and 250 °C for between 2 and 6 hours.
13. The method of making hot rolled light-gauge martensitic steel sheet as claimed in claim 11 further comprising hot rolling the steel sheet to between 15% and 35% reduction and rapidly cooling to form a steel sheet with a microstructure having at least 75% by volume martensite, a yield strength of between 700 and 1300 MPa, a tensile strength of between 1000 and 1800 MPa and an elongation of between 1 % and 10% .
14. The method of making hot rolled light-gauge martensitic steel sheet as claimed in claim 11 comprising hot rolling the steel sheet to between 15% and 35% reduction and rapidly cooling to form a steel sheet with a microstructure having by volume at least 75% martensite plus bainite, a yield strength of between 700 and 1300 MPa, a tensile strength of between 1000 and 1800 MPa and an elongation of between 1 % and 10% .
15. The method of making hot rolled light-gauge martensitic steel sheet as claimed in claim 11 where the cooled steel sheet has a total oxygen content greater than 50 ppm.
16. The method of making hot rolled light-gauge martensitic steel sheet as claimed in claim 11 where the molten melt has a free oxygen content between 5 and 70 ppm.
17. The method of making hot rolled light-gauge martensitic steel sheet as claimed in claim 11 comprising hot rolling the steel sheet to between 15% and 50% reduction and rapidly cooling to between 100 and 20 °C at a rate of more than 100 °C/s to form a steel sheet with a microstructure having at least 75% volume martensite, a yield strength of between 700 and 1300 MPa, a tensile strength of between 1000 and 1800 MPa and an elongation of between 1 % and 10% .
18. The method of making hot rolled light-gauge martensitic steel sheet hot rolled as claimed in claim 11 wherein the martensite comes from an austenite grain size of greater than 100 μπι.
19. The method of making hot rolled light-gauge martensitic steel sheet hot rolled as claimed in claim 11 wherein the martensite comes from an austenite grain size of greater than 150 μπι.
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