AU2018201165B2 - Steel alloy for a low-alloy, high-strength steel - Google Patents
Steel alloy for a low-alloy, high-strength steel Download PDFInfo
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- AU2018201165B2 AU2018201165B2 AU2018201165A AU2018201165A AU2018201165B2 AU 2018201165 B2 AU2018201165 B2 AU 2018201165B2 AU 2018201165 A AU2018201165 A AU 2018201165A AU 2018201165 A AU2018201165 A AU 2018201165A AU 2018201165 B2 AU2018201165 B2 AU 2018201165B2
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 40
- 239000010959 steel Substances 0.000 title claims abstract description 40
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 20
- 239000000956 alloy Substances 0.000 title claims abstract description 20
- 229910000851 Alloy steel Inorganic materials 0.000 title claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 20
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 15
- 238000001556 precipitation Methods 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 9
- 229910001567 cementite Inorganic materials 0.000 claims abstract description 8
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- 229910001566 austenite Inorganic materials 0.000 claims description 40
- 229910052782 aluminium Inorganic materials 0.000 claims description 36
- 230000009466 transformation Effects 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 21
- 229910000734 martensite Inorganic materials 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 20
- 229910001563 bainite Inorganic materials 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 229910052748 manganese Inorganic materials 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 238000005275 alloying Methods 0.000 claims description 8
- 238000010276 construction Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- 238000004626 scanning electron microscopy Methods 0.000 claims description 4
- 238000003723 Smelting Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 2
- 230000003019 stabilising effect Effects 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 18
- 239000011572 manganese Substances 0.000 description 17
- 239000011651 chromium Substances 0.000 description 14
- 239000010955 niobium Substances 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 238000007792 addition Methods 0.000 description 13
- 239000010936 titanium Substances 0.000 description 11
- 229910000859 α-Fe Inorganic materials 0.000 description 9
- 229910052804 chromium Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229920001296 polysiloxane Polymers 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 6
- 230000002411 adverse Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- -1 aluminum nitrides Chemical class 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000002939 deleterious effect Effects 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910001568 polygonal ferrite Inorganic materials 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 102100023053 Band 4.1-like protein 5 Human genes 0.000 description 1
- 101001049973 Homo sapiens Band 4.1-like protein 5 Proteins 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- VDSREIHVGSWINN-UHFFFAOYSA-N [V].[Mo].[Ni] Chemical compound [V].[Mo].[Ni] VDSREIHVGSWINN-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- 230000003993 interaction Effects 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
- 239000000155 melt Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of 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
- C22C38/001—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
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
-
- 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
- C21D2211/001—Austenite
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Heat Treatment Of Steel (AREA)
- Heat Treatment Of Sheet Steel (AREA)
Abstract
Abstract The invention relates to a low alloy high-strength carbide-free bainitic steel for producing strips, sheets and pipes with the following chemical composition (in weight %) 0.10 - 0.70 C, 0.25 - 4.00 Si, 0.05 - 3.00 Al, 1.00 - 3.00 Mn, 0.10 - 2.00 Cr, 0.001 - 0.50 Nb, 0.001 - 0.025 N, max 0.15 P, max 0.05 S, remainder iron and steel tramp elements with optional addition of one or more elements of Mo, Ni, Co, W, Nb, Ti, or V and Zr and rare earths with the proviso the for avoiding primary precipitations of AIN the condition Al x N < 5 x 10-3 (weight %) and for suppressing the cementite formation the condition Si + Al > 4 x C (weight %) are satisfied. 9991858 1 (GHMatters) P99274.AU.1
Description
STEEL ALLOY FOR A LOW ALLOY HIGH-STRENGTH STEEL
Description [001] The invention relates to a steel alloy for a low alloy high strength steel which at the same time is tenacious and has excellent wear resistance according to patent claim 1.
[002] In particular, the invention relates to pipes, strips and sheets made of this alloy, from which for example components for the automobile industry such as vehicle bodies, components of support structures or airbag tubes and cylinder tubes are produced. In the field of construction-machine industry, wear plates made of this alloy can for example be used in case of high wear requirements for excavator shovels. Such steels are also used for applications where sudden impact energies have to be absorbed, for example as bullet proof armor.
[003] Pipes produced from this alloy can be configured as welded pipes that are produced from hot or cold strip or in a seamlessly, and which depending on the case can have a cross section which deviates from the circular shape.
[004] Construction pipes or plates made of this alloy can also be used for welded steel constructions that are exposed to particularly high stress for example in crane construction, bridge construction, hoist construction and heavy-duty vehicle construction.
[005] The demands for ever higher strength and improved processing properties and component properties while at the same time reducing weight and/or costs have lead among other things to the development of ultra-fine grained duplex steels which are also known under the name “Super Bainite” as carbide-free steels. The generation of such a microstructure consisting of bainitic ferrite with residual
11660578_1 (GHMatters) P99274.AU.1
2018201165 29 Aug 2019 austenite lamellae is schematically shown in Figure 1 in contrast to the upper and lower bainite microstructure.
[006] Characteristic for these steels is for example a strength of 1000 to about 2000 MPa, an elongation at brake of at least 5% depending on the strength and an extremely fine (nano) structured bainitic microstructure with portions of residual austenite.
[007] The approach for generating this ultra-fine microstructure is based on the phase transformation at low temperatures in the bainite region while avoiding the precipitation of cementite and formation of martensite. Suppression of carbides that precipitate in the bainite such as cementite is necessary because on one hand, these have a strong embrittling effect as possible fracture inducers thereby preventing achieving the required tenacity, and on the other hand, the proportions of stabilized austenite, which are necessary for achieving the properties according to the invention, cannot be established.
[008] The economic use of these steels is impeded, however, because at these low transformation temperatures the transformation kinetic is strongly decelerated which depending on the alloy composition, in particular with increasing carbon content, can lead to longer isothermal holding times of many hours up to one or more days. Such long processing times are, however, not acceptable for an economic production of components so that alloy concepts were pursued as solutions to accelerate the transformation.
[009] An alloy composition which requires such a long isothermal transformation time of up to 48 hours is known from WO 2009/0-75494. It is also disadvantageous that this steel contains expensive nickel, molybdenum, boron and titanium beside carbon and iron and the achievable tenacities are not yet sufficient for the described fields of application.
11660578_1 (GHMatters) P99274.AU.1
2018201165 29 Aug 2019 [0010] Carbide-free bainitic steels for rail tracks are for example known from
DE 696 31 953 T2. Beside manganese, chromium and further elements such as molybdenum nickel vanadium wolfram titanium and boron, the steel alloy disclosed there has a silicon content between 1 and 3%.
[0011] This publication also mentions that beside silicone the addition of aluminum can reduce or suppress the formation of carbides in the bainite and can stabilize the remaining residual austenite. This steel also allows overcoming the disadvantage of a long transformation time, wherein a corresponding bainitic microstructure can be generated by continuous cooling at air (air hardening) alone.
[0012] This steel is configured for the demands on rail tracks that are exposed to strong wear stress, however it cannot be used or is uneconomical for strips, sheets and pipes for the mentioned field of application because in these cases beside the demands on wear resistance, the strength and tenacity requirements also have to be met. In addition, due the their compact cross section, the cross sectional dimensions of rails significantly differ from those of strips, sheets and pipes which requires adjustment of the alloying concept with regard to the material properties to be achieved after air cooling of the steel. A disadvantage of the known steel is also the expensive addition of titanium and other alloy elements such as nickel, molybdenum and wolfram.
[0013] A further problem in the known steels is that no information regarding the nitrogen content are given which adversely affects material properties in particular through formation of aluminum nitrides when aluminum is added.
[0014] As a result of the addition of aluminum due to the great affinity to the nitrogen present in the steel, coarse aluminum nitrides are formed during solidification which precipitate primarily in the steel which has a very negative effect on the ductility notch impact toughness the bursting behavior and the service life of
11660578_1 (GHMatters) P99274.AU.1
2018201165 29 Aug 2019 the steel and with this significantly deteriorates the mechanical properties.
[0015] As a result, this known steel alloy in which instead of silicone, aluminum or in addition further aluminum is added, is rendered unusable in praxis because the amount of precipitations and size of deleterious aluminum nitrides is dependent on the respective nitrogen and aluminum content in the steel and, because the nitrogen is not taken into account, the concrete material properties cannot be predicted. In addition, the achievable tenacities for the described field of application according to the invention are also not sufficiently high.
[0016] The demands on the mechanical properties of the steel alloy that have to be satisfied can be summarized as follows:
[0017] Strength: 1250 to 2500 MPa [0018] Elongation at break above 12% [0019] Notch impact toughness at-20°C: at least 15 J [0020] There is a need for a steel alloy for a low alloy, high-strength carbidefree bainitic steel which is tenacious and wear resistant for producing strips, sheets and pipes, which on one hand is more cost effective than the known steel alloys and on the other hand ensures uniform material properties which meet the demands such as strength, elongation at break, tenacity etc. In addition, these material properties are also to be achieved when cooling at stationary air by air hardening.
[0021] The present invention provides a method for producing a steel alloy for the production of strips, sheets and tubes, the steel alloy being a low alloy highstrength, carbide-free bainitic steel with the following chemical composition (in wt.%): 0.10-0.70 C
0.25-4.00 Si
0.05-3.00 Al
11660578_1 (GHMatters) P99274.AU.1
2018201165 29 Aug 2019
1.00-3.00 Μη
0.10-2.00 Cr
0.001 -0.50 Nb
0.001 -0.025 N max. 0.15 P max. 0.05 S remainder iron with smelting-related impurities with optional addition of one or more elements of Mo, Ni, Co, W, Ti or V and Zr and rare earths elements such as Ce, Hf, La, Re, Sc and/or Y in contents totaling up to 1 wt.%, with the proviso that, to avoid primary precipitations of AIN, the condition Al χ N < 5 χ 10'3 (wt.%) is satisfied and to suppress cementite formation the condition Si + Al > 4 χ C (wt.%) is satisfied wherein:
- the optional alloying elements have the following contents in wt. %:
max. 5.00 Ni max. 1.00 Mo max. 2.00 Co max. 1.50 W max. 0.10 Ti max. 0.20 V
- wherein the total content of Ti, V is no more than 0.20% and the total content of Ni, Mo, Co, W, Zr is no more than 5.50 wt%,
- wherein the average previous austenite grain size - determined by scanning electron microscopy - has a value of no more than 100 pm and the average interspacing of the residual austenite lamellae is less than 750 nm, the microstructure consists of carbide-free bainite and residual austenite lamellae with a fraction of at least 75% bainite, at least 10% residual austenite and up to a maximum of 5% martensite,
- wherein the steels in the bloom or slab state already have a strength (Rm) of over 1250 MPa, an elongation at break of over 12% and a toughness (notched impact strength) at -20°C of at least 15 J after cooling in air,
11660578_1 (GHMatters) P99274.AU.1
2018201165 29 Aug 2019 wherein
- to achieve the required material properties the following conditions for transformation kinetics, martensite start temperature and microstructure formation are observed:
- ferritic transformation kinetics (C, Mn, Si and Al here correspond to the element contents in wt.% and T to the cooling rate in °C/s):
(35 x C)+ (10 x Mn) - Si - (5 x Al) + Cr > 13/7” + 10
- bainitic transformation kinetics (C, Mn and Al here correspond to the element contents in wt.% and T to the cooling rate in °C/s):
400 x exp [(-7 x C) - (4 x Mn) + 8 Al + 3]/Γ > 1
- martensite start temperature (°C; C, Mn, Si, Al and Mo here correspond to the element contents in wt.%):
525 - (350 x C) - (45 x Mn) - (16 x Mo) - (5 x Si) + (15 x Al) < < 400
- stabilising the residual austenite (C, Si and Al here correspond to the element contents in wt.%):
Si + Al > 4 x C
- avoiding primary AIN precipitations (Al and N here correspond to the element contents in wt.%):
Al x N < 5 x 10-3
11660578_1 (GHMatters) P99274.AU.1
- meeting the required combination of mechanical properties:
2018201165 29 Aug 2019
C + Si/6 + Mn/4 + (Cr + Mo)/3 > 1.
[0022] Disclosed herein is also a steel alloy with the following chemical composition is proposed (in weight %):
0.10-0.70 C
0.25-4.00 Si
0.05-3.00 Al
1.00-3.00 Mn
0.10-2.00 Cr
0.001 -0.50 Nb
0.001 -0.025 N max. 0.15 P max 0.05 S remainder iron with smelting related contaminations with optional addition of one or more elements of Mo, Ni, Co, W, Nb, Ti, or V and Zr and rare earth elements; and wherein (a) Al x N < 5 x 10'3 (weight %) for avoiding primary precipitations of AIN; and (b) Si + Al > 4 x C (weight %) for suppressing the cementite formation; and (c) the elements that are to be alloyed have the following contents in weight percent:
max. 5.00 Ni max. 1.00 Mo max. 2.00 Co max. 1.50 W max. 0.10 Ti max. 0.20 V;
(d) the total content of Ti, V is maximally 0.20% and the total content of Ni, Mo, Co,
W is maximally 5.50 weight %; and
11660578_1 (GHMatters) P99274.AU.1
2018201165 29 Aug 2019 (e) a microstructure that includes at least 10% retained austenite, at most 5% martensite and lamellae offerrite and residual austenite with an average distance of the residual austenite lamellae being less than 750 nm.
[0023] Optionally rare earths and reactive elements such as Ce, Hf, La, Re, Sc and/or Y of a\overall up to 1 weight % can be added.
[0024] In the puddle lump or slab state, steels according to the invention have already after cooling at air a strength (Rm) of over 1250 MPa, an elongation at break of over 12% and a tenacity (KBZ) at -20°C of at least 15 J (cf. Table 1). The microstructure consists of carbide-free bainite and residual austenite with a proportion of at least 75% bainitic ferrite, at least 10 % residual austenite and up to maximally 5% martensite (or martensite phase and/or decomposed austenite).
[0025] The steel alloy according to the invention is based on the development of the carbide-free bainitic steel form DE 6906 953 T2 and WO 2009/075494 A1.
[0026] Tests that were carried out in the context of the present invention have surprisingly shown that compared to known steel alloys for achieving the demanded material properties already can be achieved by an air hardening by targeted addition of aluminum in the range of 0.05 to 3.0 weight % and niobium in the range of 0.001 to 0.5 weight % beside an excellent material strength and wear resistance, very good tenacity can be achieved. In particular, the addition of niobium results in a significant improvement of the tenacity properties through grain refinement, so that this alloy meets the high requirements regarding mechanical properties and wear resistance.
[0027] Also, as a result of the advantageous addition of chromium in the range of 0.10 to 2.00 weight %, the kinetic of the ferrite formation can be decisively controlled so that the formation of coarse polygonal ferrite bodies, which can adversely affect the material properties, can be effectively avoided. Important in this
11660578_1 (GHMatters) P99274.AU.1
2018201165 29 Aug 2019 regard is the interaction between aluminum and chromium. While aluminum accelerates the ferritic and bainitic transformation, addition of chromium delays the ferritic transformation (cf. Figure 2). Targeted combination of these two elements, allows controlling the kinetic of the ferrite and bainite formation.
[0028] Beside the known advantageous effect of adding aluminum on avoiding carbide precipitations in the bainite, tests have shown that the addition of aluminum compared to silicone significantly accelerates the kinetic of the bainitic transformation. The latter also increases with increasing contents of aluminum which mean that the tenacity and strength of the steel according to the invention is significantly improved after continuous cooling compared to steel which are only alloyed with silicone, i.e., higher tenacity and strength values can be achieved. Advantageous are cooling rates greater than 10°C/s in order to achieve the demanded combination of mechanical properties also in thicker sheets (for example above 10 mm); the demanded mechanical properties can also be achieved by means of cooling at stationary air in the case of thinner sheets or by adjusting the alloying concept. The influence of different alloying elements on the kinetic of the transformation is shown in Figure 2. The effects of C, Si, Al, Mn, Cr and Mo on the transformation kinetic offerrite, perlite and bainite and on the martensite start temperature are shown schematically.
[0029] According to the invention, compared to the known steel, it is strictly necessary for achieving these advantageous properties that the nitrogen content does not exceed the stated upper limit of 0.025%, better 0.015% or optimally 0.010 weight % in order to minimize the number and size of the deleterious aluminum nitrides as primary precipitations in the steel, wherein in addition the condition Al χ N < 5 χ 10'3 has to be satisfied. Otherwise, a minimal content of nitrogen of 0.001 weight %, optimally 0.0020 is required in order to enable a required niobium carbonitride formation for increasing tenacity by grain refinement.
11660578_1 (GHMatters) P99274.AU.1
2018201165 29 Aug 2019 τ
[0030] The tested alloy compositions and the determined mechanical characteristics are shown in Table 1. All samples where heated to about 950°C and then cooled at stationary air or subjected to accelerated cooling. The required cooling speed is selected depending on the sheet thickness and the composition. As the results of the mechanical sampling show, the demanded properties could not be achieved with the sample melt 14 due to the too low Cr content. The test melt 16 satisfied the demands due to the greater sheet thickness of 12 mm only after accelerated cooling. Typical temperature profiles for the cooling at stationary air or with quenching are shown in Figure 3.
[0031] In Figure 4 some of the tested test melts and their mechanical characteristics and cooling conditions are shown in comparison to the conventional and high strength steel materials. It can be seen that in the developed steel the region of higher strength materials at improved stretch properties.
[0032] The results confirm the excellent mechanical properties (strength and tenacity of the steel alloy according to the invention already for semi-finished products such as puddle lumps or slabs) in the hardened state (Table 1).
[0033] As essential element, aluminum plays an important role which beside accelerating the transformation kinetic also suppresses the carbide precipitation in the bainite in combination with silicone, as a result, residual austenite is stabilized because carbon only has a limited solubility in the ferrite. A high proportion of residual austenite of at least 10% in the bainite causes beside the extremely fine lamellar microstructure the excellent mechanical properties. The different microstructure components were determined by scanning electron microscopy, wherein a mean lamellar interspacing of 300 nm was determined. A schematic representation of a previous austenite grain with substructure (such as for example sub grains) with fine lamellar microstructure is schematically shown in figure 5. Here, the previous austenite grain structure is stabilized via Nb(C,N) precipitations.
11660578_1 (GHMatters) P99274.AU.1
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| o IX | N W O CN rM | | ιΛ O ΓΝ rd | 0760 | c0 in o | 0796 | ||
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| < | © o' | 0,280 | o © o' | 0,092 | 0,107 | ||
| !Z! | 0,002 | 0,003 | CN o o o | 0,002 | CN O o o' | ||
| 0- | m o o' | 0,016 | ΓΝ G o' | 0,013 | 0,015 | ||
| in Ch | 1,938 | G rn | 1,937 | in σγ | |||
| in | o | 3,040 | o CN | 1,080 | o | ||
| U | Ch N o' | LD Ch o' | 0,197 | cn o' | 0,299 | ||
| <p | £ | tn o | 5 | <£ | |||
| « -5 8 “§ g § α> δ H ·= > .2 E- ° .2 ~ | Test steels not according to the invention |
11660578J (GHMatters) P99274.AU.1
2018201165 29 Aug 2019 [0034] With corresponding proportions of residual austenite a so called TRIPeffect can then also be advantageously used. Steels which usually are referred to by the term TRIP (“Transformation Induced Plasticity”) are steels which at the same time have a very high strength and a high ductility, which makes them especially suited for cold forming. These properties are obtained owing to their special microscopic structure, wherein the deformation-induced martensite formation and the work hardening associated therewith is inhibited and the ductility is increased. The effect of the TRIP effect is optimal for a residual austenite proportion of about 1 to 20%.
[0035] In the following, the alloying concept according to the invention is explained in more detail.
- Carbon: for reason of sufficient strength of the material the minimal content should not be below 0.10 weight %. With regard to a sufficiently low martensite start temperature and with this the establishment of a very fine microstructure, however still good weldability, the carbon content should not be above 0.70 weight %. Carbon contents between 0.15 and 0.60 weight % have proven advantageous, wherein optimal properties are achieved when the carbon content is between 0.18 and 0.50 weight %.
- Aluminum/silicone: the essential element for achieving the demanded material properties after continuous cooling is aluminum which strongly accelerates the transformation kinetic.
In order to achieve this effect the aluminum content should be at least 0.05% weight % but maximally 3.00% weight % because otherwise coarse polygonal ferrite bodies could form which in turn adversely affect the material properties. If the aluminum content is too low the bainitic transformation becomes too slow so that the formation of martensite is promoted which adversely affects the elongation at break and the notch impact toughness. For a sufficient suppression of carbides in the bainite, silicone at contents of 0.25 to 4.00
11660578_1 (GHMatters) P99274.AU.1
2018201165 29 Aug 2019 weight % can be added. Good material properties are achieved at aluminum contents between 0.07 and 1.50 weight % and optimal ones between 0.09 and
0.75 weight %. Corresponding silicone contents are between 0.50 to 1.75 weight % or between 0.75 and 1.50 weight %.
- As a result of the targeted addition of chromium of at least 0.10 to 2.00 weight % the ferritic transformation can be decelerated and via a combination with aluminum the kinetic of the ferrite and bainite formation can be controlled in a targeted manner. Advantageous chromium contents are between 0.10 to 1.75 weight % or between 0.10 and 1.50 weight %.
- Manganese: the addition of Manganese in the range of 1.00 to 3.00 weight % results in dependence on the respective demands on the steel alloy as a compromise between strength, which can be achieved by higher additions, and a sufficient tenacity which can be achieved at lower contents. With regard to a very good or optimal property combination, the manganese content should be between 1.50 and 2.50 weight % or between 1.70 and 2.70 weight %.
- Niobium/nitrogen: A niobium content of 0.001 to 0.50 weight % has to be established for ensuring formation of Nb(C,N). The resulting grain refinement contributes to a significant improvement of the tenacity properties. In addition a nitrogen content of 0.001 to 0.025 weight % is recommended for forming Nb(N) because NbN is more stable than NbC and thus leads to an increased grain refinement. Advantageous niobium contents are 0.001 to 0.10 or 0.001 to 0.05 weight % at advantageous nitrogen contents of 0.001 to 0.015 or 0.002 to 0.010 weight %. In addition, adding nitrogen prevents excessive binding of C via Nb because otherwise the austenite stabilizing effect of C could be lost.
- If needed for example molybdenum (up to 1.00 weight %), nickel (up to 5.00
11660578_1 (GHMatters) P99274.AU.1
2018201165 29 Aug 2019 weight %) cobalt (up to 2.00 weight %) or wolfram (up to1.50 weight %) can be added as solid solution hardener for further increasing strength. As an alternative or in addition micro-alloying elements such as vanadium at up to 0.2 weight % and/or titanium up to 0.10 weight % can be added. A total content of Ti, V of max 0.20 weight % and Ni, Mo, Co, W, Zr of max 5.50 weight % should be observed. In order to take advantage of the effect of these alloy elements, a minimal content of 0.01 weight % should be observed.
Rare earths and reactive elements: rare earths and reactive elements such as Ce, Hf, La, Re, Sc and/or Y can be optionally added to achieve an optimal lamellar interspacing and thus for further increase of strength and tenacity at total contents of up to 1 weight %. If necessary a total content of 20 ppm should be added.
[0036] In the alloy composition the following conditions should be adhered to for achieving the demanded material properties in particular of the mechanical technological properties for the transformation kinetic and the transformation behavior (Figure 2) the stabilizing of the residual austenite and the martensite start temperature while taking the cooling rate into account wherein in the mentioned empirically determined formulas the contents of C, Mn, Si, Al, Cr and Mo in weight % and T as cooling rate in °C/s have to be inserted. The units of the coefficients that are used in the formula are to be selected according to the variables used in the formula.
[0037] Kinetic of the ferritic transformation:
For adhering to or setting the mechanical-technical properties and in particular for avoiding the formation of the coarse polygonal ferrite grains which adversely affect the material properties, the following condition has to be satisfied:
(35 x C) + (10 x Mn) - Si - (5 x Al) + Cr > 134/T+ 10
11660578_1 (GHMatters) P99274.AU.1
2018201165 29 Aug 2019 [0038] Kinetic of the bainitic transformation:
The following equation for the kinetic of the bainitic transformation has to be established to achieve a suitable microstructure with very finely configured bainitic ferrite/residual austenite lamellae for the mechanical technological properties:
400 x exp [(-7 xC) - (4 x Mn) + 8 Al + 3]/ T > 1 [0039] Martensite start temperature (°C):
for avoiding greater martensitic microstructure proportions which deteriorate the mechanical technological properties the martensite start temperature has to be determined as follows:
525 - (350 x C) - (45 x Mn) - (16 x Mo) - (5 x Si) + (15 Al) « 400 [0040] For stabilizing the residual austenite, formation of cementite has to be suppressed. This is achieved by a targeted alloying with Si and Al because both elements have a very low solubility in cementite. For this, the following condition has to be satisfied:
Si + Al > 43 x C [0041] For avoiding deleterious primary AIN precipitations, the following condition has to be satisfied:
Al χ N > 5x 10-3
In Figure 6, this relationship is again shown schematically.
[0042] Transformation capacity:
For establishing the properties according to the invention on the basis of the describe microstructure a complete austeniziation of the steels according to the invention has to be achieved prior to the final heat treatment (cf. Figure 1).
[0043] In order to achieve the demanded combination of the mechanical properties (strength ductility and tenacity) the following relationship of the ferrite and
11660578_1 (GHMatters) P99274.AU.1
2018201165 29 Aug 2019 austenite formers is to be satisfied:
C+Si/6+Mn/4+(Cr+Mo)/3>1.
[0044] The microstructure of the steel according to the invention consist of ferrite and residual austenite lamellae. It can have proportions of martensite of up to 5% (or martensite/austenite phase and/or decomposed austenite). The two most important characteristics of the microstructure which significantly influence the mechanical properties of the steel are the lamella spacing and the proportion of residual austenite. The smaller the lamellar interspacing and the higher the proportion of residual austenite the higher are the strength and elongation at break of the material.
[0045] In order to achieve the demanded high strength of the material of at least 1250 to 2500 MPa the average lamellar interspacing should be smaller than 750 nm, advantageously smaller than 500 nm.
[0046] In order to achieve the stretch values of at least 12% (and elongation at break) a residual austenite proportion of at least 10% and a martensite proportion of at most 5% should be present.
[0047] In order to achieve the high tenacity by grain refinement by means of niobium carbonitride formation, the average previous austenite grain size should not exceed a value of 100 pm.
[0048] Because the microstructure is very fine, the components of the microstructure can hardly be distinguished from each other microscopically so that depending on the case a combination of electron microscopy and x-ray diffraction has to be used.
11660578_1 (GHMatters) P99274.AU.1
2018201165 29 Aug 2019 [0049] The components of the microstructure can be distinguished by means of scanning electron microscopy. In this way, an average lamellar interspacing of about 300 nm was determined.
[0050] The result of an x-ray diffraction measurement is shown in Figure 7. From the intensity distribution of the x-ray spectrum, the crystal structure of the present microstructure components and their phase proportions can be determined.
[0051] Residual austenite proportions between 10% and 20% were determined using the x-ray diffraction method.
[0052] It is to be understood that, if any prior art publication is referred to herein and if any information is referred to herein as “known”, such reference does not constitute an admission that the publication or information forms a part of the common general knowledge in the art, in Australia or any other country.
Claims (6)
1. A method for producing a steel alloy for the production of strips, sheets and tubes, the steel alloy being a low alloy high-strength, carbide-free bainitic steel with the following chemical composition (in wt.%):
0.10-0.70 C
0.25-4.00 Si
0.05-3.00 Al
1.00-3.00 Mn
0.10-2.00 Cr
0.001 -0.50 Nb
0.001 -0.025 N max. 0.15 P max. 0.05 S remainder iron with smelting-related impurities with optional addition of one or more elements of Mo, Ni, Co, W, Ti or V and Zr and rare earths elements such as Ce, Hf, La, Re, Sc and/or Y in contents totaling up to 1 wt.%, with the proviso that, to avoid primary precipitations of AIN, the condition Al χ N < 5 x 10'3 (wt.%) is satisfied and to suppress cementite formation the condition Si + Al > 4 χ C (wt.%) is satisfiedwherein:
- the optional alloying elements have the following contents in wt. %:
max. 5.00 Ni max. 1.00 Mo max. 2.00 Co max. 1.50 W max. 0.10 Ti max. 0.20 V
- wherein the total content of Ti, V is no more than 0.20% and the total content of Ni, Mo, Co, W, Zr is no more than 5.50 wt%,
- wherein the average previous austenite grain size - determined by
11660578_1 (GHMatters) P99274.AU.1
2018201165 29 Aug 2019 scanning electron microscopy - has a value of no more than 100 pm and the average interspacing of the residual austenite lamellae is less than 750 nm, the microstructure consists of carbide-free bainite and residual austenite lamellae with a fraction of at least 75% bainite, at least 10% residual austenite and up to a maximum of 5% martensite,
- wherein the steels in the bloom or slab state already have a strength (Rm) of over 1250 MPa, an elongation at break of over 12% and a toughness (notched impact strength) at -20°C of at least 15 J after cooling in air, wherein
- to achieve the required material properties the following conditions for transformation kinetics, martensite start temperature and microstructure formation are observed:
- ferritic transformation kinetics (C, Mn, Si and Al here correspond to the element contents in wt.% and T to the cooling rate in °C/s):
(35 x C)+ (10 x Mn) - Si - (5 x Al) + Cr > 13/7” + 10
- bainitic transformation kinetics (C, Mn and Al here correspond to the element contents in wt.% and T to the cooling rate in °C/s):
400 x exp [(-7 x C) - (4 x Mn) + 8 Al + 3]/T > 1
- martensite start temperature (°C; C, Mn, Si, Al and Mo here correspond to the element contents in wt.%):
525 - (350 x C) - (45 x Mn) - (16 x Mo) - (5 x Si) + (15 x Al) < < 400
- stabilising the residual austenite (C, Si and Al here correspond to the element contents in wt.%):
11660578_1 (GHMatters) P99274.AU.1
2018201165 29 Aug 2019
Si + Al > 4 χ C
- avoiding primary AIN precipitations (Al and N here correspond to the element contents in wt.%):
Al χ N < 5 χ 10-3
- meeting the required combination of mechanical properties:
C + Si/6 + Mn/4 + (Cr + Mo)/3 > 1.
2. The method of claim 1, wherein the alloy has the following contents in wt.%:
0.15-0.60 C
0.50-1.75 Si
0.07-1.50 Al
1.50-2.50 Mn
0.10-1.75 Cr
0.001 -0.10 Nb
0.001 -0.015 N
3. The method according to claim 2, wherein the alloy has the following contents in wt.%:
0.18-0.50 C
0.75-1.5 Si
0.09-0.75 Al
1.70-2.50 Mn
0.10-1.5 Cr
0.001 -0.05 Nb
0.002-0.010 N
11660578_1 (GHMatters) P99274.AU.1
2018201165 29 Aug 2019
4. The method according to claim 2, wherein the average interspacing of the residual austenite lamellae is less than 500 nm
5. Use of a steel alloy produced according to at least one of the preceding claims 1 to 4 for hot- or cold-rolled strips, sheets, tubes, profiles or for forged parts for the automotive industry, construction industry and machine construction; and rods and wires.
6. Use of a steel alloy produced according to one of the method claims 1 to 4 for wear parts and parts for armor.
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| WO2010013054A2 (en) * | 2008-07-31 | 2010-02-04 | The Secretary Of State For Defence | Bainite steel and methods of manufacture thereof |
| JP5287770B2 (en) * | 2010-03-09 | 2013-09-11 | Jfeスチール株式会社 | High strength steel plate and manufacturing method thereof |
| JP5126326B2 (en) * | 2010-09-17 | 2013-01-23 | Jfeスチール株式会社 | High strength hot-rolled steel sheet with excellent fatigue resistance and method for producing the same |
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2013
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110209803A1 (en) * | 2008-10-31 | 2011-09-01 | Usui Kokusai Sangyo Kaisha Limited | High-Strength Steel Machined Product and Method for Manufacturing the Same, and Method for Manufacturing Diesel Engine Fuel Injection Pipe and Common Rail |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2018201165A1 (en) | 2018-03-22 |
| TW201432061A (en) | 2014-08-16 |
| SI2895635T1 (en) | 2019-06-28 |
| EP2895635B1 (en) | 2019-03-06 |
| JP6513568B2 (en) | 2019-05-15 |
| PE20151042A1 (en) | 2015-07-27 |
| TR201903460T4 (en) | 2019-04-22 |
| WO2014040585A1 (en) | 2014-03-20 |
| KR20150070150A (en) | 2015-06-24 |
| BR112015005216A2 (en) | 2022-07-26 |
| KR102079612B1 (en) | 2020-02-20 |
| ZA201502450B (en) | 2016-09-28 |
| EP2895635A1 (en) | 2015-07-22 |
| RU2620216C2 (en) | 2017-05-23 |
| AR092556A1 (en) | 2015-04-22 |
| ES2729562T3 (en) | 2019-11-04 |
| JP2015533942A (en) | 2015-11-26 |
| MX376714B (en) | 2025-03-07 |
| PL2895635T3 (en) | 2019-08-30 |
| DK2895635T3 (en) | 2019-05-20 |
| UA116111C2 (en) | 2018-02-12 |
| MX2015003103A (en) | 2015-10-22 |
| AU2013314787A1 (en) | 2015-04-30 |
| US20150267282A1 (en) | 2015-09-24 |
| CL2015000634A1 (en) | 2015-11-20 |
| CA2881686A1 (en) | 2014-03-20 |
| RU2015113522A (en) | 2016-11-10 |
| US20200131608A1 (en) | 2020-04-30 |
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