WO2013007729A1 - Hot-rolled high-strength steel strip with improved haz-softening resistance and method of producing said steel - Google Patents
Hot-rolled high-strength steel strip with improved haz-softening resistance and method of producing said steel Download PDFInfo
- Publication number
- WO2013007729A1 WO2013007729A1 PCT/EP2012/063515 EP2012063515W WO2013007729A1 WO 2013007729 A1 WO2013007729 A1 WO 2013007729A1 EP 2012063515 W EP2012063515 W EP 2012063515W WO 2013007729 A1 WO2013007729 A1 WO 2013007729A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- steel
- hot
- martensite
- rolled
- strength
- Prior art date
Links
- 229910000831 Steel Inorganic materials 0.000 title claims description 82
- 239000010959 steel Substances 0.000 title claims description 82
- 238000000034 method Methods 0.000 title claims description 12
- 229910000734 martensite Inorganic materials 0.000 claims abstract description 29
- 229910001563 bainite Inorganic materials 0.000 claims abstract description 14
- 229910000742 Microalloyed steel Inorganic materials 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 21
- 238000005096 rolling process Methods 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000011575 calcium Substances 0.000 claims description 11
- 239000011651 chromium Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 238000005098 hot rolling Methods 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 10
- 229910052758 niobium Inorganic materials 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 238000007792 addition Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010955 niobium Substances 0.000 description 14
- 229910001566 austenite Inorganic materials 0.000 description 11
- 239000011572 manganese Substances 0.000 description 11
- 229910052796 boron Inorganic materials 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 229910000859 α-Fe Inorganic materials 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 230000009466 transformation Effects 0.000 description 8
- 238000003466 welding Methods 0.000 description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 7
- 239000004411 aluminium Substances 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 150000001247 metal acetylides Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 238000005266 casting Methods 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005496 tempering Methods 0.000 description 4
- -1 titanium nitrides Chemical class 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- RMLPZKRPSQVRAB-UHFFFAOYSA-N tris(3-methylphenyl) phosphate Chemical compound CC1=CC=CC(OP(=O)(OC=2C=C(C)C=CC=2)OC=2C=C(C)C=CC=2)=C1 RMLPZKRPSQVRAB-UHFFFAOYSA-N 0.000 description 3
- 229910052582 BN Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000746 Structural steel Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910001562 pearlite Inorganic materials 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 229910014460 Ca-Fe Inorganic materials 0.000 description 1
- 229910014458 Ca-Si Inorganic materials 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000003698 laser cutting Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000005088 metallography Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
Classifications
-
- 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
- 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
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
-
- 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
- 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
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
-
- 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
- the invention rel ates to a hot-rolled high-strength steel strip with improved HAZ-softening resistance and method of producing said steel
- EP1375694 describes a method for prod ucing a h ig h-strength, high- toughness steel with good workability and weldability by means of hot rolling .
- HAZ heat-affected zone
- the heat-affected zone (HAZ) is the area of base material which has had its microstructure and properties altered by welding or heat intensive cutting operations. The heat from the welding process and subsequent re- cooling causes this change in the area surrounding the weld .
- the heat-affected zone which forms adjacent to the weld in steels is one of the most common regions of weld failure.
- TMCP thermo-mechanically rolled
- HAZ softening is often the result of high heat-input welding procedure because of the slow heat dissipation in the HAZ.
- HAZ softening can happen even under moderate welding heat-input because of the base metal's ultra fine grain size and its bainite- and martensite-dominated microstructure. This reduction in hardness and strength in HAZ makes it a weak point in a welded pipeline structure.
- WO2007/129676 relates to a hot pressed steel member made from a hig h carbon cold-rolled steel sheet which is austenitised, hot-pressed to produce a steel member and quenched to achieve a minimum tensile strength of 1.8 GPa.
- the hot-rolled steel that is to be cold rolled contains at least 50% ferrite.
- EP2028284 discloses a seamless steel pipe and EP1662014 discloses a low carbon hot rolled steel plate which is coiled between 450 to 650°C and subsequently promptly reheated to between 550 and 750°C to achieve a three-phase ferrite, bainite and island martensite structure.
- the object of the present invention is to achieve a high-strength hot- rolled steel strip that is less susceptible to HAZ-softening than the currently available high strength hot-rolled steel strip.
- this object is reached by a hot-rolled high-strength micro- alloyed steel strip having a thickness of between 2 and 16 mm with improved HAZ-softening resistance having a microstructure comprising martensite, tempered martensite and/or bainite, and where the steel contains, in percentages by weight:
- the yield strength of the steel strip being at least 960 MPa. All compositional percentages are given as weight percent, unless indicated otherwise.
- the inventive idea is based on the fact that by selecting the combination of chemical elements in the amounts prescribed and in particular the presence of niobium and molybdenum good hardening can be maintained .
- the steel structure is not critical for the segregation of manganese and carbon during the casting process owing to the low manganese and carbon content.
- the steel properties are not critical for local fluctuations of the coiling temperature in the strip, which facilitates the steel production and has an advantageous effect in the homogeneity of its mechanical properties, which again has a positive influence both in the flatness of the end product and in the residual stress.
- the steel sheet is highly suitable for welding and laser cutting, and at the same time it has a good fatigue strength irrespective of said thermal treatments.
- the steel sheet has excellent bending properties, a good impact toughness as well as a good resistance to softening in tempering.
- the presence of the precipitating elements in sol ution which are subsequently available for precipitation during the cooling of the HAZ after welding ensures a significant improvement of the HAZ-softening resistance.
- the steel according to the invention can be thermally cut, for instance by laser, into precisely defined shapes. It has been observed that a remarkably smooth cutting surface is achieved in a laser cut object. On the other hand, it has been found out that the strength difference between the basic material and the soft zone created in the technical cutting process, which zone is located in the immediate vicinity of the hardened zone, is small or absent also as a result of the presence of the precipitating elements in solution which are subsequently available for precipitation during the cooling of after thermal cutting . These together have an advantageous affect in the fatigue strength . In addition, the relatively low carbon content reduces the peak hardness of the hardened zone, so that the cutting surface is not sensitive to embrittlement and cracking, neither in the working of the object nor in practical use.
- Carbon is an important element in controlling the strength, but needs to be limited to some extent to give a good balance in toughness, weldability and formability.
- the C content is kept relatively low between 0.07 and 0.30% to achieve a good toughness (all percentages in compositions are expressed in weight percent).
- the microstructures In combination with a low temperature coiling temperature the microstructures will contain martensite and/or bainite. The exact amounts strongly depend on the composition, cooling rate on the run-out table and the coiling temperature. At relatively low C contents, the Ms temperature will be quite high, so the martensite will auto temper to some extent. Depending on the strength requirement suitable carbon-windows were found .
- the carbon content is preferably at least 0.07 and/or at most 0.13%.
- the carbon content is preferably at least 0.13 and/or at most 0.18%, and for a steel having a yield strength of at least 1300 MPa the carbon content is preferably at least 0.19%, more preferably at least between 0.23 and/or at most 0.30%.
- a suitable maximum carbon content is 0.27% or even 0.25%.
- Elements like manganese, chromium, molybdenum and boron provide hardenability to promote the formation of bainite and/or martensite.
- the manganese content is limited to between 0.8 and 2.0%. When the manganese exceeds the upper boundary, the risk of segregation becomes significant and this may adversely affect the homogeneity of the microstructure. At levels below 0.8% the effect on hardenability is insufficient.
- a suitable minimum manganese level is 1.1%.
- Boron is added to promote the hardenability. It is important to avoid the formation of boron nitrides as this wil l render the boron ineffective for the promotion of the hardenabil ity.
- the role of titanium in the composition according to the invention is to protect the boron because Ti forms titanium nitrides and as a consequence no BN is formed .
- the amount of alloyed boron is at least 0.0005% B (i.e. 5 ppm) but no more than 0.005% B (i.e. 50 ppm) in order to reduce grain size and to increase the hardenability.
- titanium is added as an alloying element
- the amount of titanium is typically at least 0.01% Ti but no more than 0.05% in order to bind the nitrogen N and to prevent the creation of boron nitrides BN.
- An alternative within the scope of the invention is to use aluminium to bind the nitrogen and thereby protect the boron .
- TiN-particles is deemed undesirable, e.g . because of their effect on Charpy-toughness
- protecting the free boron by aluminium may be the preferred option.
- Niobium partly precipitates in the austenite during hot-rolling, thereby contributing to the grain refinement of the final transformed microstructure by the retardation of the recrystallisation of austenite.
- the niobium remaining in sol ution at transformation has a powerful effect on red ucing transformation temperatures, especially at faster cooling rates, so it is also beneficial for ha rdena bi l ity .
- a suitable Nb content is at least 0.02%, preferably at least 0.025%.
- V has a similar but less powerful effect as Nb in this case.
- the main reason for the addition of N b and V is to improve the HAZ-softening resistance.
- the thermal cycle is su ch that temperatures are reached which will allow precipitation strengthening by Nb and V, thus causing an increase in hardness as a result of the precipitation of elements which were kept in solution by the low coiling temperature.
- the major contribution is believed to be made by Nb and V carbides, nitrides or carbo-nitrides. To a lesser extent it is believed that MoC precipitates may form having a similar effect. If present, a suitable minimum V-content is 0.04%.
- the steels according to the invention are aluminium-killed or aluminium- silicon killed steels in order to reduce the oxygen content to a minimum so that no reaction occurs between carbon and oxygen during solidification.
- the amounts of aluminium added to the steel during production therefore include those needed for deoxidation .
- the remaining amount in the end product, also called soluble aluminium (Al SO i) is between 0.01 and 0.08% Al.
- the aluminium content referred to is soluble aluminium.
- Silicon may also serve as a deoxidant in the steel of the present invention in addition to aluminium. It also acts as a solid solution hardener starting from about at least 0. 10% Si and up to 0.50 % Si, which has an advantageous effect on the impact toug h ness and workabil ity. Above 0.5% the sil icon adversely affects the surface quality of the steel to an unacceptable extent and the removal of the hot rolling scale by pickling becomes increasingly difficult with increasing silicon content.
- Phosphorus P contained as an impurity should be at most 0.03%, and sulphur S should be even lower and should be limited to at most 0.015%, which means that these contents are restricted in order to achieve good impact toughness and bendability.
- further properties can be improved by treating the melt with cored wire containing Ca-Si or Ca-Fe(Ni).
- the alumina and silica inclusions are converted to molten calcium aluminates and silicate which are globular in shape because of the surface tension effect.
- the calcium aluminates inclusions retained in liquid steel suppress the formation of MnS stringers during solidification of steel .
- Chromium should be between 0 . 2 a n d 1.5%.
- Molybdenum should preferably be between 0.1% Mo and 0.7% Mo. Both elements are added in o rder to i n crease h a rd en i n g and tempering resistance. This enables precipitation at higher coiling temperatures, which can be used for decreasing and even preventing the softening of the steel , as well as for al leviating strength fl uctuations caused by local temperatu re d ifferences during the cooling of the coil.
- a suitable minimum molybdenum content is 0.15%.
- Alloying with elements like copper and nickel, often used in steels of this strength level are preferably avoided in view of the surface issues associated with copper. As copper is often alloyed in conjunction with nickel to alleviate the adverse effects of copper this is also not needed . So nickel and/or copper are preferably present at most at impurity level or more preferably completely absent.
- the microstructure is free from ferrite and pearlite constituents as these will deleteriously affect the strength level to be reached . In practice it may be unavoidable that some minor patches of ferrite are present, but the amount may not exceed the level where the strength levels is significantly affected .
- the hot-rolled steel strip according to the invention that is directly hot- rolled to the thickness 2 mm - 16 mm can be manufactured as wear-resistant and with different minimum yield strength .
- Typical threshold values in the marketplace are 960, 1100 and 1300 M Pa, on ly by chang ing the analysis and/or the post-rolling cooling rate of the strip, and/or temperature before the coiling, within the scope of the invention.
- This kind of high yield strength steel can also be used in targets where the structures require properties typically demanded of structural steel, such as good workability, weldability and impact toug hness, wh ich means that the hot-rolled steel strip according to the invention is feasible also as weldable structural steel.
- a l l content percentages are percentages by weight, and the rest of the steel that is otherwise not defined is naturally iron, Fe, and unavoidable impurities.
- the value of 960 MPa can be reached even to thickness values of the hot strip of up to 16 mm .
- the higher thickness results in a somewhat lower cooling rate, and therefore in a less enriched austenite prior to the phase transformation .
- the SHOO or S1300 level cannot be obtained for thicknesses of the hot strip over 12 m m .
- the minimum thickness is 3 mm and/or the maximum thickness is 10 mm.
- the val ues of the strength as defined in this invention are measured in the longitudinal direction (i.e. the tensile specimen is taken in the longitudinal direction of the strip (the direction of movement through the rolling mill)). Values in the transverse direction (i.e. the tensile specimen is taken in the width direction of the strip) may be different from the values in the longitudinal direction, and are usually higher than those in the longitudinal direction for strength and lower for elongation.
- the carbon content of the steel is between 0.07 and 0.13% and the yield strength is at least 960 MPa. In an embodiment the carbon content of the steel is between 0.13 and 0.18% and the yield strength is at least 1100 MPa.
- the carbon content is at least 0.19%, preferably between 0.23 and 0.30%, and the yield strength is at least 1300 MPa.
- a suitable maximum tensile strength of the hot-rolled steel according to the invention is 1700 MPa.
- the invention is embodied in a method for manufacturing a hot-rolled high-strength micro-alloyed steel strip having a thickness of between 2 and 16 mm with improved HAZ-softening resistance and a yield strength of at least 960 MPa having a microstructure comprising martensite, tempered martensite and/or bainite, and where the steel contains, in percentages by weight:
- the strip being finish hot-rolled above the Ar 3 -temperature, wherein the method includes at least the following steps:
- the hot-rolling process is the conventional hot-rolling process, either starting from a slab having a thickness of between 150 to 350 m m, i .e . conventionally continuously cast slabs, or below 150, i.e. thin slab casting or even strip casting .
- Finish rolling is preferably while the steel is still austenitic to provide the steel with a fine grain and thereby good impact toughness.
- the coiling temperature is preferably low to achieve the desired mechanical p ro pe rties .
- Prefe ra b l y th e co i l i n g te m pe ratu re is be l ow 400 °C .
- a n excel lent i m pact to ug h ness is o bta i ned beca use the phase transformation into martensite and/or bainite takes place from a fine-grained, worked austenite. It also improves the surface quality because the primary scale is removed in a descaler prior to the rolling . Moreover, there is no need for a very expensive lengthy additional annealing treatment to dissolve all precipitates.
- the slabs to be rolled are reheated in a reheating furnace to a temperature range between 1100 to 1250°C, and held for several hours.
- the growing of the austenite grain at the high heating temperature does not make the end product more brittle, because the austenite grains are refined first by recrystallisation during high temperature rolling in the initial stages of the rolling process and by transformation of the deformed austenite grain formed as a result of the retardation of austenite transformation during thermo-mechanical rolling in the last stages of the hot rolling process.
- the heavily deformed austenite grains transform into a very fine transformation product during cooling on the run-out table. This results in a h i g h y i e l d s stress , combined with an excellent impact toughness.
- the cooling of the strip begins no later than 10 seconds after the last hot rol l ing pass, and it is cooled sufficiently rapidly to al low the austenite to transform into a bainitic and/or martensitic microstructure, the cooling rate preferably being at least 30°C/s, down to a coiling temperature in the range 20°C - 500°C, preferably down to a coiling temperature in the range 20°C - 450°C.
- the obtained result is typical ly a nearly completely bainitic and/or martensitic microstructure, so that the bainite and/or martensite content preferably is at least 90 % by volume, preferably at least 95%.
- the microstructure is also preferably free from ferrite formed at high temperatures and free from pearlite constituents, thus rendering the microstructure substantially fully bainitic/martensitic, where Widmannstatten fe rrite o r acicular ferrite is considered to be a bainitic structure for this purpose.
- the martensite In the coiling temperature range of below 100°C the martensite is not tempered, although some auto-tempering may occur at these low temperatures for the low carbon grades, whereas when the coiling temperature is at least 100°C, the martensite is tempered . At temperatures above 200°C the martensite is tempered and the carbon precipitated.
- the coiling temperature is at most 450°C, more preferably 425°C, for steels containing a carbon content of at most 0.12% or at most 275°C, more preferably 250 or 225°C, for steels containing a carbon content of at least 0.13%.
- the cooling rate during the accelerated cooling after hot rolling and before coiling is between 5 and 100°C/s.
- finish rolling temperature is above Ar 3 and also below 920°C, and preferably also below 900°C.
- the steel according to the invention is used in the production of a part for an automobile, a lorry, ship-building, construction work, heavy haul equipment, earth-moving equipment or mobile cranes.
- Table 1 shows com positions of steels for each of the categories S700, S960, SHOO and S1300.
- Base 250 100 1490 27 14 3 480 510 20 60 3 imp 29
- SEM microstructures show that all hot-rolled steel samples have a microstructure that consists predominantly of tempered martensite, characterised by small carbides in a Widmanstatten pattern.
- the tempering of the martensite will have resulted due to the high M s temperature of these relatively low C steels, and also due to the slow cooling to simulate coil cooling .
- the pattern of the carbides showing several variants of an orientation relationship between the carbide and the matrix, is characteristic of tempered martensite.
- the prior austenite grain boundaries were also visible, and showed some elongation along the rolling direction, as was observed using optical metallography.
- the strength levels depend strongly on the coiling temperature (see figure 1 for the SHOO materials and figure 2 for the S1300 material) which is to be understood in view of the desired microstructure that consists predominantly of tempered martensite.
- Figure 3 shows the effect of HAZ-softening on the Y-axis for steels (a, c) according to the invention and for comparative steels (b, d). It is clearly visible that the inventive steels outperform the comparative steels in terms of a reduced softening of the HAZ.
- Steels b and d are S960 -Nb and S960 +Cr-Nb respectively (see table 1) and a and c are S960 Base and S960 +V respectively.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Heat Treatment Of Sheet Steel (AREA)
- Heat Treatment Of Steel (AREA)
Abstract
Hot-rolled high-strength micro-alloyed steel strip with improved HAZ-softening resistance having a microstructure comprising martensite, tempered martensite and/or bainite.
Description
Hot-rol led hig h-strength steel strip with improved HAZ-softening resistance and method of producing said steel
The invention rel ates to a hot-rolled high-strength steel strip with improved HAZ-softening resistance and method of producing said steel
Traditionally steels with a high yield strength have been made by austenitising and q uench ing , but by th is tech n iq ue, for insta nce optimal surface quality and impact toughness may not be achieved . Manufacturing expenses have also been high.
EP1375694 describes a method for prod ucing a h ig h-strength, high- toughness steel with good workability and weldability by means of hot rolling . However, the inventors have found that these steels are susceptible to HAZ- softening. The heat-affected zone (HAZ) is the area of base material which has had its microstructure and properties altered by welding or heat intensive cutting operations. The heat from the welding process and subsequent re- cooling causes this change in the area surrounding the weld . The heat-affected zone which forms adjacent to the weld in steels is one of the most common regions of weld failure. Modern thermo-mechanically rolled (TMCP) steels, because of their lean chemistry, and in particular the low carbon content, require carefully controlled welding parameters in order to achieve adequate strength in the weld HAZ. For conventional low-carbon steels and some TMCP pipeline steels such as X70 and X80, HAZ softening is often the result of high heat-input welding procedure because of the slow heat dissipation in the HAZ. For higher grade TMCP steels such as X100, HAZ softening can happen even under moderate welding heat-input because of the base metal's ultra fine grain size and its bainite- and martensite-dominated microstructure. This reduction in hardness and strength in HAZ makes it a weak point in a welded pipeline structure. Consequently it is important to limit the degree to which this softening takes place, given the nature of the base metal and the welding conditions. The areas wh ich have received most study i n rega rds to HAZ softening are high strength plate steels e.g . for linepipe applications and, more recently, AHSS for automotive applications.
WO2007/129676 relates to a hot pressed steel member made from a hig h carbon cold-rolled steel sheet which is austenitised, hot-pressed to
produce a steel member and quenched to achieve a minimum tensile strength of 1.8 GPa. The hot-rolled steel that is to be cold rolled contains at least 50% ferrite.
EP2028284 discloses a seamless steel pipe and EP1662014 discloses a low carbon hot rolled steel plate which is coiled between 450 to 650°C and subsequently promptly reheated to between 550 and 750°C to achieve a three-phase ferrite, bainite and island martensite structure.
The object of the present invention is to achieve a high-strength hot- rolled steel strip that is less susceptible to HAZ-softening than the currently available high strength hot-rolled steel strip.
In a first aspect this object is reached by a hot-rolled high-strength micro- alloyed steel strip having a thickness of between 2 and 16 mm with improved HAZ-softening resistance having a microstructure comprising martensite, tempered martensite and/or bainite, and where the steel contains, in percentages by weight:
0.07 - 0.30% C;
0.8 - 2.0% Mn;
0.01-0.08% A ;
0.2 - 1.5% Cr;
· 0.1-0.7% Mo;
0.0005-0.005 B;
0.01-0.07% Nb;
at most 0.5% Si;
at most 0.03% P;
· at most 0.015% S;
at most 0.05% Ti;
at most 0.1% V;
at most 0.2% Cu;
at most 0.2% Ni;
· at most 0.008% N;
optionally calcium additions for sulphide shape control, at most 0.015%; other elements in amounts of impurity level, balance iron;
the yield strength of the steel strip being at least 960 MPa.
All compositional percentages are given as weight percent, unless indicated otherwise.
The inventive idea is based on the fact that by selecting the combination of chemical elements in the amounts prescribed and in particular the presence of niobium and molybdenum good hardening can be maintained . The steel structure is not critical for the segregation of manganese and carbon during the casting process owing to the low manganese and carbon content. The steel properties are not critical for local fluctuations of the coiling temperature in the strip, which facilitates the steel production and has an advantageous effect in the homogeneity of its mechanical properties, which again has a positive influence both in the flatness of the end product and in the residual stress. The steel sheet is highly suitable for welding and laser cutting, and at the same time it has a good fatigue strength irrespective of said thermal treatments. Further, the steel sheet has excellent bending properties, a good impact toughness as well as a good resistance to softening in tempering. The presence of the precipitating elements in sol ution which are subsequently available for precipitation during the cooling of the HAZ after welding ensures a significant improvement of the HAZ-softening resistance.
The steel according to the invention can be thermally cut, for instance by laser, into precisely defined shapes. It has been observed that a remarkably smooth cutting surface is achieved in a laser cut object. On the other hand, it has been found out that the strength difference between the basic material and the soft zone created in the technical cutting process, which zone is located in the immediate vicinity of the hardened zone, is small or absent also as a result of the presence of the precipitating elements in solution which are subsequently available for precipitation during the cooling of after thermal cutting . These together have an advantageous affect in the fatigue strength . In addition, the relatively low carbon content reduces the peak hardness of the hardened zone, so that the cutting surface is not sensitive to embrittlement and cracking, neither in the working of the object nor in practical use.
Carbon is an important element in controlling the strength, but needs to be limited to some extent to give a good balance in toughness, weldability and formability. The C content is kept relatively low between 0.07 and 0.30% to achieve a good toughness (all percentages in compositions are expressed in
weight percent). In combination with a low temperature coiling temperature the microstructures will contain martensite and/or bainite. The exact amounts strongly depend on the composition, cooling rate on the run-out table and the coiling temperature. At relatively low C contents, the Ms temperature will be quite high, so the martensite will auto temper to some extent. Depending on the strength requirement suitable carbon-windows were found . For a steel having a yield strength of at least 960 MPa the carbon content is preferably at least 0.07 and/or at most 0.13%. For a steel having a yield strength of at least 1 100 M Pa the carbon content is preferably at least 0.13 and/or at most 0.18%, and for a steel having a yield strength of at least 1300 MPa the carbon content is preferably at least 0.19%, more preferably at least between 0.23 and/or at most 0.30%.
A suitable maximum carbon content is 0.27% or even 0.25%.
Elements like manganese, chromium, molybdenum and boron provide hardenability to promote the formation of bainite and/or martensite. The manganese content is limited to between 0.8 and 2.0%. When the manganese exceeds the upper boundary, the risk of segregation becomes significant and this may adversely affect the homogeneity of the microstructure. At levels below 0.8% the effect on hardenability is insufficient. A suitable minimum manganese level is 1.1%.
Boron is added to promote the hardenability. It is important to avoid the formation of boron nitrides as this wil l render the boron ineffective for the promotion of the hardenabil ity. The role of titanium in the composition according to the invention is to protect the boron because Ti forms titanium nitrides and as a consequence no BN is formed . The amount of alloyed boron is at least 0.0005% B (i.e. 5 ppm) but no more than 0.005% B (i.e. 50 ppm) in order to reduce grain size and to increase the hardenability. If titanium is added as an alloying element, the amount of titanium is typically at least 0.01% Ti but no more than 0.05% in order to bind the nitrogen N and to prevent the creation of boron nitrides BN. An alternative within the scope of the invention is to use aluminium to bind the nitrogen and thereby protect the boron . In cases where the formation of TiN-particles is deemed undesirable, e.g . because of their effect on Charpy-toughness, protecting the free boron by aluminium may be the preferred option.
Niobium partly precipitates in the austenite during hot-rolling, thereby contributing to the grain refinement of the final transformed microstructure by the retardation of the recrystallisation of austenite. In addition, the niobium remaining in sol ution at transformation has a powerful effect on red ucing transformation temperatures, especially at faster cooling rates, so it is also beneficial for ha rdena bi l ity . At l ow coil i ng tem peratu res ( < 500°C) the contribution of niobium by precipitation strengthening is expected to be small because the temperature is too low for precipitation of fine NbC. A suitable Nb content is at least 0.02%, preferably at least 0.025%.
V has a similar but less powerful effect as Nb in this case. However, the main reason for the addition of N b and V is to improve the HAZ-softening resistance. In relevant parts of the HAZ, the thermal cycle is su ch that temperatures are reached which will allow precipitation strengthening by Nb and V, thus causing an increase in hardness as a result of the precipitation of elements which were kept in solution by the low coiling temperature. The major contribution is believed to be made by Nb and V carbides, nitrides or carbo-nitrides. To a lesser extent it is believed that MoC precipitates may form having a similar effect. If present, a suitable minimum V-content is 0.04%.
The steels according to the invention are aluminium-killed or aluminium- silicon killed steels in order to reduce the oxygen content to a minimum so that no reaction occurs between carbon and oxygen during solidification. The amounts of aluminium added to the steel during production therefore include those needed for deoxidation . The remaining amount in the end product, also called soluble aluminium (AlSOi) is between 0.01 and 0.08% Al. In the context of this invention the aluminium content referred to is soluble aluminium.
Silicon may also serve as a deoxidant in the steel of the present invention in addition to aluminium. It also acts as a solid solution hardener starting from about at least 0. 10% Si and up to 0.50 % Si, which has an advantageous effect on the impact toug h ness and workabil ity. Above 0.5% the sil icon adversely affects the surface quality of the steel to an unacceptable extent and the removal of the hot rolling scale by pickling becomes increasingly difficult with increasing silicon content.
Phosphorus P contained as an impurity should be at most 0.03%, and sulphur S should be even lower and should be limited to at most 0.015%,
which means that these contents are restricted in order to achieve good impact toughness and bendability. When necessary, further properties can be improved by treating the melt with cored wire containing Ca-Si or Ca-Fe(Ni). During calcium treatment, the alumina and silica inclusions are converted to molten calcium aluminates and silicate which are globular in shape because of the surface tension effect. The calcium aluminates inclusions retained in liquid steel suppress the formation of MnS stringers during solidification of steel . This change in the composition and mode of precipitation of sulphide incl usion during solid ification of steel is known as sulphide morphology or sul phide shape control . This results in less nozzle clogg ing d u ring casting , better mechan ica l properties as the l ong stretched M nS stringers act as crack initiating points. Typical amounts of calcium in the steel for sulphide shape control is 0.0015 to 0.015% Ca. A suitable maximum is 0.005% Ca.
Chromium should be between 0 . 2 a n d 1.5%. Molybdenum should preferably be between 0.1% Mo and 0.7% Mo. Both elements are added in o rder to i n crease h a rd en i n g and tempering resistance. This enables precipitation at higher coiling temperatures, which can be used for decreasing and even preventing the softening of the steel , as well as for al leviating strength fl uctuations caused by local temperatu re d ifferences during the cooling of the coil. A suitable minimum molybdenum content is 0.15%.
Alloying with elements like copper and nickel, often used in steels of this strength level are preferably avoided in view of the surface issues associated with copper. As copper is often alloyed in conjunction with nickel to alleviate the adverse effects of copper this is also not needed . So nickel and/or copper are preferably present at most at impurity level or more preferably completely absent.
Th e m icrostru ctu re of the stee l s a cco rd i n g to the i nve nti o n a re characterised as a microstructure that consists predominantly of tempered martensite, characterised by small carbides in a Widmanstatten pattern, and/or bainite. Ideally the microstructure is free from ferrite and pearlite constituents as these will deleteriously affect the strength level to be reached . In practice it may be unavoidable that some minor patches of ferrite are present, but the amount may not exceed the level where the strength levels is significantly affected . The abovementioned deleterious and subsequently
undesirable ferrite constituents which form at h ig h tra nsfo rmatio n temperatures should be clearly distinguished from the ferritic part of bainite or Widmanstatten ferrite or acicular ferrite which form at low transformation temperatures. The former constituents are undesirable, the latter are not.
The hot-rolled steel strip according to the invention that is directly hot- rolled to the thickness 2 mm - 16 mm can be manufactured as wear-resistant and with different minimum yield strength . Typical threshold values in the marketplace are 960, 1100 and 1300 M Pa, on ly by chang ing the analysis and/or the post-rolling cooling rate of the strip, and/or temperature before the coiling, within the scope of the invention. This kind of high yield strength steel can also be used in targets where the structures require properties typically demanded of structural steel, such as good workability, weldability and impact toug hness, wh ich means that the hot-rolled steel strip according to the invention is feasible also as weldable structural steel. In the steel analysis to be ex p l a i n ed i n th e s pecifi cati o n be l ow, a l l content percentages are percentages by weight, and the rest of the steel that is otherwise not defined is naturally iron, Fe, and unavoidable impurities. The value of 960 MPa can be reached even to thickness values of the hot strip of up to 16 mm . For 1100 and 1300 MPa the values can be reached for val ues of up to 12 mm . The higher thickness results in a somewhat lower cooling rate, and therefore in a less enriched austenite prior to the phase transformation . This leads to a somewhat lower strength level, meaning that with these lean compositions the SHOO or S1300 level cannot be obtained for thicknesses of the hot strip over 12 m m . Preferably the minimum thickness is 3 mm and/or the maximum thickness is 10 mm. It should be noted that the val ues of the strength as defined in this invention are measured in the longitudinal direction (i.e. the tensile specimen is taken in the longitudinal direction of the strip (the direction of movement through the rolling mill)). Values in the transverse direction (i.e. the tensile specimen is taken in the width direction of the strip) may be different from the values in the longitudinal direction, and are usually higher than those in the longitudinal direction for strength and lower for elongation.
In an embodiment the carbon content of the steel is between 0.07 and 0.13% and the yield strength is at least 960 MPa.
In an embodiment the carbon content of the steel is between 0.13 and 0.18% and the yield strength is at least 1100 MPa.
In an embod iment wherein the carbon content is at least 0.19%, preferably between 0.23 and 0.30%, and the yield strength is at least 1300 MPa.
A suitable maximum tensile strength of the hot-rolled steel according to the invention is 1700 MPa.
According to a second aspect the invention is embodied in a method for manufacturing a hot-rolled high-strength micro-alloyed steel strip having a thickness of between 2 and 16 mm with improved HAZ-softening resistance and a yield strength of at least 960 MPa having a microstructure comprising martensite, tempered martensite and/or bainite, and where the steel contains, in percentages by weight:
0.07 - 0.30% C;
· 0.8 - 2.0% Mn;
0.01-0.08% A ;
0.2 - 1.5% Cr;
0.1-0.7% Mo;
0.0005-0.005 B;
· 0.01-0.07% Nb;
at most 0.5% Si;
at most 0.03% P;
at most 0.015% S;
at most 0.05% Ti;
· at most 0.1% V;
at most 0.2% Cu;
at most 0.2% Ni;
at most 0.008% N;
optionally calcium additions for sulphide shape control, at most 0.015%; · other elements in amounts of impurity level, balance iron;
the strip being finish hot-rolled above the Ar3-temperature, wherein the method includes at least the following steps:
• finish rolling to a final thickness of from 2 to 16 mm
• cooling the hot rolled strip within at most 10 seconds from the last hot rolling pass to a coiling temperature of between 20 and 500°C at a cooling rate sufficient to transform the rolled microstructure into a microstructure comprising martensite and/or bainite.
The hot-rolling process is the conventional hot-rolling process, either starting from a slab having a thickness of between 150 to 350 m m, i .e . conventionally continuously cast slabs, or below 150, i.e. thin slab casting or even strip casting . Finish rolling is preferably while the steel is still austenitic to provide the steel with a fine grain and thereby good impact toughness. The coiling temperature is preferably low to achieve the desired mechanical p ro pe rties . Prefe ra b l y th e co i l i n g te m pe ratu re is be l ow 400 °C . By manufacturing this type of steel by fast cooling or quenching directly after hot rol l i n g , a n excel lent i m pact to ug h ness is o bta i ned beca use the phase transformation into martensite and/or bainite takes place from a fine-grained, worked austenite. It also improves the surface quality because the primary scale is removed in a descaler prior to the rolling . Moreover, there is no need for a very expensive lengthy additional annealing treatment to dissolve all precipitates. In a hot strip rolling line, the slabs to be rolled are reheated in a reheating furnace to a temperature range between 1100 to 1250°C, and held for several hours. In that case the dissolution of special carbides, such as Cr and Mo carbides, and the homogenization of the structure is as complete as possible. On the other hand, the growing of the austenite grain at the high heating temperature does not make the end product more brittle, because the austenite grains are refined first by recrystallisation during high temperature rolling in the initial stages of the rolling process and by transformation of the deformed austenite grain formed as a result of the retardation of austenite transformation during thermo-mechanical rolling in the last stages of the hot rolling process. The heavily deformed austenite grains transform into a very fine transformation product during cooling on the run-out table. This results in a h i g h y i e l d s stress , combined with an excellent impact toughness. Manufacturing costs and production time can be further reduced if a thin slab casting and direct rolling facility is used where the elements like Cr and Mo carbides have not even yet precipitated before the rolling starts.
Accord ing to the i nvention , steel is ma n ufactu red at a fina l rol l i ng temperature at which the steel is still austenitic, i.e. above Ar3 to a final hot rolled thickness. The cooling of the strip begins no later than 10 seconds after the last hot rol l ing pass, and it is cooled sufficiently rapidly to al low the austenite to transform into a bainitic and/or martensitic microstructure, the cooling rate preferably being at least 30°C/s, down to a coiling temperature in the range 20°C - 500°C, preferably down to a coiling temperature in the range 20°C - 450°C. The obtained result is typical ly a nearly completely bainitic and/or martensitic microstructure, so that the bainite and/or martensite content preferably is at least 90 % by volume, preferably at least 95%. The microstructure is also preferably free from ferrite formed at high temperatures and free from pearlite constituents, thus rendering the microstructure substantially fully bainitic/martensitic, where Widmannstatten fe rrite o r acicular ferrite is considered to be a bainitic structure for this purpose. In the coiling temperature range of below 100°C the martensite is not tempered, although some auto-tempering may occur at these low temperatures for the low carbon grades, whereas when the coiling temperature is at least 100°C, the martensite is tempered . At temperatures above 200°C the martensite is tempered and the carbon precipitated.
In a preferable embodiment the coiling temperature is at most 450°C, more preferably 425°C, for steels containing a carbon content of at most 0.12% or at most 275°C, more preferably 250 or 225°C, for steels containing a carbon content of at least 0.13%.
In an embodiment the cooling rate during the accelerated cooling after hot rolling and before coiling is between 5 and 100°C/s.
In an embodiment the finish rolling temperature is above Ar3 and also below 920°C, and preferably also below 900°C.
According to a third aspect the steel according to the invention is used in the production of a part for an automobile, a lorry, ship-building, construction work, heavy haul equipment, earth-moving equipment or mobile cranes.
The invention is now further explained by means of the following, non limiting examples. Table 1 shows com positions of steels for each of the categories S700, S960, SHOO and S1300.
Table 1. Composition of the steels (all in weight% x1000, except B and N (ppm).AII
steels are Ca-treated, imp=impurity level)
Type ID C Si Mn Al P S Cr Mo B N Ti V Nb
S960
High Mn 4587 100 250 1770 30 14 5 260 250 20 48 33 imp 39
High Mn 4588 91 240 1780 34 15 5 500 5 20 60 35 imp 39
Low Mn 4589 110 220 1210 31 15 4 490 510 20 50 30 imp 38
Low Mn 4590 110 240 1180 32 15 4 1030 5 20 80 32 imp 39
Low Si 4591 90 100 1600 30 14 5 500 250 20 50 30 imp 40
Low Si m 94 108 1590 38 11 2 502 263 25 52 27 47 40
Base 4699 99 230 1490 33 15 4 510 250 30 60 29 imp 40
+V 4671 94 240 1510 33 15 3 530 250 25 60 31 51 39
-Nb 4670 97 230 1500 35 15 4 540 250 25 60 30 imp imp
+Cr-Nb 4673 110 240 910 32 15 4 1130 300 30 60 29 imp imp
SHOO
B 4814 155 140 1460 23 15 5 490 240 30 60 26 imp 29
+c 4815 170 140 1460 22 15 5 490 240 30 60 29 imp 29
+ Mo 4816 165 140 1470 22 15 5 490 510 30 60 30 imp 30
-Cr 4817 155 140 1460 21 15 5 260 240 30 60 29 12 19
+ Mo-Cr 4818 155 140 1460 22 15 5 250 500 30 60 28 imp 29
-Ti+AI 4819 145 140 1460 59 15 5 450 240 30 60 6 imp 29
+V 4820 155 150 1460 23 15 5 490 240 20 60 29 50 29
-Ti+AI+V 4819* 145 140 1460 59 15 5 450 240 30 60 6 50 29
S1300
Base 250 100 1490 27 14 3 480 510 20 60 3 imp 29
+ B 230 100 1510 27 14 4 490 510 16 60 2 imp 30
+AI 250 110 1500 64 14 4 480 510 18 60 2 imp 28
+Ti 270 110 1510 27 14 4 490 510 20 60 25 imp 30
SEM microstructures show that all hot-rolled steel samples have a microstructure that consists predominantly of tempered martensite, characterised by small carbides in a Widmanstatten pattern. The tempering of the martensite will have resulted due to the high Ms temperature of these relatively low C steels, and also due to the slow cooling to simulate coil cooling . The pattern of the carbides, showing several variants of an orientation relationship between the carbide and the matrix, is characteristic of tempered martensite. The prior austenite grain boundaries were also visible, and showed some elongation along the rolling direction, as was observed using optical metallography. The strength levels depend strongly on the coiling temperature (see figure 1 for the SHOO materials and figure 2 for the S1300 material) which is to be understood in view of the desired microstructure that consists predominantly of tempered martensite.
Figure 3 shows the effect of HAZ-softening on the Y-axis for steels (a, c) according to the invention and for comparative steels (b, d). It is clearly visible that the inventive steels outperform the comparative steels in terms of a reduced softening of the HAZ. Steels b and d are S960 -Nb and S960 +Cr-Nb respectively (see table 1) and a and c are S960 Base and S960 +V respectively.
Claims
1. Hot-rolled high-strength micro-alloyed steel strip having a thickness of between 2 and 16 mm with improved HAZ-softening resistance having a microstructure comprising martensite, tempered martensite and/or bainite, and where the steel contains, in percentages by weight:
0.07 - 0.30% C;
0.8 - 2.0% Mn;
0.01-0.08% A ;
0.2 - 1.5% Cr;
0.1-0.7% Mo;
0.0005-0.005 B;
0.01-0.07% Nb;
• at most 0.5% Si;
at most 0.03% P;
at most 0.015% S;
• at most 0.05% Ti;
at most 0.1% V;
• at most 0.2% Cu;
• at most 0.2% Ni;
• at most 0.008% N;
• optionally calcium additions for sulphide shape control, at most 0.015%;
• other elements in amounts of impurity level, balance iron;
the yield strength of the steel strip being at least 960 MPa.
2. Steel according to any one of the preceding claims having a chromium content of at least 0.2%.
3. Steel according to any one of the preceding claims having a nickel content at impurity level.
4. Steel according to any one of the preceding claims having a copper content at impurity level.
5. Steel according to any one of the preceding claims wherein the carbon content is between 0.07 and 0.13% and having a yield strength of at least 960 MPa. Steel according to any one of claims 1 to 4 wherein the carbon content is between 0.13 and 0.18% and having a yield strength of at least 1100 MPa.
Steel according to any one of claims 1 to 4 wherein the carbon content is at least 0.19%, preferably between 0.23 and 0.30%, and having a yield strength of at least 1300 MPa.
A method for manufacturing a hot-rolled high-strength micro-alloyed steel strip having a thickness of between 2 and 16 mm with improved HAZ-softening resistance and a yield strength of at least 960 MPa having a microstructure comprising martensite, tempered martensite and/or bainite, and where the steel contains, in percentages by weight:
0.07 - 0.30% C;
0.8 - 2.0% Mn;
0.01-0.08% A ;
0.2 - 1.5% Cr;
0.1-0.7% Mo;
0.0005-0.005 B;
0.01-0.07% Nb;
• at most 0.5% Si;
at most 0.03% P;
at most 0.015% S;
• at most 0.05% Ti;
at most 0.1% V;
• at most 0.2% Cu;
• at most 0.2% Ni;
• at most 0.008% N;
• optionally calcium additions for sulphide shape control, at most 0.015%;
• other elements in amounts of impurity level, balance iron;
the strip being finish hot-rolled above the Ar3-temperature, wherein the method includes at least the following steps:
• finish rolling to a final thickness of from 2 to 16 mm
• cooling the hot rolled strip within at most 10 seconds from the last hot rolling pass to a coiling temperature of between 20 and 500°C at a cooling rate sufficient to transform the rolled microstructure into a microstructure comprising martensite and/or bainite.
Method according to claim 8 wherein the coiling temperature is:
• at most 450°C for steels containing a carbon content of at most 0.12% or
• at most 275°C for steels containing a carbon content of at least 0.13%.
Method according to any one of claims 8 to 9 wherein the cooling rate during the accelerated cooling after hot rolling and before coiling is between 5 and 100°C/s.
Method according to any one of claims 8 to 10 wherein the finish rolling temperature is above Ar3 and also below 920°C, and preferably also below 900°C.
Use of the steel according to claim 1 to 7 in the production of a part for an automobile, a lorry, heavy haul equipment, earth-moving equipment or mobile cranes.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201280034223.9A CN103649355B (en) | 2011-07-10 | 2012-07-10 | Have the HAZ-of improvement soften repellence hot-rolled high-strength steel band and the method that produces described steel |
EP12735134.4A EP2729590B1 (en) | 2011-07-10 | 2012-07-10 | Hot-rolled high-strength steel strip with improved haz-softening resistance and method of producing said steel |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP11173383.8 | 2011-07-10 | ||
EP11173383 | 2011-07-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013007729A1 true WO2013007729A1 (en) | 2013-01-17 |
Family
ID=46508348
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2012/063515 WO2013007729A1 (en) | 2011-07-10 | 2012-07-10 | Hot-rolled high-strength steel strip with improved haz-softening resistance and method of producing said steel |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP2729590B1 (en) |
CN (1) | CN103649355B (en) |
WO (1) | WO2013007729A1 (en) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104046918A (en) * | 2013-03-14 | 2014-09-17 | 特纳瑞斯盘管有限公司 | High Performance Material For Coiled Tubing Applications And The Method Of Producing The Same |
US9163296B2 (en) | 2011-01-25 | 2015-10-20 | Tenaris Coiled Tubes, Llc | Coiled tube with varying mechanical properties for superior performance and methods to produce the same by a continuous heat treatment |
EP2998414A4 (en) * | 2013-05-14 | 2017-01-04 | Nippon Steel & Sumitomo Metal Corporation | Hot-rolled steel sheet and production method therefor |
DE102015111177A1 (en) * | 2015-07-10 | 2017-01-12 | Salzgitter Flachstahl Gmbh | High strength multi-phase steel and method of making a cold rolled steel strip therefrom |
US9598746B2 (en) | 2011-02-07 | 2017-03-21 | Dalmine S.P.A. | High strength steel pipes with excellent toughness at low temperature and sulfide stress corrosion cracking resistance |
US9644248B2 (en) | 2013-04-08 | 2017-05-09 | Dalmine S.P.A. | Heavy wall quenched and tempered seamless steel pipes and related method for manufacturing said steel pipes |
US9657365B2 (en) | 2013-04-08 | 2017-05-23 | Dalmine S.P.A. | High strength medium wall quenched and tempered seamless steel pipes and related method for manufacturing said steel pipes |
JP2017525844A (en) * | 2014-06-30 | 2017-09-07 | 宝山鋼鉄股▲分▼有限公司 | Ultra-high strength and ultra-tough oil well pipe and method for producing the same |
US9970242B2 (en) | 2013-01-11 | 2018-05-15 | Tenaris Connections B.V. | Galling resistant drill pipe tool joint and corresponding drill pipe |
WO2020169410A1 (en) * | 2019-02-18 | 2020-08-27 | Tata Steel Ijmuiden B.V. | High strength steel with improved mechanical properties |
US10837079B2 (en) | 2014-01-24 | 2020-11-17 | Rautaruukki Oyj | Hot-rolled ultrahigh strength steel strip product |
US10844669B2 (en) | 2009-11-24 | 2020-11-24 | Tenaris Connections B.V. | Threaded joint sealed to internal and external pressures |
US11105501B2 (en) | 2013-06-25 | 2021-08-31 | Tenaris Connections B.V. | High-chromium heat-resistant steel |
US11124852B2 (en) | 2016-08-12 | 2021-09-21 | Tenaris Coiled Tubes, Llc | Method and system for manufacturing coiled tubing |
CN115698363A (en) * | 2020-06-16 | 2023-02-03 | 瑞典钢铁技术有限公司 | High strength steel product and method for manufacturing same |
RU2798180C2 (en) * | 2013-03-14 | 2023-06-16 | Тенарис Койлд Тьюбз, ЛЛК | High-quality material for flexible long-dimensional pipes and method for its manufacture |
US12129533B2 (en) | 2015-04-14 | 2024-10-29 | Tenaris Connections B.V. | Ultra-fine grained steels having corrosion- fatigue resistance |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102014017273A1 (en) | 2014-11-18 | 2016-05-19 | Salzgitter Flachstahl Gmbh | High strength air hardening multiphase steel with excellent processing properties and method of making a strip of this steel |
US10434554B2 (en) | 2017-01-17 | 2019-10-08 | Forum Us, Inc. | Method of manufacturing a coiled tubing string |
CN108486494B (en) * | 2018-06-05 | 2019-06-21 | 西北工业大学 | Production method of vanadium microalloyed 1300MPa grade high-strength hot-rolled steel sheet and cold-rolled dual-phase steel sheet |
CN109680211A (en) * | 2018-12-28 | 2019-04-26 | 首钢集团有限公司 | A kind of steel for automobile structure and its manufacturing method and manufacturing method of automobile structural parts |
EP3744862A1 (en) | 2019-05-29 | 2020-12-02 | ThyssenKrupp Steel Europe AG | Hot rolled flat steel product with optimised welding properties and method for producing such a flat steel product |
CN113106336B (en) * | 2021-03-17 | 2022-06-10 | 唐山钢铁集团有限责任公司 | Ultrahigh-strength dual-phase steel capable of reducing softening degree of laser welding head and production method thereof |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0867520A2 (en) * | 1997-03-26 | 1998-09-30 | Sumitomo Metal Industries, Ltd. | Welded high-strength steel structures and methods of manufacturing the same |
WO1999005336A1 (en) * | 1997-07-28 | 1999-02-04 | Exxonmobil Upstream Research Company | Ultra-high strength, weldable, boron-containing steels with superior toughness |
EP1375694A1 (en) | 2002-06-19 | 2004-01-02 | Rautaruukki OYJ | Hot-rolled steel strip and method for manufacturing the same |
EP1520912A2 (en) * | 2000-02-10 | 2005-04-06 | Nippon Steel Corporation | Steel excellent in toughness of weld heat-affected zone |
EP1662014A1 (en) | 2003-06-12 | 2006-05-31 | JFE Steel Corporation | Steel plate and welded steel tube exhibiting low yield ratio, high strength and high toughness and method for production thereof |
WO2007129676A1 (en) | 2006-05-10 | 2007-11-15 | Sumitomo Metal Industries, Ltd. | Hot-pressed steel sheet member and process for production thereof |
EP2028284A1 (en) | 2006-03-28 | 2009-02-25 | Nippon Steel Corporation | High-strength seamless steel pipe for mechanical structure which has excellent toughness and weldability, and method for manufacture thereof |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5900075A (en) | 1994-12-06 | 1999-05-04 | Exxon Research And Engineering Co. | Ultra high strength, secondary hardening steels with superior toughness and weldability |
US6364968B1 (en) | 2000-06-02 | 2002-04-02 | Kawasaki Steel Corporation | High-strength hot-rolled steel sheet having excellent stretch flangeability, and method of producing the same |
CN100494451C (en) | 2005-03-30 | 2009-06-03 | 宝山钢铁股份有限公司 | Ultra-high-strength steel plate with a yield strength of 960 MPa or more and its manufacturing method |
CN100372962C (en) | 2005-03-30 | 2008-03-05 | 宝山钢铁股份有限公司 | Ultra-high-strength steel plate with a yield strength of 1100Mpa or more and its manufacturing method |
CN101676425B (en) | 2008-09-18 | 2011-07-20 | 宝山钢铁股份有限公司 | Martensite abrasion-resistant steel with high strength |
FI20095528A7 (en) | 2009-05-11 | 2010-11-12 | Rautaruukki Oyj | Method for manufacturing a hot-rolled strip steel product and a hot-rolled strip steel product |
JP5609383B2 (en) | 2009-08-06 | 2014-10-22 | Jfeスチール株式会社 | High strength hot rolled steel sheet with excellent low temperature toughness and method for producing the same |
JP5630125B2 (en) | 2009-08-06 | 2014-11-26 | Jfeスチール株式会社 | High strength hot rolled steel sheet with excellent low temperature toughness and method for producing the same |
KR101185320B1 (en) | 2009-10-29 | 2012-09-21 | 현대제철 주식회사 | ultra-high strength Hot-rolled steel sheet, and method for producing the same |
CN101748346B (en) | 2009-12-25 | 2012-02-01 | 舞阳钢铁有限责任公司 | High-grade wear-resistant steel plate and production method thereof |
FI122313B (en) | 2010-06-07 | 2011-11-30 | Rautaruukki Oyj | Process for the production of hot rolled steel product and hot rolled steel |
-
2012
- 2012-07-10 WO PCT/EP2012/063515 patent/WO2013007729A1/en active Application Filing
- 2012-07-10 CN CN201280034223.9A patent/CN103649355B/en not_active Expired - Fee Related
- 2012-07-10 EP EP12735134.4A patent/EP2729590B1/en not_active Revoked
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0867520A2 (en) * | 1997-03-26 | 1998-09-30 | Sumitomo Metal Industries, Ltd. | Welded high-strength steel structures and methods of manufacturing the same |
WO1999005336A1 (en) * | 1997-07-28 | 1999-02-04 | Exxonmobil Upstream Research Company | Ultra-high strength, weldable, boron-containing steels with superior toughness |
EP1520912A2 (en) * | 2000-02-10 | 2005-04-06 | Nippon Steel Corporation | Steel excellent in toughness of weld heat-affected zone |
EP1375694A1 (en) | 2002-06-19 | 2004-01-02 | Rautaruukki OYJ | Hot-rolled steel strip and method for manufacturing the same |
EP1662014A1 (en) | 2003-06-12 | 2006-05-31 | JFE Steel Corporation | Steel plate and welded steel tube exhibiting low yield ratio, high strength and high toughness and method for production thereof |
EP2028284A1 (en) | 2006-03-28 | 2009-02-25 | Nippon Steel Corporation | High-strength seamless steel pipe for mechanical structure which has excellent toughness and weldability, and method for manufacture thereof |
WO2007129676A1 (en) | 2006-05-10 | 2007-11-15 | Sumitomo Metal Industries, Ltd. | Hot-pressed steel sheet member and process for production thereof |
Non-Patent Citations (1)
Title |
---|
See also references of EP2729590A1 * |
Cited By (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10844669B2 (en) | 2009-11-24 | 2020-11-24 | Tenaris Connections B.V. | Threaded joint sealed to internal and external pressures |
US10480054B2 (en) | 2011-01-25 | 2019-11-19 | Tenaris Coiled Tubes, Llc | Coiled tube with varying mechanical properties for superior performance and methods to produce the same by a continuous heat treatment |
US9163296B2 (en) | 2011-01-25 | 2015-10-20 | Tenaris Coiled Tubes, Llc | Coiled tube with varying mechanical properties for superior performance and methods to produce the same by a continuous heat treatment |
US11952648B2 (en) | 2011-01-25 | 2024-04-09 | Tenaris Coiled Tubes, Llc | Method of forming and heat treating coiled tubing |
US9598746B2 (en) | 2011-02-07 | 2017-03-21 | Dalmine S.P.A. | High strength steel pipes with excellent toughness at low temperature and sulfide stress corrosion cracking resistance |
US9970242B2 (en) | 2013-01-11 | 2018-05-15 | Tenaris Connections B.V. | Galling resistant drill pipe tool joint and corresponding drill pipe |
US11377704B2 (en) | 2013-03-14 | 2022-07-05 | Tenaris Coiled Tubes, Llc | High performance material for coiled tubing applications and the method of producing the same |
CN104046918A (en) * | 2013-03-14 | 2014-09-17 | 特纳瑞斯盘管有限公司 | High Performance Material For Coiled Tubing Applications And The Method Of Producing The Same |
EP3845672A1 (en) * | 2013-03-14 | 2021-07-07 | Tenaris Coiled Tubes, LLC | High performance material for coiled tubing applications and the method of producing the same |
CN104046918B (en) * | 2013-03-14 | 2017-10-24 | 特纳瑞斯盘管有限公司 | The high performance material and its production method applied for continuous pipe |
US9803256B2 (en) | 2013-03-14 | 2017-10-31 | Tenaris Coiled Tubes, Llc | High performance material for coiled tubing applications and the method of producing the same |
RU2798180C2 (en) * | 2013-03-14 | 2023-06-16 | Тенарис Койлд Тьюбз, ЛЛК | High-quality material for flexible long-dimensional pipes and method for its manufacture |
EP2778239A1 (en) * | 2013-03-14 | 2014-09-17 | Tenaris Coiled Tubes, LLC | High performance material for coiled tubing applications and the method of producing the same |
US10378074B2 (en) | 2013-03-14 | 2019-08-13 | Tenaris Coiled Tubes, Llc | High performance material for coiled tubing applications and the method of producing the same |
US10378075B2 (en) | 2013-03-14 | 2019-08-13 | Tenaris Coiled Tubes, Llc | High performance material for coiled tubing applications and the method of producing the same |
US9657365B2 (en) | 2013-04-08 | 2017-05-23 | Dalmine S.P.A. | High strength medium wall quenched and tempered seamless steel pipes and related method for manufacturing said steel pipes |
US9644248B2 (en) | 2013-04-08 | 2017-05-09 | Dalmine S.P.A. | Heavy wall quenched and tempered seamless steel pipes and related method for manufacturing said steel pipes |
US11208702B2 (en) | 2013-05-14 | 2021-12-28 | Nippon Steel Corporation | Hot-rolled steel sheet and manufacturing method thereof |
US10260124B2 (en) | 2013-05-14 | 2019-04-16 | Nippon Steel & Sumitomo Metal Corporation | Hot-rolled steel sheet and manufacturing method thereof |
EP2998414A4 (en) * | 2013-05-14 | 2017-01-04 | Nippon Steel & Sumitomo Metal Corporation | Hot-rolled steel sheet and production method therefor |
US11105501B2 (en) | 2013-06-25 | 2021-08-31 | Tenaris Connections B.V. | High-chromium heat-resistant steel |
US10837079B2 (en) | 2014-01-24 | 2020-11-17 | Rautaruukki Oyj | Hot-rolled ultrahigh strength steel strip product |
JP2017525844A (en) * | 2014-06-30 | 2017-09-07 | 宝山鋼鉄股▲分▼有限公司 | Ultra-high strength and ultra-tough oil well pipe and method for producing the same |
US12129533B2 (en) | 2015-04-14 | 2024-10-29 | Tenaris Connections B.V. | Ultra-fine grained steels having corrosion- fatigue resistance |
DE102015111177A1 (en) * | 2015-07-10 | 2017-01-12 | Salzgitter Flachstahl Gmbh | High strength multi-phase steel and method of making a cold rolled steel strip therefrom |
US11124852B2 (en) | 2016-08-12 | 2021-09-21 | Tenaris Coiled Tubes, Llc | Method and system for manufacturing coiled tubing |
US11732320B2 (en) | 2019-02-18 | 2023-08-22 | Tata Steel Ijmuiden B.V. | High strength steel with improved mechanical properties |
WO2020169410A1 (en) * | 2019-02-18 | 2020-08-27 | Tata Steel Ijmuiden B.V. | High strength steel with improved mechanical properties |
CN115698363A (en) * | 2020-06-16 | 2023-02-03 | 瑞典钢铁技术有限公司 | High strength steel product and method for manufacturing same |
Also Published As
Publication number | Publication date |
---|---|
CN103649355A (en) | 2014-03-19 |
EP2729590A1 (en) | 2014-05-14 |
CN103649355B (en) | 2016-08-17 |
EP2729590B1 (en) | 2015-10-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2729590B1 (en) | Hot-rolled high-strength steel strip with improved haz-softening resistance and method of producing said steel | |
US4572748A (en) | Method of manufacturing high tensile strength steel plates | |
US6290789B1 (en) | Ultrafine-grain steel pipe and process for manufacturing the same | |
KR101635008B1 (en) | Thick-walled, high tensile strength steel with excellent ctod characteristics of the weld heat-affected zone, and manufacturing method thereof | |
US9023158B2 (en) | Steel material superior in high temperature characteristics and toughness and method of production of same | |
JP7411072B2 (en) | High-strength, extra-thick steel material with excellent low-temperature impact toughness and method for producing the same | |
US4591396A (en) | Method of producing steel having high strength and toughness | |
US20100047107A1 (en) | Steel material superior in high temperature strength and toughness and method of production of same | |
CN109023036A (en) | Ultrahigh-strength hot-rolled complex-phase steel plate and production method thereof | |
CN109536846A (en) | Yield strength 700MPa grade high ductility hot rolled steel plate and its manufacturing method | |
CN106498296A (en) | Manufacturing method of high-strength steel with yield strength of 1100MPa | |
KR20220085820A (en) | Hot-rolled H-shaped steel based on deformed billet rolling forming and manufacturing method thereof | |
JP7244718B2 (en) | Steel material for thick high-strength line pipe with excellent low-temperature toughness, elongation and small yield ratio, and method for producing the same | |
CA3078690A1 (en) | Hot rolled steel sheet and method for producing same | |
EP1375694A1 (en) | Hot-rolled steel strip and method for manufacturing the same | |
US11021769B2 (en) | Micro alloyed steel and method for producing said steel | |
RU2734216C9 (en) | Method of making a flat steel product from steel with manganese content and such a flat steel product | |
CN101512033B (en) | Fire-resistant steel excellent in high-temperature strength, toughness and reheat embrittlement resistance and process for production of the same | |
EP3556890B1 (en) | High-strength steel plate having excellent burring workability in low temperature range and manufacturing method therefor | |
CA3108674C (en) | Steel for pressure vessel having excellent surface quality and impact toughness, and method for manufacturing same | |
CN111051555B (en) | Steel sheet and method for producing same | |
JP5082500B2 (en) | Manufacturing method of high toughness and high strength steel sheet with excellent strength-elongation balance | |
US12258648B2 (en) | Method for producing thermo-mechanically produced profiled hot-rolled strip products | |
KR100825650B1 (en) | Low-mote thick thick plate with excellent plate deformation characteristics and manufacturing method | |
US20030221753A1 (en) | Super fine granular steel pipe and method for producing the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12735134 Country of ref document: EP Kind code of ref document: A1 |
|
DPE1 | Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2012735134 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |