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 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
  • C21D8/0221—Modifying the physical properties 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
  • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
  • C21D1/18—Hardening; Quenching with or without subsequent tempering
  • C21D1/19—Hardening; Quenching with or without subsequent tempering by interrupted quenching
• • 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
  • C21D6/001—Heat treatment of ferrous alloys containing Ni
• • 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
  • C21D6/02—Hardening by precipitation
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/04—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
  • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
• • 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
  • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
• • 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
  • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
• • 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
  • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D2211/00—Microstructure comprising significant phases
  • C21D2211/002—Bainite
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D2211/00—Microstructure comprising significant phases
  • C21D2211/008—Martensite

Definitions

• This invention relates to ultra-high strength, weldable, low alloy steel plates . with excellent cryogenic temperature toughness in both the base plate and in the heat affected zone (HAZ) when welded. Furthermore, this invention relates to a method for producing such steel plates.
• cryogenic temperatures i.e., at temperatures lower than about -40°C (-40°F).
• PLNG pressurized liquefied natural gas
• Welded steels used in the construction of storage and transportation containers for the aforementioned cryogenic temperature applications and for other load-bearing, cryogenic temperature service must have DBTTs well below the service temperature in both the base steel and the HAZ to avoid failure by low energy cleavage fracture.
• Nickel-containing steels conventionally used for cryogenic temperature structural applications e.g., steels with nickel contents of greater than about 3 wt%, have low DBTTs, but also have relatively low tensile strengths.
• 3.5 wt% Ni, 5.5 wt% Ni, and 9 wt% Ni steels have DBTTs of about -100°C (-150°F), -155°C (-250°F), and -175°C (-280°F), respectively, and tensile strengths of up to about 485 MPa (70 ksi), 620 MPa (90 ksi), and 830 MPa (120 ksi), respectively.
• these steels In order to achieve these combinations of strength and toughness, these steels generally undergo costly processing, e.g., double annealing treatment.
• HSLA state-of-the-art, low and medium carbon high strength, low alloy
• AISI 4320 or 4330 steels have the potential to offer superior tensile strengths (e.g., greater than about 830 MPa (120 ksi)) and low cost, but suffer from relatively high DBTTs in general and especially in the weld heat affected zone (HAZ).
• HTZ weld heat affected zone
• weldability and low temperature toughness to decrease as tensile strength increases. It is for this reason that currently commercially available, state-of-the-art HSLA steels are not generally considered for cryogenic temperature applications.
• the high DBTT of the HAZ in these steels is generally due to the formation of undesirable microstructures arising from the weld thermal cycles in the coarse grained and intercritically reheated HAZs, i.e., HAZs heated to a temperature of from about the Aci transformation temperature to about the Ac 3 transformation temperature.
• HAZs heated to a temperature of from about the Aci transformation temperature to about the Ac 3 transformation temperature See Glossary for definitions of Aci and Ac 3 transformation temperatures.
• DBTT increases significantly with increasing grain size and embrittling microstructural constituents, such as martensite-austenite (MA) islands, in the HAZ.
• MA martensite-austenite
• the DBTT for the HAZ in a state-of-the-art HSLA steel, XI 00 linepipe for oil and gas transmission is higher than about -50°C (-60°F).
• the primary objects of the present invention are to improve the state-of-the-art high strength, low alloy steel technology for applicability at cryogenic temperatures in three key areas: (i) lowering of the DBTT to less than about -73 °C (-100°F) in the base steel and in the weld HAZ, (ii) achieving tensile strength greater than 830 MPa (120 ksi), and (iii) providing superior weldability.
• Other objects of the present invention are to achieve the aforementioned HSLA steels with substantially uniform through-thickness microstructures and properties in thicknesses greater than about 2.5 cm (1 inch) and to do so using current commercially available processing techniques so that use of these steels in commercial cryogenic temperature processes is economically feasible.
• a processing methodology is provided wherein a low alloy steel slab of the desired chemistry is reheated to an appropriate temperature then hot rolled to form steel plate and rapidly cooled, at the end of hot rolling, by quenching with a suitable fluid, such as water, to a suitable Quench Stop Temperature (QST), to transform the microstructure of the steel to preferably predominantly fine-grained lath martensite, fine-grained lower bainite, or mixtures thereof, and then by tempering within a suitable temperature range to produce a microstructure in the tempered steel preferably comprising predominantly tempered fine-grained lath martensite, tempered fine-grained lower bainite, or mixtures thereof, or, more preferably comprising substantially 100% tempered fine-grained lath martensite.
• a suitable fluid such as water
• QST Quench Stop Temperature
• quenching refers to accelerated cooling by any means whereby a fluid selected for its tendency to increase the cooling rate of the steel is utilized, as opposed to air cooling the steel to ambient temperature.
• the steel plate is air cooled to ambient temperature after quenching is stopped and prior to tempering.
• steels processed according to the present invention are especially suitable for many cryogenic temperature applications in that the steels have the following characteristics, preferably for steel plate thicknesses of about 2.5 cm (1 inch) and greater: (i) DBTT lower than about -73 °C (-100°F) in the base steel and in the weld HAZ, (ii) tensile strength greater than 830 MPa (120 ksi), preferably greater than about 860 MPa (125 ksi), and more preferably greater than about 900 MPa (130 ksi), (iii) superior weldability, (iv) substantially uniform through-thickness microstructure and properties, and (v) improved toughness over standard, commercially available, HSLA steels.
• These steels can have a tensile strength of greater than about 930 MPa (135 ksi), or greater than about 965 MPa (140 ksi), or greater than about 1000 MPa (145 ksi).
• FIG. 1 A is a schematic illustration of austenite grain size in a steel slab after reheating according to the present invention
• FIG. IB is a schematic illustration of prior austenite grain size (see Glossary) in a steel slab after hot rolling in the temperature range in which austenite recrystallizes, but prior to hot rolling in the temperature range in which austenite does not recrystallize, according to the present invention.
• FIG. 1C is a schematic illustration of the elongated, pancake grain structure in austenite, with very fine effective grain size in the through-thickness direction, of a steel plate upon completion of TMCP according to the present invention.
• the present invention relates to the development of new HSLA steels meeting the above-described challenges.
• the invention is based on a novel combination of steel chemistry and processing for providing both intrinsic and microstructural toughening to lower DBTT as well as to enhance toughness at high tensile strengths.
• Intrinsic toughening is achieved by the judicious balance of critical alloying elements in the steel as described in detail in this specification.
• Microstructural toughening results from achieving a very fine effective grain size as well as producing fine-grained martensitic and/or lower bainitic laths occurring in fine packets with a mean dimension much finer than the prior austenite grain.
• dispersion strengthening from fine copper precipitates and mixed carbides and/or carbonitrides is utilized to optimize strength and toughness during the tempering of the martensitic/bainitic structure.
• a method for preparing a steel plate having a microstructure comprising predominantly tempered fine-grained lath martensite, tempered fine-grained lower bainite, or mixtures thereof comprising the steps of (a) heating a steel slab to a reheating temperature sufficiently high to (i) substantially homogenize the steel slab, (ii) dissolve substantially all carbides and carbonitrides of niobium and vanadium in the steel slab, and (iii) establish fine initial austenite grains in the steel slab; (b) reducing the steel slab to form steel plate in one or more hot rolling passes in a first temperature range in which austenite recrystallizes; (c) further reducing the steel plate in one or more hot rolling passes in a second temperature range below about the T m temperature and above about the Ar 3 transformation temperature; (d) quenching the steel plate at a cooling rate of about 10°C per second to about 40°C per second (18°F/sec - 72°F/sec
• steels according to this invention preferably have a microstructure comprised of predominantly tempered fine-grained lower bainite, tempered fine-grained lath martensite, or mixtures thereof. It is preferable to substantially minimize the formation of embrittling constituents such as upper bainite, twinned martensite and MA.
• embrittling constituents such as upper bainite, twinned martensite and MA.
• "predominantly" means at least about 50 volume percent. More preferably, the microstructure comprises at least about 60 volume percent to about 80 volume percent tempered fine-grained lower bainite, tempered fine-grained lath martensite, or mixtures thereof.
• the microstructure comprises at least about 90 volume percent tempered fine-grained lower bainite, tempered fine-grained lath martensite, or mixtures thereof. Most preferably, the microstructure comprises substantially 100% tempered fine-grained lath martensite.
• a steel slab processed according to this invention is manufactured in a customary fashion and, in one embodiment, comprises iron and the following alloying elements, preferably in the weight ranges indicated in the following Table I:
• Vanadium (V) is sometimes added to the steel, preferably up to about 0.10 wt%, and more preferably about 0.02 wt% to about 0.05 wt%.
• Chromium (Cr) is sometimes added to the steel, preferably up to about 1.0 wt%, and more preferably about 0.2 wt% to about 0.6 wt%.
• Silicon (Si) is sometimes added to the steel, preferably up to about 0.5 wt%, more preferably about 0.01 wt% to about 0.5 wt%, and even more preferably about 0.05 wt% to about 0.1 wt%.
• Boron (B) is sometimes added to the steel, preferably up to about 0.0020 wt%, and more preferably about 0.0006 wt% to about 0.0010 wt%.
• the steel preferably contains at least about 1 wt% nickel.
• Nickel content of the steel can be increased above about 3 wt% if desired to enhance performance after welding. Each 1 wt% addition of nickel is expected to lower the DBTT of the steel by about 10°C (18°F).
• Nickel content is preferably less than 9 wt%, more preferably less than about 6 wt%.
• Nickel content is preferably minimized in order to minimize cost of the steel. If nickel content is increased above about 3 wt%, manganese content can be decreased below about 0.5 wt% down to 0.0 wt%. Additionally, residuals are preferably substantially minimized in the steel.
• Phosphorous (P) content is preferably less than about 0.01 wt%.
• Sulfur (S) content is preferably less than about 0.004 wt%.
• Oxygen (O) content is preferably less than about 0.002 wt%.
• Achieving a low DBTT is a key challenge in the development of new HSLA steels for cryogenic temperature applications.
• the technical challenge is to maintain/increase the strength in the present HSLA technology while lowering the DBTT, especially in the HAZ.
• the present invention utilizes a combination of alloying and processing to alter both the intrinsic as well as microstructural contributions to fracture resistance in a way to produce a low alloy steel with excellent cryogenic temperature properties in the base plate and in the HAZ, as hereinafter described.
• microstructural toughening is exploited for lowering the base steel DBTT.
• a key component of this microstructural toughening consists of refining prior austenite grain size and modifying the grain morphology, aimed at enhancing the interfacial area of the high angle boundaries per unit volume in the steel plate.
• grain as used herein means an individual crystal in a polycrystalline material
• grain boundary as used herein means a narrow zone in a metal corresponding to the transition from one crystallographic orientation to another, thus separating one grain from another.
• a "high angle grain boundary” is a grain boundary that separates two adjacent grains whose crystallographic orientations differ by more than about 8°.
• a "high angle boundary” is a boundary that effectively behaves as a high angle grain boundary, i.e., a boundary that tends to deflect a propagating crack or fracture and, thus, induces tortuosity in a fracture path.
• TMCP fhermo-mechanical controlled rolling processing
• d is the average austenite grain size in a hot-rolled steel plate prior to rolling in the temperature range in which austenite does not recrystallize (prior austenite grain size);
• R is the reduction ratio (original steel slab thickness/final steel plate thickness); and r is the percent reduction in thickness of the steel due to hot rolling in the temperature range in which austenite does not recrystallize.
• a relatively low reheating temperature preferably between about 955°C and about 1065°C (1750°F - 1950°F) is used to obtain initially an average austenite grain size D' of less than about 120 microns in reheated steel slab 10' before hot deformation.
• Processing according to this invention avoids the excessive austenite grain growth that results from the use of higher reheating temperatures, i.e., greater than about 1095°C (2000°F), in conventional TMCP.
• processing according to this invention provides an average prior austenite grain size D" (i.e., d ) of less than about 30 microns, preferably less than about 20 microns, and even more preferably less than about 10 microns, in steel slab 10" after hot rolling (deformation) in the temperature range in which austenite recrystallizes, but prior to hot rolling in the temperature range in which austenite does not recrystallize.
• D average prior austenite grain size
• d average prior austenite grain size of less than about 30 microns, preferably less than about 20 microns, and even more preferably less than about 10 microns, in steel slab 10" after hot rolling (deformation) in the temperature range in which austenite recrystallizes, but prior to hot rolling in the temperature range in which austenite does not recrystallize.
• heavy reductions preferably exceeding about 70%.
• TMCP leads to the formation of an elongated, pancake grain structure in austenite in a finish rolled steel plate 10'" with very fine effective grain size D'" in the through-thickness direction, e.g., effective grain size D'" less than about 10 microns, preferably less than about 8 microns, and even more preferably less than about 5 microns, thus enhancing the interfacial area of high angle boundaries, e.g., 11, per unit volume in steel plate 10'", as will be understood by those skilled in the art.
• a steel according to this invention is prepared by forming a slab of the desired composition as described herein; heating the slab to a temperature of from about 955°C to about 1065°C (1750°F - 1950°F); hot rolling the slab to form steel plate in one or more passes providing about 30 percent to about 70 percent reduction in a first temperature range in which austenite recrystallizes, i.e., above about the T ⁇ - temperature, and further hot rolling the steel plate in one or more passes providing about 40 percent to about 80 percent reduction in a second temperature range below about the T m temperature and above about the Ar 3 transformation temperature.
• the hot rolled steel plate is then quenched at a cooling rate of about 10°C per second to about 40°C per second (18°F/sec - 72°F/sec) to a suitable QST below about the M s transformation temperature plus 200°C (360°F), at which time the quenching is terminated.
• the steel plate is then air cooled to ambient temperature.
• This processing is used to produce a microstructure preferably comprising predominantly fine-grained lath martensite, fine-grained lower bainite, or mixtures thereof, or, more preferably comprising substantially 100%> fine-grained lath martensite.
• the thus direct quenched martensite in steels according to this invention has high strength but its toughness can be improved by tempering at a suitable temperature from above about 400°C (752°F) up to about the Aci transformation temperature. Tempering of steel within this temperature range also leads to reduction of the quenching stresses which in turn leads to enhanced toughness. While tempering can enhance the toughness of the steel, it normally leads to substantial loss of strength.
• the usual strength loss from tempering is offset by inducing precipitate dispersion hardening. Dispersion hardening from fine copper precipitates and mixed carbides and/or carbonitrides are utilized to optimize strength and toughness during the tempering of the martensitic structure.
• the unique chemistry of the steels of this invention allows for tempering within the broad range of about 400°C to about 650°C (750°F - 1200°F) without any significant loss of the as-quenched strength.
• the steel plate is preferably tempered at a tempering temperature from above about 400°C (752°F) to below the Aci transformation temperature for a period of time sufficient to cause precipitation of hardening particles (as defined herein).
• This processing facilitates transformation of the microstructure of the steel plate to predominantly tempered fine-grained lath martensite, tempered fine-grained lower bainite, or mixtures thereof.
• the period of time sufficient to cause precipitation of hardening particles depends primarily on the thickness of the steel plate, the chemistry of the steel plate, and the tempering temperature, and can be determined by one skilled in the art.
• percent reduction in thickness refers to percent reduction in the thickness of the steel slab or plate prior to the reduction referenced.
• a steel slab of about 25.4 cm (10 inches) thickness may be reduced about 50%> (a 50 percent reduction), in a first temperature range, to a thickness of about 12.7 cm (5 inches) then reduced about 80%> (an 80 percent reduction), in a second temperature range, to a thickness of about 2.5 cm (1 inch).
• slab means a piece of steel having any dimensions.
• the steel slab is preferably heated by a suitable means for raising the temperature of substantially the entire slab, preferably the entire slab, to the desired reheating temperature, e.g., by placing the slab in a furnace for a period of time.
• a suitable means for raising the temperature of substantially the entire slab, preferably the entire slab, to the desired reheating temperature e.g., by placing the slab in a furnace for a period of time.
• the specific reheating temperature that should be used for any steel composition within the range of the present invention may be readily determined by a person skilled in the art, either by experiment or by calculation using suitable models.
• the furnace temperature and reheating time necessary to raise the temperature of substantially the entire slab, preferably the entire slab, to the desired reheating temperature may be readily determined by a person skilled in the art by reference to standard industry publications.
• temperatures referenced in describing the processing method of this invention are temperatures measured at the surface of the steel.
• the surface temperature of steel can be measured by use of an optical pyrometer, for example, or by any other device suitable for measuring the surface temperature of steel.
• the cooling rates referred to herein are those at the center, or substantially at the center, of the plate thickness; and the Quench Stop Temperature (QST) is the highest, or substantially the highest, temperature reached at the surface of the plate, after quenching is stopped, because of heat transmitted from the mid-thickness of the plate.
• QST Quench Stop Temperature
• thermocouple is placed at the center, or substantially at the center, of the steel plate thickness for center temperature measurement, while the surface temperature is measured by use of an optical pyrometer.
• a correlation between center temperature and surface temperature is developed for use during subsequent processing of the same, or substantially the same, steel composition, such that center temperature may be determined via direct measurement of surface temperature.
• the required temperature and flow rate of the quenching -fluid to accomplish the desired accelerated cooling rate may be determined by one skilled in the art by reference to standard industry publications.
• the temperature that defines the boundary between the recrystallization range and non-recrystallization range depends on the chemistry of the steel, particularly the carbon concentration and the niobium concentration, on the reheating temperature before rolling, and on the amount of reduction given in the rolling passes. Persons skilled in the art may determine this temperature for a particular steel according to this invention either by experiment or by model calculation. Similarly, the Aci, Ar , and M s transformation temperatures referenced herein may be determined by persons skilled in the art for any steel according to this invention either by experiment or by model calculation.
• the present invention provides a method for maintaining sufficiently low DBTT in the coarse grained regions of the weld HAZ by utilizing intrinsic effects of alloying elements, as described in the following.
• Leading ferritic cryogenic temperature steels are generally based on body-centered cubic (BCC) crystal lattice. While this crystal system offers the potential for providing high strengths at low cost, it suffers from a steep transition from ductile to brittle fracture behavior as the temperature is lowered. This can be fundamentally attributed to the strong sensitivity of the critical resolved shear stress (CRSS) (defined herein) to temperature in BCC systems, wherein CRSS rises steeply with a decrease in temperature thereby making the shear processes and consequently ductile fracture more difficult.
• CRSS critical resolved shear stress
• the critical stress for brittle fracture processes such as cleavage is less sensitive to temperature.
• CRSS is an intrinsic property of the steel and is sensitive to the ease with which dislocations can cross slip upon deformation; that is, a steel in which cross slip is easier will also have a low CRSS and hence a low DBTT.
• FCC face-centered cubic
• BCC stabilizing alloying elements such as Si, Al, Mo, Nb and V discourage cross slip.
• content of FCC stabilizing alloying elements is preferably optimized, taking into account cost considerations and the beneficial effect for lowering DBTT, with Ni alloying of preferably at least about 1.0 wt% and more preferably at least about 1.5 wt%; and the content of BCC stabilizing alloying elements in the steel is substantially minimized.
• the steels have excellent cryogenic temperature toughness in both the base plate and the HAZ after welding.
• DBTTs in both the base plate and the HAZ after welding of these steels are lower than about -73 °C (-100°F) and can be lower than about -107°C (-160°F).
• the desired strength is obtained at a relatively low carbon content with the attendant advantages in weldability and excellent toughness in both the base steel and in the HAZ.
• a minimum of about 0.04 wt%> C is preferred in the overall alloy for attaining tensile strength greater than 830 MPa (120 ksi).
• alloying elements other than C, in steels according to this invention are substantially inconsequential as regards the maximum attainable strength in the steel, these elements are desirable to provide the required through-thickness uniformity of microstructure and strength for plate thickness greater than about 2.5 cm (1 inch) and for a range of cooling rates desired for processing flexibility. This is important as the actual cooling rate at the mid section of a thick plate is lower than that at the surface.
• the microstructure of the surface and center can thus be quite different unless the steel is designed to eliminate its sensitivity to the difference in cooling rate between the surface and the center of the plate.
• Mn and Mo alloying additions, and especially the combined additions of Mo and B are particularly effective.
• these additions are optimized for hardenability, weldability, low DBTT and cost considerations.
• the preferred chemistry targets and ranges are set to meet these and the other requirements of this invention.
• the steels of this invention are designed for superior weldability.
• the most important concern, especially with low heat input welding, is cold cracking or hydrogen cracking in the coarse grained HAZ. It has been found that for steels of the present invention, cold cracking susceptibility is critically affected by the carbon content and the type of HAZ microstructure, not by the hardness and carbon equivalent, which have been considered to be the critical parameters in the art.
• the preferred upper limit for carbon addition is about 0.1 wt%>.
• "low heat input welding” means welding with arc energies of up to about 2.5 kilojoules per millimeter (kJ/mm) (7.6 kJ/inch).
• Lower bainite or auto-tempered lath martensite microstructures offer superior resistance to cold cracking.
• Other alloying elements in the steels of this invention are carefully balanced, commensurate with the hardenability and strength requirements, to ensure the formation of these desirable microstructures in the coarse grained HAZ.
• Carbon (C) is one of the most effective strengthening elements in steel. It also combines with the strong carbide formers in the steel such as Ti, Nb, V and Mo to provide grain growth inhibition and precipitation strengthening during tempering. Carbon also enhances hardenability, i.e., the ability to form harder and stronger microstructures in the steel during cooling. If the carbon content is less than about 0.04 wt%>, it is not sufficient to induce the desired strengthening, viz., greater than 830 MPa (120 ksi) tensile strength, in the steel. If the carbon content is greater than about 0.12 wt%>, the steel will be susceptible to cold cracking during welding and the toughness is reduced in the steel plate and its HAZ on welding.
• Carbon content in the range of about 0.04 wt% to about 0.12 w ⁇ % is preferred to produce the desired strength and HAZ microstructures, viz., auto-tempered lath martensite and lower bainite. Even more preferably, the upper limit for carbon content is about 0.07 wt%>.
• Manganese (Mn) is a matrix strengthener in steels and also contributes strongly to the hardenability. A minimum amount of 0.5 wt% Mn is preferred for achieving the desired high strength in plate thickness exceeding about 2.5 cm (1 inch), and a minimum of at least about 1.0 wt% Mn is even more preferred. However, too much Mn can be harmful to toughness, so an upper limit of about 2.5 wt%> Mn is preferred in the present invention.
• This upper limit is also preferred to substantially minimize centerline segregation that tends to occur in high Mn and continuously cast steels and the attendant through-thickness non-uniformity in microstructure and properties. More preferably, the upper limit for Mn content is about 1.8 wt%. If nickel content is increased above about 3 wt%, the desired high strength can be achieved without the addition of manganese. Therefore, in a broad sense, up to about 2.5 wt% manganese is preferred. Silicon (Si) may be added to steel for deoxidation purposes and a minimum of about 0.01 wt% is preferred for this purpose. However, Si is a strong BCC stabilizer and thus raises DBTT and also has an adverse effect on the toughness.
• an upper limit of about 0.5 wt% Si is preferred. More preferably, when Si is added, the upper limit for Si content is about 0.1 wt%. Silicon is not always necessary for deoxidation since aluminum or titanium can perform the same function.
• Niobium fNb is added to promote grain refinement of the rolled microstructure of the steel, which improves both the strength and toughness.
• Niobium carbide and carbonitride precipitation during hot rolling serves to retard recrystallization and to inhibit grain growth, thereby providing a means of austenite grain refinement.
• precipitation of carbides and carbonitrides of niobium during tempering provides the desired secondary hardening to offset the strength loss normally observed in steel when it is tempered above about 500°C (930°F).
• at least about 0.02 wt% Nb is preferred, and at least about 0.03 wt% Nb is even more preferred.
• Nb is a strong BCC stabilizer and thus raises DBTT. Too much Nb can be harmful to the weldability and HAZ toughness, so a maximum of about 0.1 wt% is preferred. More preferably, the upper limit for Nb content is about 0.05 wt%.
• Vanadium (V) is sometimes added to give precipitation strengthening by forming fine particles of the carbides and carbonitrides of vanadium in the steel on tempering and in its HAZ on cooling after welding.
• V When dissolved in austenite, V has a strong beneficial effect on hardenability.
• V When V is added to the steels of the present invention, at least about 0.02 wt%> V is preferred. However, excessive V will help cause cold cracking on welding, and also deteriorate toughness of the base steel and its HAZ.
• the V addition therefore, is preferably limited to a maximum of about 0.1 wt%, and even more preferably is limited to a maximum of about 0.05 wt%. Titanium (Ti).
• TiN titanium nitride
• TiC titanium carbide
• a Ti content below about 0.008 wt% generally can not provide sufficiently fine grain size or tie up the N in the steel as TiN while more than about 0.03 wt% can cause deterioration in toughness. More preferably, the steel contains at least about 0.01 wt%> Ti and no more than about 0.02 wt% Ti.
• Aluminum (Al) is added to the steels of this invention for the purpose of deoxidation. At least about 0.001 wt%> Al is preferred for this purpose, and at least about 0.005 wt%> Al is even more preferred. Al also ties up nitrogen dissolved in the HAZ. However, Al is a strong BCC stabilizer and thus raises DBTT. Ifthe Al content is too high, i.e., above about 0.05 wt%, there is a tendency to form aluminum oxide (Al 2 O 3 ) type inclusions, which tend to be harmful to the toughness of the steel and its HAZ. Even more preferably, the upper limit for Al content is about 0.03 wt%.
• Molybdenum increases the hardenability of steel on direct quenching, especially in combination with boron and niobium. Mo is also desirable for promoting secondary hardening during tempering of the steel by providing fine Mo 2 C carbides. At least about 0.1 wt%> Mo is preferred, and at least about 0.2 wt% Mo is even more preferred. However, Mo is a strong BCC stabilizer and thus raises DBTT. Excessive Mo helps to cause cold cracking on welding, and also tends to deteriorate the toughness of the steel and HAZ, so a maximum of about 0.8 wt% is preferred, and a maximum of about 0.5 wt%> is even more preferred.
• Chromium (Cr) tends to increase the hardenability of steel on direct quenching. It also improves corrosion resistance and hydrogen induced cracking (HIC) resistance. Similar to Mo, excessive Cr tends to cause cold cracking in weldments, and also tends to deteriorate the toughness of the steel and its HAZ, so when Cr is added, a maximum of about 1.0 wt% Cr is preferred. More preferably, when Cr is added the Cr content is about 0.2 wt% to about 0.6 wt%.
• Nickel (Ni) is an important alloying addition to the steels of the present invention to obtain the desired DBTT, especially in the HAZ. It is one of the strongest FCC stabilizers in steel.
• Ni addition to the steel enhances the cross slip and thereby lowers DBTT. Although not to the same degree as Mn and Mo additions, Ni addition to the steel also promotes hardenability and therefore through-thickness uniformity in microstructure and properties in thick sections (i.e., thicker than about 2.5 cm (1 inch)).
• the minimum Ni content is preferably about 1.0 wt%, more preferably about 1.5 wt%.
• the Ni content of the steel is preferably less than about 3.0 wt%, more preferably less than about 2.5 wt%>, more preferably less than about 2.0 wt%, and even more preferably less than about 1.8 wt%, to substantially minimize cost of the steel.
• Copper (Cu) is a useful alloying addition to provide hardening during tempering via ⁇ -copper precipitation.
• Cu is also an FCC stabilizer in steel and can contribute to lowering of DBTT in small amounts.
• Cu is also beneficial for corrosion and HIC resistance. At higher amounts, Cu induces excessive precipitation hardening and can lower the toughness and raise the DBTT both in the base plate and HAZ. Higher Cu can also cause embrittlement during slab casting and hot rolling, requiring co-additions of Ni for mitigation.
• an upper limit of about 1.5 wt%> Cu is preferred, and an upper limit of about 1.0 wt% is even more preferred.
• Boron (B) in small quantities can greatly increase the hardenability of steel and promote the formation of steel microstructures of lath martensite, lower bainite, and ferrite by suppressing the formation of upper bainite both in the base plate and the coarse grained HAZ.
• B Boron
• at least about 0.0004 wt% B is needed for this purpose.
• boron is added to steels of this invention, from about 0.0006 wt%> to about 0.0020 wt%> is preferred, and an upper limit of about 0.0010 wt% is even more preferred.
• boron may not be a required addition if other alloying in the steel provides adequate hardenability and the desired microstructure.
• This step-out combination of properties in the steels of the present invention provides a low cost enabling technology for certain cryogenic temperature operations, for example, storage and transport of natural gas at low temperatures.
• These new steels can provide significant material cost savings for cryogenic temperature applications over the current state-of-the-art commercial steels, which generally require far higher nickel contents (up to about 9 wt%) and are of much lower strengths (less than about 830 MPa (120 ksi)).
• Chemistry and microstructure design are used to lower DBTT and provide uniform mechanical properties in the through-thickness for section thicknesses exceeding about 2.5 cm. (1 inch).
• These new steels preferably have nickel contents lower than about 3 wt%>, tensile strength greater than 830 MPa (120 ksi), preferably greater than about 860 MPa (125 ksi), and more preferably greater than about 900 MPa (130 ksi), ductile to brittle transition temperatures (DBTTs) below about -73 °C (-100°F), and offer excellent toughness at DBTT.
• These new steels can have a tensile strength of greater than about 930 MPa (135 ksi), or greater than about 965 MPa (140 ksi), or greater than about 1000 MPa (145 ksi). Nickel content of these steel can be increased above about 3 wt%> if desired to enhance performance after welding.
• Nickel content is preferably less than 9 wt%, more preferably less than about 6 wt%. Nickel content is preferably minimized in order to minimize cost of the steel.
• Aci transformation temperature the temperature at which austenite begins to form during heating
• Ac 3 transformation temperature the temperature at which transformation of ferrite to austenite is completed during heating
• Al 2 O 3 aluminum oxide
• Ar transformation temperature the temperature at which austenite begins to transform to ferrite during cooling
• BCC body-centered cubic
• cooling rate cooling rate at the center, or substantially at the center, of the plate thickness
• CRSS critical resolved shear stress
• cryogenic temperature any temperature lower than about -40°C (-40°F); DBTT (Ductile to Brittle Transition Temperature): delineates the two fracture regimes in structural steels; at temperatures below the DBTT, failure tends to occur by low energy cleavage (brittle) fracture, while at temperatures above the DBTT, failure tends to occur by high energy ductile fracture;
• FCC face-centered cubic
• grain boundary a narrow zone in a metal corresponding to the transition from one crystallographic orientation to another, thus separating one grain from another;
• hardening particles one or more of ⁇ -copper, Mo C, or the carbides and carbonitrides of niobium and vanadium;
• HAZ heat affected zone
• HIC hydrogen induced cracking
• high angle boundary a boundary that effectively behaves as a high angle grain boundary, i.e., a boundary that tends to deflect a propagating crack or fracture and, thus, induces tortuosity in a fracture path;
• high angle grain boundary a grain boundary that separates two adjacent grains whose crystallographic orientations differ by more than about 8°;
• HSLA high strength, low alloy
• intercritically reheated heated (or reheated) to a temperature of from about the Aci transformation temperature to about the Ac 3 transformation temperature;
• low alloy steel a steel containing iron and less than about 10 wt% total alloy additives
• low heat input welding welding with arc energies of up to about 2.5 kJ/mm (7.6 kJ/inch);
• Mo 2 C a form of molybdenum carbide
• M s transformation temperature the temperature at which transformation of austenite to martensite starts during cooling
• prior austenite grain size average austenite grain size in a hot-rolled steel plate prior to rolling in the temperature range in which austenite does not recrystallize; quenching: as used in describing the present invention, accelerated cooling by any means whereby a fluid selected for its tendency to increase the cooling rate of the steel is utilized, as opposed to air cooling;
• QST Quench Stop Temperature
• slab a piece of steel having any dimensions
• tensile strength in tensile testing, the ratio of maximum load to original cross-sectional area
• TiC titanium carbide
• TiN titanium nitride
• T m temperature the temperature below which austenite does not recrystallize
• TMCP thermo-mechanical controlled rolling processing.

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